WO2010058901A2 - Secondary zinc alkaline battery including surface-modified negative electrodes and separators - Google Patents

Secondary zinc alkaline battery including surface-modified negative electrodes and separators Download PDF

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Publication number
WO2010058901A2
WO2010058901A2 PCT/KR2009/005218 KR2009005218W WO2010058901A2 WO 2010058901 A2 WO2010058901 A2 WO 2010058901A2 KR 2009005218 W KR2009005218 W KR 2009005218W WO 2010058901 A2 WO2010058901 A2 WO 2010058901A2
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WIPO (PCT)
Prior art keywords
alkaline battery
zinc
secondary zinc
battery according
negative electrode
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PCT/KR2009/005218
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French (fr)
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WO2010058901A3 (en
Inventor
Tae Hyuk Kang
Yun Jung Kwak
Dong Pil Park
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Energreen Co., Ltd.
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Priority claimed from KR1020080115338A external-priority patent/KR20100056257A/en
Priority claimed from KR1020080115336A external-priority patent/KR20100056256A/en
Application filed by Energreen Co., Ltd. filed Critical Energreen Co., Ltd.
Publication of WO2010058901A2 publication Critical patent/WO2010058901A2/en
Publication of WO2010058901A3 publication Critical patent/WO2010058901A3/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/244—Zinc electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/26—Selection of materials as electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/28—Construction or manufacture
    • H01M10/281—Large cells or batteries with stacks of plate-like electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a secondary zinc alkaline battery employing an alkaline electrolyte solution and, more particularly, to a secondary zinc alkaline battery that can prevent deformation of a zinc negative electrode or formation of dendrites caused by dissolution of the negative electrode in an alkaline electrolyte solution.
  • a nickel (Ni)/zinc (Zn) secondary battery has an operating voltage of 1.6 V/cell or more, high energy density per unit weight and volume, and a specific power density of 875 W/kg, which is superior to the specific power density, 535 W/kg, of the lead acid battery.
  • the Ni/Zn secondary battery has a charge/discharge cycle life of 500 cycles or more to a capacity equivalent to 80% of the maximum capacity of the secondary battery, which is more stable that the charge/discharge cycle number of 200 ⁇ 700 cycles of the lead acid battery.
  • secondary zinc alkaline batteries employ zinc for an anode active material and are widely applied to secondary batteries not only for driving but also for stationary power storage due to its inexpensive price.
  • Japanese Laid-open Publication No. 1985-185372 discloses a nickel/zinc secondary battery that includes zinc electrodes containing an oxide and a hydride of In and Ti to maintain high energy density in order to increase charge/discharge cycle number of the nickel/zinc secondary battery.
  • Japanese Laid-open Publication No. 1987-108467 discloses a zinc alkaline battery that includes zinc electrodes containing indium metal, indium oxide and thallium, and an electrolyte containing germanium ions to increase charge/discharge cycle life of the zinc alkaline battery.
  • Japanese Laid-open Publication No. 1986-016366 discloses a zinc alkaline battery that includes zinc electrodes containing inactive and non-conductive organic compounds to increase charge/discharge cycle life of the zinc alkaline battery while preventing deformation of zinc electrode plates thereof.
  • PCT/US2004/026859 discloses a method of fabricating a nickel/zinc secondary battery which includes a separator layer to prevent formation of dendrites on a negative electrode and contains a borate and a fluoride in a potassium hydroxide electrolyte solution.
  • the inventors searched for a more effective method for solving such problems and found that zinc dendrites can be effectively suppressed when coating the zinc electrodes or separators of the secondary zinc alkaline battery with a dispersion solution containing calcium zincate having a lower solubility in the alkaline solution than zinc or calcium hydroxide (Ca(OH) 2 ) chemically coupled to charged products of zinc to prevent dissolution of the electrodes in the alkaline solution. Further, the inventors found that the formation of zinc dendrites can be effectively suppressed when the zinc electrode or separators of the secondary zinc alkaline battery are coated with a gel electrolyte comprising a gel polymer and potassium hydroxide.
  • a secondary zinc alkaline battery includes zinc negative electrodes or negative electrode separators coated with a dispersion solution prepared by uniformly dispersing calcium zincate powder, calcium hydroxide powder or a mixture thereof in a binder or a thickening agent.
  • the calcium zincate powder, the calcium hydroxide powder or the mixture thereof may be prepared into a dispersion solution having 75 ⁇ 99 % by weight solid content.
  • the binder may include PTFE, PE and SBR, and the thickening agent may include CMC, HEC and acrylic ester.
  • the powder may be dispersed in at least one of the binder and the thickening agent.
  • the dispersion solution may comprise the calcium zincate powder, the calcium hydroxide powder or the mixture thereof in an amount of 1 ⁇ 5 wt% with reference to an average active material for each negative electrode plate.
  • a secondary zinc alkaline battery includes zinc negative electrodes or negative electrode separators coated with a gel electrolyte for coating.
  • the gel electrolyte contains 1 ⁇ 10 wt% of at least one gel polymer selected from the group consisting of polyethylene oxide (PEO), polyvinyl alcohol (PVA) and potassium poly(acrylic acid) (PAAK), and 90 ⁇ 99 wt% of a potassium hydroxide (KOH) solution.
  • the gel electrolyte may further contain 1 ⁇ 10 parts by weight of porous ceramic or silica with reference to the gel polymer.
  • the gel electrolyte may further contain 1 ⁇ 10 parts by weight of calcium zincate powder, calcium hydroxide powder or a mixture thereof with reference to the gel polymer.
  • the secondary zinc alkaline battery prevents deformation of a negative electrode or formation of dendrites caused by dissolution of the negative electrode in an alkaline electrolyte solution, thereby improving life span and charge/discharge efficiency of the battery.
  • Fig. 1 is a diagram of a secondary zinc alkaline battery in accordance with one embodiment of the present invention
  • Fig. 2 is a diagram of the secondary zinc alkaline battery in accordance with the embodiment, in which positive electrodes and negative electrodes having coating layers are stacked on each other;
  • Fig. 3 (a) is a side sectional view of a zinc negative electrode having a coating layer and two negative electrode separators consecutively formed thereon in accordance with one embodiment of the present invention
  • Fig. 3 (b) is a side sectional view of a zinc negative electrode having a coating layer between two bag-shaped or laminated separators on the negative electrode in accordance with another embodiment of the present invention
  • Fig. 4 is a graph depicting performance of a secondary zinc alkaline battery fabricated by Example 1.
  • Fig. 5 is a graph depicting performance of a secondary zinc alkaline battery fabricated by Example 2.
  • a secondary zinc alkaline battery includes zinc negative electrodes or negative electrode separators coated with a dispersion solution prepared by uniformly dispersing calcium zincate powder, calcium hydroxide powder or a mixture thereof in a binder or a thickening agent.
  • Fig. 1 is a diagram of a secondary zinc alkaline battery including surface-treated zinc negative electrodes or negative electrode separators in accordance with one embodiment of the invention.
  • the secondary zinc alkaline battery has a coating layer 104 that is formed on a surface of a zinc negative electrode 103 or a negative electrode separator 107 by coating a coating material, for example, a dispersion solution containing the calcium zincate powder, the calcium hydroxide powder or the mixture thereof, thereon.
  • a coating material for example, a dispersion solution containing the calcium zincate powder, the calcium hydroxide powder or the mixture thereof, thereon.
  • Calcium zincate has a lower solubility in an alkaline solution than zinc and calcium hydroxide (Ca(OH) 2 ) is chemically coupled to charged products of zinc as expressed by the following Formula 1.
  • the calcium zincate powder, the calcium hydroxide powder or the mixture thereof may be contained in an amount of 1 ⁇ 5 wt% with reference to an average active material for each negative electrode plate. If the content of the calcium zincate powder, the calcium hydroxide powder or the mixture thereof is less than 1 wt% with reference to an average active material for each negative electrode plate, formation of the dendrites cannot be effectively prevented. If the content of the calcium zincate powder, the calcium hydroxide powder or the mixture thereof exceeds 5 wt% with reference to an average active material for each negative electrode plate, the resistance of the electrode increases, thereby deteriorating performance of the battery.
  • the calcium zincate powder, the calcium hydroxide powder or the mixture thereof may be prepared into a dispersion.
  • the binder may include PTFE, PE, SBR, and the like.
  • the thickening agent may be at least one elected from CMC, HEC, and acrylic ester.
  • the powder is dispersed in at least one of the binder and the thickening agent solution that has 75 ⁇ 99 wt% solid content.
  • the coating layer 104 shown in Fig. 1 may be a gel polymer coating layer 104 coated with another coating material, that is, a gel electrolyte solution that contains 1 ⁇ 10 wt% of at least one gel polymer selected from the group consisting of polyethylene oxide (PEO), polyvinyl alcohol (PVA) and potassium poly(acrylic acid) (PAAK), and 90 ⁇ 99 wt% of a potassium hydroxide (KOH) solution.
  • the gel polymer is at least one selected from the group consisting of PEO, PVA and PAAK, but is not limited thereto.
  • the negative electrode 103 or the separator 107 is coated with the gel electrolyte solution, thereby lowering the solubility of the charge products in the alkaline electrolyte solution and effectively suppressing the formation of the zinc dendrites.
  • the gel electrolyte solution contains 1 ⁇ 10 wt% of the at least one gel polymer selected from the group consisting of PEO, PVA and PAAK. If the content of the gel polymer is less than 1 wt%, the coated gel polymer flows down from the electrode plate, so that desired effects of coating cannot be obtained. If the content of the gel polymer exceeds 10 wt%, discharge efficiency of the battery is lowered.
  • the gel electrolyte solution may further contain calcium zincate powder, calcium hydroxide powder, or a mixture thereof.
  • Calcium zincate has a lower solubility in the alkaline solution than zinc and calcium hydroxide (Ca(OH) 2 ) is chemically coupled to the charged products of zinc.
  • Ca(OH) 2 calcium hydroxide
  • the gel electrolyte solution may contain 1 ⁇ 10 wt% of the calcium zincate powder, the calcium hydroxide powder or the mixture thereof with reference to the gel polymer.
  • the gel electrolyte solution may further contain porous ceramic or silica.
  • the porous ceramic or silica added to the gel electrolyte solution increases the amount of electrolyte in the gel, so that the gel electrolyte solution has suitable properties for coating and has high ion mobility.
  • the porous ceramic or silica may be contained in an amount of 1 ⁇ 10 wt% with reference to the gel polymer.
  • Fig. 2 is a diagram of the secondary zinc alkaline battery in accordance with the embodiment, in which positive electrodes and negative electrodes having coating layers are stacked on each other. As shown in Fig. 2, in the secondary zinc alkaline battery according to this embodiment, negative electrodes 103 having coating layers 104 are alternately stacked with positive electrodes 105, thereby improving charge capacity of the battery.
  • Celgard 3407 microporous polyolefin films may be used as the negative electrode separators.
  • each of the negative electrodes is provided with at least one separator to prevent short circuit caused by dendrites.
  • the separator is used in a roll shape or a sheet shape and coated with the dispersion solution or the gel electrolyte solution. Then, the separator is covered in a box shape or laminated on the negative electrode after being dried.
  • the coating layer may be coated on the surface of the zinc negative electrode or the negative electrode separator to prevent the zinc negative electrode from being dissolved in the electrolyte solution.
  • a surface of a zinc negative electrode 103 is coated with the dispersion solution or the gel electrolyte solution for coating to form a coating layer 104 and is covered by one or more negative electrode separators 107 in a box shape or a laminate shape, thereby forming the zinc electrode 103.
  • the coating layer 104 is formed between two negative electrode separators 107, which in turn cover the zinc electrode 103 in a box shape or a laminate shape, thereby forming the zinc electrode 103.
  • the zinc negative electrode is prepared by mixing an anode active material and activated carbon using a ball-mill process to prepare a mixture in operation 1; wetting the mixture, followed by adding a thickening agent to prepare a slurry in operation 2; adding a binder to the slurry to prepare a composition for negative electrodes in operation 3; coating the composition on a current collector in operation 4; and drying the composition coated on the current collector in operation 5.
  • the activated carbon or graphite is mixed with the active material using the ball-mill process, thereby improving electrical conductivity of the electrode while preventing agglomeration of the active material in the slurry or paste during fabrication of the electrode.
  • the anode active material is mixed with the activated carbon using the ball mill process.
  • the anode active material may include, but is not limited to, at least one selected from the group consisting of zinc oxide, calcium zincate, and zinc powder.
  • the activated carbon may include, but is not limited to, at least one selected from the group consisting of acetylene black and Ketjen black.
  • the activated carbon and graphite may be provided in the form of powders having an average particle size less than 10.
  • the activated carbon such as acetylene black and Ketjen black has a large volume to cause a decrease in tap density when used as a conductive agent. Since the decrease in tap density leads to a decrease in energy density of the battery, it is necessary to keep the tap density as high as possible.
  • the active material and the activated carbon can be strongly bonded to each other while keeping the tap density as high as possible, thereby preventing agglomeration of the active material.
  • the anode active material and the activated carbon are mixed in a ratio of 95 ⁇ 99% wt% and 1 ⁇ 5 wt%, respectively. If the content of activated carbon exceeds 5 wt%, the electrode is lowered in activity, and, if the content of activated carbon is less than 1 wt%, the electrode is lowered in electrical conductivity.
  • additives may be added to the anode active material and the activated carbon.
  • the additives may include various metal oxides such as Ca(OH) 2 , Bi 2 O 3 , Tl 2 O 3 , In 2 O 3 , and SnO.
  • Ca(OH) 2 may be added to prevent zincate ions from being dissolved in the electrolyte solution, and the metal oxides such as Bi 2 O 3 and the like may be added to reduce gas generation by increasing hydrogen overvoltage.
  • a thickening agent is added to the mixture to prepare a slurry in operation 2.
  • the thickening agent may include, but is not limited to, at least one selected from the group consisting of CMC, HEC and acrylic ester.
  • the thickening agent may be used after being substituted Na+ with K+. When the thickening agent are substituted Na+ with K+, it is possible to prevent rapid agglomeration of Ca(OH) 2 , which is an additive used to prevent the zincate ions from being dissolved after charging the battery, by reaction with a water mixed binder.
  • the content of the thickening agent may be 0.5 ⁇ 5 wt% with reference to the mixture of the anode active material and the activated carbon. If the content of the thickening agent exceeds 5 wt%, the slurry increases in viscosity and the electrode resistance increases, thereby making it difficult to coat the compound on the current collector while deteriorating performance of the battery. If the content of the thickening agent is less than 0.5 wt%, the slurry becomes watery, thereby making it difficult to form the electrode.
  • a binder is added to the slurry to prepare a composition for negative electrodes in operation 3.
  • the binder may include PTFE, PE, SBR, and the like.
  • the binder may be added in an amount of 0.5 ⁇ 5 wt% with reference to the mixture of the anode active material and the activated carbon. If the content of the binder exceeds 5 wt%, the viscosity of the slurry increases and the electrode resistance increases, thereby deteriorating performance of the battery. If the content of the binder is less than 0.5 wt%, a binding force with respect to the current collector and other anode active materials is lowered, thereby deteriorating performance of the battery, and the binder is liable to be dissolved in the electrolyte solution.
  • composition is coated on the current collector in operation 4, and is then dried thereon in operation 5.
  • the prepared electrode may be subjected to roll pressing. Roll pressing more densely couples the active material, activated carbon and the like to each other.
  • the current collector may include a metal sheet, an expanded metal, a punching metal, a metal foam, and the like.
  • ZnO 1764 g, AB 40g, Ca(OH) 2 44g, and Bi 2 O 3 72g were mixed at 180 rpm in a container for 3 hours using a ball mill process, and passed through a sieve to separate anode materials from balls. After wetting the prepared anode materials using distilled water, substituted CMC was added to the anode materials to prepare a viscous slurry. Then, binders were added to the slurry in the sequence of PTFE, PE and SBR, and stirred to prepare a composition for negative electrodes, which was coated on current collectors. The coated electrodes were dried at 90 for 2 hours in an oven and roll-pressed to 30% of an initial thickness thereof.
  • a battery having a desired capacity was fabricated by alternately stacking the prepared positive and negative electrodes. 11 positive electrode plates and 12 negative electrode plates were alternately stacked on each other to produce a battery having a capacity of 50 Ah.
  • the stacked electrode plates were received in a battery case and capped by a cover. Then, an electrolyte solution was supplied into the battery case, which in turn was subjected to aging in a vacuum at room temperature for 6 hours to activate the battery, thereby forming a final nickel/zinc secondary battery.
  • Fig. 4 is a graph depicting performance of the secondary zinc alkaline battery fabricated by Example 1. It can be corroborated from Fig. 4 that the secondary zinc alkaline battery fabricated in Example 1 has superior discharge efficiency and cycle life.
  • ZnO 1764 g, AB 40g, Ca(OH) 2 44g, and Bi 2 O 3 72g were mixed at 180 rpm in a container for 3 hours using a ball mill process, and passed through a sieve to separate anode materials from balls. After wetting the prepared anode materials using distilled water, substituted CMC was added to the anode materials to prepare a viscous slurry. Then, binders were added to the slurry in the sequence of PTFE, PE and SBR, and stirred to prepare a composition for negative electrodes, which was coated on current collectors. The coated electrodes were dried at 90 for 2 hours in an oven and roll-pressed to 30% of an initial thickness thereof.
  • a gel electrolyte solution for coating was prepared by mixing 5 wt% PAAK and 95 wt% of 3 ⁇ 12M potassium hydroxide solution. 2 parts by weight of calcium hydroxide and 2 parts by weight of porous ceramics with reference to PAAK were added to the gel electrolyte solution, which in turn was coated and dried on the surfaces of the negative electrodes. Separators were stacked on the negative electrodes, thereby forming final negative electrodes. Here, two Celgard 3407 films were used as separators for each electrode. A compositional ratio of the materials for fabrication of the negative electrodes is shown in Table 3.
  • a battery having a desired capacity was fabricated by alternately stacking the prepared positive and negative electrodes. 11 positive electrode plates and 12 negative electrode plates were alternately stacked on each other to produce a battery having a capacity of 50 Ah.
  • the stacked electrode plates were received in a battery case and capped by a cover. Then, an electrolyte solution was supplied into the battery case, which in turn was subjected to aging in a vacuum at room temperature for 6 hours to activate the battery, thereby forming a final nickel/zinc secondary battery.
  • Fig. 5 is a graph depicting performance of the secondary zinc alkaline battery fabricated by Example 2. It can be corroborated from Fig. 14 that the secondary zinc alkaline battery fabricated in Example 2 has superior discharge efficiency and cycle life.

Abstract

The present disclosure relates to a secondary zinc alkaline battery including surface modified negative electrodes and separators. The surface modified negative electrodes and separators may be coated with a dispersion solution or a gel electrolyte for coating. The dispersion solution is prepared by uniformly dispersing calcium zincate powder, calcium hydroxide powder or a mixture thereof in a binder or a thickening agent. The gel electrolyte contains 1~10 wt% of at least one gel polymer selected from the group consisting of PEO, PVA and PAAK, and 90~99 wt% of 3~12M KOH solution. The secondary zinc alkaline battery relieves deformation of the zinc negative electrode and formation of dendrites caused by dissolution of the zinc negative electrode in an alkaline solution, thereby improving lifespan and charge/discharge efficiency.

Description

SECONDARY ZINC ALKALINE BATTERY INCLUDING SURFACE-MODIFIED NEGATIVE ELECTRODES AND SEPARATORS
The present invention relates to a secondary zinc alkaline battery employing an alkaline electrolyte solution and, more particularly, to a secondary zinc alkaline battery that can prevent deformation of a zinc negative electrode or formation of dendrites caused by dissolution of the negative electrode in an alkaline electrolyte solution.
Currently, most countries have introduced a variety of environmental regulations for preservation of the environment. As part of this movement, lead acid batteries and nickel/cadmium batteries are replaced by nickel/hydrogen batteries, lithium ion batteries and the like in the field of small batteries. In the field of large industrial batteries, however, the lead acid batteries and nickel/cadmium batteries are still used due to failure to develop substitute batteries. Accordingly, development of environmentally friendly batteries having high capacity is attracting increasing attention and is intensively carried out in the art.
As one of batteries developed to replace the lead acid battery, a nickel (Ni)/zinc (Zn) secondary battery has an operating voltage of 1.6 V/cell or more, high energy density per unit weight and volume, and a specific power density of 875 W/kg, which is superior to the specific power density, 535 W/kg, of the lead acid battery. Further, advantageously, the Ni/Zn secondary battery has a charge/discharge cycle life of 500 cycles or more to a capacity equivalent to 80% of the maximum capacity of the secondary battery, which is more stable that the charge/discharge cycle number of 200~700 cycles of the lead acid battery. Furthermore, secondary zinc alkaline batteries employ zinc for an anode active material and are widely applied to secondary batteries not only for driving but also for stationary power storage due to its inexpensive price. In the secondary zinc alkaline batteries, however, since the zinc negative electrode is dissolved in an alkaline solution and undergoes repetitious elution and precipitation of zinc by charge/discharge reaction, electrode plates are deformed by the charge/discharge reaction. Further, the eluted zinc is not uniformly precipitated but grows in a dendritic phase during charging of the battery, so that the zinc dendritic phase penetrates separators of the secondary battery and causes short circuit of the battery, thereby decreasing life span of the secondary battery.
Various techniques have been developed to solve such problems.
Japanese Laid-open Publication No. 1985-185372 discloses a nickel/zinc secondary battery that includes zinc electrodes containing an oxide and a hydride of In and Ti to maintain high energy density in order to increase charge/discharge cycle number of the nickel/zinc secondary battery.
Japanese Laid-open Publication No. 1987-108467 discloses a zinc alkaline battery that includes zinc electrodes containing indium metal, indium oxide and thallium, and an electrolyte containing germanium ions to increase charge/discharge cycle life of the zinc alkaline battery.
Japanese Laid-open Publication No. 1986-016366 discloses a zinc alkaline battery that includes zinc electrodes containing inactive and non-conductive organic compounds to increase charge/discharge cycle life of the zinc alkaline battery while preventing deformation of zinc electrode plates thereof.
Further, as an example of conventional techniques for preventing formation of dendrites, PCT/US2004/026859 discloses a method of fabricating a nickel/zinc secondary battery which includes a separator layer to prevent formation of dendrites on a negative electrode and contains a borate and a fluoride in a potassium hydroxide electrolyte solution.
As such, various attempts have been made to solve the problems of the nickel/zinc secondary battery in the art, resulting not only in an increase of manufacturing costs, but also in unsatisfactory effects.
The inventors searched for a more effective method for solving such problems and found that zinc dendrites can be effectively suppressed when coating the zinc electrodes or separators of the secondary zinc alkaline battery with a dispersion solution containing calcium zincate having a lower solubility in the alkaline solution than zinc or calcium hydroxide (Ca(OH)2) chemically coupled to charged products of zinc to prevent dissolution of the electrodes in the alkaline solution. Further, the inventors found that the formation of zinc dendrites can be effectively suppressed when the zinc electrode or separators of the secondary zinc alkaline battery are coated with a gel electrolyte comprising a gel polymer and potassium hydroxide.
It is an aspect of the present invention to provide a secondary zinc alkaline battery that can prevent deformation of a zinc negative electrode or formation of dendrites caused by dissolution of the negative electrode in an alkaline electrolyte solution.
In accordance with an aspect of the present invention, a secondary zinc alkaline battery includes zinc negative electrodes or negative electrode separators coated with a dispersion solution prepared by uniformly dispersing calcium zincate powder, calcium hydroxide powder or a mixture thereof in a binder or a thickening agent.
The calcium zincate powder, the calcium hydroxide powder or the mixture thereof may be prepared into a dispersion solution having 75~99 % by weight solid content. The binder may include PTFE, PE and SBR, and the thickening agent may include CMC, HEC and acrylic ester. In the dispersion solution, the powder may be dispersed in at least one of the binder and the thickening agent.
The dispersion solution may comprise the calcium zincate powder, the calcium hydroxide powder or the mixture thereof in an amount of 1~5 wt% with reference to an average active material for each negative electrode plate.
In accordance with another aspect of the present invention, a secondary zinc alkaline battery includes zinc negative electrodes or negative electrode separators coated with a gel electrolyte for coating. Here, the gel electrolyte contains 1~10 wt% of at least one gel polymer selected from the group consisting of polyethylene oxide (PEO), polyvinyl alcohol (PVA) and potassium poly(acrylic acid) (PAAK), and 90~99 wt% of a potassium hydroxide (KOH) solution.
The gel electrolyte may further contain 1~10 parts by weight of porous ceramic or silica with reference to the gel polymer.
The gel electrolyte may further contain 1~10 parts by weight of calcium zincate powder, calcium hydroxide powder or a mixture thereof with reference to the gel polymer.
According to embodiments of the invention, the secondary zinc alkaline battery prevents deformation of a negative electrode or formation of dendrites caused by dissolution of the negative electrode in an alkaline electrolyte solution, thereby improving life span and charge/discharge efficiency of the battery.
The above and other aspects, features and advantages of the invention will be more clearly understood from the detailed description taken in conjunction with the accompanying drawings, in which:
Fig. 1 is a diagram of a secondary zinc alkaline battery in accordance with one embodiment of the present invention;
Fig. 2 is a diagram of the secondary zinc alkaline battery in accordance with the embodiment, in which positive electrodes and negative electrodes having coating layers are stacked on each other;
Fig. 3 (a) is a side sectional view of a zinc negative electrode having a coating layer and two negative electrode separators consecutively formed thereon in accordance with one embodiment of the present invention, and Fig. 3 (b) is a side sectional view of a zinc negative electrode having a coating layer between two bag-shaped or laminated separators on the negative electrode in accordance with another embodiment of the present invention;
Fig. 4 is a graph depicting performance of a secondary zinc alkaline battery fabricated by Example 1; and
Fig. 5 is a graph depicting performance of a secondary zinc alkaline battery fabricated by Example 2.
Embodiments of the invention will hereinafter be described in detail with reference to the accompanying drawings.
In accordance with one embodiment of the invention, a secondary zinc alkaline battery includes zinc negative electrodes or negative electrode separators coated with a dispersion solution prepared by uniformly dispersing calcium zincate powder, calcium hydroxide powder or a mixture thereof in a binder or a thickening agent.
Fig. 1 is a diagram of a secondary zinc alkaline battery including surface-treated zinc negative electrodes or negative electrode separators in accordance with one embodiment of the invention. Referring to Fig. 1, the secondary zinc alkaline battery has a coating layer 104 that is formed on a surface of a zinc negative electrode 103 or a negative electrode separator 107 by coating a coating material, for example, a dispersion solution containing the calcium zincate powder, the calcium hydroxide powder or the mixture thereof, thereon. Calcium zincate has a lower solubility in an alkaline solution than zinc and calcium hydroxide (Ca(OH)2) is chemically coupled to charged products of zinc as expressed by the following Formula 1. Thus, when calcium zincate and calcium hydroxide are coated on the negative electrode plate or the separator, they lower solubility of charged products in the alkaline solution and effectively suppress generation of zinc dendrites, thereby significantly improving the lifespan and charge/discharge efficiency of the battery.
Chemical Formula 1
Ca(OH)2(S) + 2(ZnO)soln + 4(H2O)soln Ca(OH)22Zn(OH)22H2O(S)
The calcium zincate powder, the calcium hydroxide powder or the mixture thereof may be contained in an amount of 1~5 wt% with reference to an average active material for each negative electrode plate. If the content of the calcium zincate powder, the calcium hydroxide powder or the mixture thereof is less than 1 wt% with reference to an average active material for each negative electrode plate, formation of the dendrites cannot be effectively prevented. If the content of the calcium zincate powder, the calcium hydroxide powder or the mixture thereof exceeds 5 wt% with reference to an average active material for each negative electrode plate, the resistance of the electrode increases, thereby deteriorating performance of the battery.
In this embodiment, the calcium zincate powder, the calcium hydroxide powder or the mixture thereof may be prepared into a dispersion.
The binder may include PTFE, PE, SBR, and the like.
The thickening agent may be at least one elected from CMC, HEC, and acrylic ester.
In preparation of the dispersion solution, the powder is dispersed in at least one of the binder and the thickening agent solution that has 75~99 wt% solid content.
In accordance with another embodiment of the invention, the coating layer 104 shown in Fig. 1 may be a gel polymer coating layer 104 coated with another coating material, that is, a gel electrolyte solution that contains 1~10 wt% of at least one gel polymer selected from the group consisting of polyethylene oxide (PEO), polyvinyl alcohol (PVA) and potassium poly(acrylic acid) (PAAK), and 90~99 wt% of a potassium hydroxide (KOH) solution. In this embodiment, the gel polymer is at least one selected from the group consisting of PEO, PVA and PAAK, but is not limited thereto. In this way, the negative electrode 103 or the separator 107 is coated with the gel electrolyte solution, thereby lowering the solubility of the charge products in the alkaline electrolyte solution and effectively suppressing the formation of the zinc dendrites.
The gel electrolyte solution contains 1~10 wt% of the at least one gel polymer selected from the group consisting of PEO, PVA and PAAK. If the content of the gel polymer is less than 1 wt%, the coated gel polymer flows down from the electrode plate, so that desired effects of coating cannot be obtained. If the content of the gel polymer exceeds 10 wt%, discharge efficiency of the battery is lowered.
Further, in order to lower the solubility of the charge products in the alkaline electrolyte solution and to effectively suppress the formation of the zinc dendrites, the gel electrolyte solution may further contain calcium zincate powder, calcium hydroxide powder, or a mixture thereof. Calcium zincate has a lower solubility in the alkaline solution than zinc and calcium hydroxide (Ca(OH)2) is chemically coupled to the charged products of zinc. Thus, when calcium zincate and calcium hydroxide are coated on the negative electrode plate or the separator, they lower the solubility of the charge products in the alkaline solution and effectively suppress the formation of the zinc dendrites, thereby significantly improving life span and charge/discharge efficiency of the battery. The gel electrolyte solution may contain 1~10 wt% of the calcium zincate powder, the calcium hydroxide powder or the mixture thereof with reference to the gel polymer.
The gel electrolyte solution may further contain porous ceramic or silica. The porous ceramic or silica added to the gel electrolyte solution increases the amount of electrolyte in the gel, so that the gel electrolyte solution has suitable properties for coating and has high ion mobility. The porous ceramic or silica may be contained in an amount of 1~10 wt% with reference to the gel polymer.
Fig. 2 is a diagram of the secondary zinc alkaline battery in accordance with the embodiment, in which positive electrodes and negative electrodes having coating layers are stacked on each other. As shown in Fig. 2, in the secondary zinc alkaline battery according to this embodiment, negative electrodes 103 having coating layers 104 are alternately stacked with positive electrodes 105, thereby improving charge capacity of the battery.
In this embodiment, Celgard 3407 microporous polyolefin films may be used as the negative electrode separators. Here, each of the negative electrodes is provided with at least one separator to prevent short circuit caused by dendrites. In this embodiment, the separator is used in a roll shape or a sheet shape and coated with the dispersion solution or the gel electrolyte solution. Then, the separator is covered in a box shape or laminated on the negative electrode after being dried.
In this invention, the coating layer may be coated on the surface of the zinc negative electrode or the negative electrode separator to prevent the zinc negative electrode from being dissolved in the electrolyte solution. As shown in Fig. 3(a), according to one embodiment, a surface of a zinc negative electrode 103 is coated with the dispersion solution or the gel electrolyte solution for coating to form a coating layer 104 and is covered by one or more negative electrode separators 107 in a box shape or a laminate shape, thereby forming the zinc electrode 103. Further, as shown in Fig. 3(b), according to another embodiment, the coating layer 104 is formed between two negative electrode separators 107, which in turn cover the zinc electrode 103 in a box shape or a laminate shape, thereby forming the zinc electrode 103.
In accordance with one embodiment of the invention, the zinc negative electrode is prepared by mixing an anode active material and activated carbon using a ball-mill process to prepare a mixture in operation 1; wetting the mixture, followed by adding a thickening agent to prepare a slurry in operation 2; adding a binder to the slurry to prepare a composition for negative electrodes in operation 3; coating the composition on a current collector in operation 4; and drying the composition coated on the current collector in operation 5.
For the zinc negative electrode, the activated carbon or graphite is mixed with the active material using the ball-mill process, thereby improving electrical conductivity of the electrode while preventing agglomeration of the active material in the slurry or paste during fabrication of the electrode.
A method of fabricating the zinc negative electrode according to the embodiments of the invention will be described in more detail.
In operation 1, the anode active material is mixed with the activated carbon using the ball mill process.
The anode active material may include, but is not limited to, at least one selected from the group consisting of zinc oxide, calcium zincate, and zinc powder.
The activated carbon may include, but is not limited to, at least one selected from the group consisting of acetylene black and Ketjen black. The activated carbon and graphite may be provided in the form of powders having an average particle size less than 10.
The activated carbon such as acetylene black and Ketjen black has a large volume to cause a decrease in tap density when used as a conductive agent. Since the decrease in tap density leads to a decrease in energy density of the battery, it is necessary to keep the tap density as high as possible. When using the ball-mill process, the active material and the activated carbon can be strongly bonded to each other while keeping the tap density as high as possible, thereby preventing agglomeration of the active material.
In the mixture prepared by operation 1, the anode active material and the activated carbon are mixed in a ratio of 95~99% wt% and 1~5 wt%, respectively. If the content of activated carbon exceeds 5 wt%, the electrode is lowered in activity, and, if the content of activated carbon is less than 1 wt%, the electrode is lowered in electrical conductivity.
In this operation, additives may be added to the anode active material and the activated carbon. The additives may include various metal oxides such as Ca(OH)2, Bi2O3, Tl2O3, In2O3, and SnO. Ca(OH)2 may be added to prevent zincate ions from being dissolved in the electrolyte solution, and the metal oxides such as Bi2O3 and the like may be added to reduce gas generation by increasing hydrogen overvoltage.
Then, after wetting the mixture prepared in operation 1, a thickening agent is added to the mixture to prepare a slurry in operation 2. The thickening agent may include, but is not limited to, at least one selected from the group consisting of CMC, HEC and acrylic ester. The thickening agent may be used after being substituted Na+ with K+. When the thickening agent are substituted Na+ with K+, it is possible to prevent rapid agglomeration of Ca(OH)2, which is an additive used to prevent the zincate ions from being dissolved after charging the battery, by reaction with a water mixed binder.
In this operation, the content of the thickening agent may be 0.5~5 wt% with reference to the mixture of the anode active material and the activated carbon. If the content of the thickening agent exceeds 5 wt%, the slurry increases in viscosity and the electrode resistance increases, thereby making it difficult to coat the compound on the current collector while deteriorating performance of the battery. If the content of the thickening agent is less than 0.5 wt%, the slurry becomes watery, thereby making it difficult to form the electrode.
Next, a binder is added to the slurry to prepare a composition for negative electrodes in operation 3.
The binder may include PTFE, PE, SBR, and the like.
In this operation, the binder may be added in an amount of 0.5~5 wt% with reference to the mixture of the anode active material and the activated carbon. If the content of the binder exceeds 5 wt%, the viscosity of the slurry increases and the electrode resistance increases, thereby deteriorating performance of the battery. If the content of the binder is less than 0.5 wt%, a binding force with respect to the current collector and other anode active materials is lowered, thereby deteriorating performance of the battery, and the binder is liable to be dissolved in the electrolyte solution.
Next, the composition is coated on the current collector in operation 4, and is then dried thereon in operation 5.
After coating and drying the composition, the prepared electrode may be subjected to roll pressing. Roll pressing more densely couples the active material, activated carbon and the like to each other. The current collector may include a metal sheet, an expanded metal, a punching metal, a metal foam, and the like.
Next, preferred examples will be descried for thorough understanding of the present invention. Here, it should be understood that the following examples are given by way of illustration only and do not limit the scope of the invention. Further, it will be apparent that various modifications and changes can be made without departing from the spirit and scope of the invention. The scope of the invention should be limited only by the accompanying claims.
Example 1
ZnO 1764 g, AB 40g, Ca(OH)2 44g, and Bi2O3 72g were mixed at 180 rpm in a container for 3 hours using a ball mill process, and passed through a sieve to separate anode materials from balls. After wetting the prepared anode materials using distilled water, substituted CMC was added to the anode materials to prepare a viscous slurry. Then, binders were added to the slurry in the sequence of PTFE, PE and SBR, and stirred to prepare a composition for negative electrodes, which was coated on current collectors. The coated electrodes were dried at 90 for 2 hours in an oven and roll-pressed to 30% of an initial thickness thereof. Then, the surfaces of the negative electrodes were coated with a dispersion solution prepared by uniformly dispersing 95 parts calcium zincate powders and 5 parts CMC by weight respectively, and covered with box-shaped separators, thereby providing final negative electrodes. Here, two Celgard 3407 films were used separators for each electrode. A compositional ratio of the materials for fabrication of the negative electrodes is shown in Table 1.
Table 1
ZnO AB Ca(OH)2 Bi2O3 PTFE PE SBR CMC
Composition (wt%) 88.2 2.0 2.2 3.6 0.6 2.0 0.4 1.0
On the other hand, after loading Ni(OH)2 3657 g, Ni powder 116 g, and CoO 116 g in a mixer, CMC was added to prepare a viscous slurry. Then, binders were added to the slurry in the sequence of PTFE and PE, and stirred to prepare a composition for positive electrodes, which was coated on current collectors. The coated electrodes were dried at 90 for 2 hours in an oven, roll-pressed to 30% of an initial thickness thereof, and covered with box-shaped separators, thereby providing positive electrodes. Here, two NKK non-woven films were used as separators for each electrode. A compositional ratio of the materials for fabrication of the positive electrodes is shown in Table 2.
Table 2
Ni(OH)2 Ni powder CoO PTFE PE CMC
Composition (wt%) 91.43 2.9 2.9 0.6 1.97 0.2
A battery having a desired capacity was fabricated by alternately stacking the prepared positive and negative electrodes. 11 positive electrode plates and 12 negative electrode plates were alternately stacked on each other to produce a battery having a capacity of 50 Ah. The stacked electrode plates were received in a battery case and capped by a cover. Then, an electrolyte solution was supplied into the battery case, which in turn was subjected to aging in a vacuum at room temperature for 6 hours to activate the battery, thereby forming a final nickel/zinc secondary battery.
Fig. 4 is a graph depicting performance of the secondary zinc alkaline battery fabricated by Example 1. It can be corroborated from Fig. 4 that the secondary zinc alkaline battery fabricated in Example 1 has superior discharge efficiency and cycle life.
Example 2
ZnO 1764 g, AB 40g, Ca(OH)2 44g, and Bi2O3 72g were mixed at 180 rpm in a container for 3 hours using a ball mill process, and passed through a sieve to separate anode materials from balls. After wetting the prepared anode materials using distilled water, substituted CMC was added to the anode materials to prepare a viscous slurry. Then, binders were added to the slurry in the sequence of PTFE, PE and SBR, and stirred to prepare a composition for negative electrodes, which was coated on current collectors. The coated electrodes were dried at 90 for 2 hours in an oven and roll-pressed to 30% of an initial thickness thereof. Then, a gel electrolyte solution for coating was prepared by mixing 5 wt% PAAK and 95 wt% of 3~12M potassium hydroxide solution. 2 parts by weight of calcium hydroxide and 2 parts by weight of porous ceramics with reference to PAAK were added to the gel electrolyte solution, which in turn was coated and dried on the surfaces of the negative electrodes. Separators were stacked on the negative electrodes, thereby forming final negative electrodes. Here, two Celgard 3407 films were used as separators for each electrode. A compositional ratio of the materials for fabrication of the negative electrodes is shown in Table 3.
Table 3
ZnO AB Ca(OH)2 Bi2O3 PTFE PE SBR CMC
Composition (wt%) 88.2 2.0 2.2 3.6 0.6 2.0 0.4 1.0
On the other hand, after loading Ni(OH)2 3657 g, Ni powder 116 g, and CoO 116 g in a mixer, CMC was added to prepare a viscous slurry. Then, binders were added to the slurry in the sequence of PTFE and PE, stirred to prepare a composition for positive electrodes, which was coated on current collectors. The coated electrode was dried at 90 for 2 hours in an oven, roll-pressed to 30% of an initial thickness thereof, and covered with box-shaped separators, thereby providing final positive electrodes. Here, two NKK non-woven films were used as separators for each electrode. A compositional ratio of the materials for fabrication of the positive electrodes is shown in Table 4.
Table 4
Ni(OH)2 Ni powder CoO PTFE PE CMC
Composition (wt%) 91.43 2.9 2.9 0.6 1.97 0.2
A battery having a desired capacity was fabricated by alternately stacking the prepared positive and negative electrodes. 11 positive electrode plates and 12 negative electrode plates were alternately stacked on each other to produce a battery having a capacity of 50 Ah. The stacked electrode plates were received in a battery case and capped by a cover. Then, an electrolyte solution was supplied into the battery case, which in turn was subjected to aging in a vacuum at room temperature for 6 hours to activate the battery, thereby forming a final nickel/zinc secondary battery.
Fig. 5 is a graph depicting performance of the secondary zinc alkaline battery fabricated by Example 2. It can be corroborated from Fig. 14 that the secondary zinc alkaline battery fabricated in Example 2 has superior discharge efficiency and cycle life.

Claims (14)

  1. A secondary zinc alkaline battery comprising a positive electrode, a zinc negative electrode, a positive electrode separator, a negative electrode separator, and an alkaline electrolyte solution, wherein the zinc negative electrode or the negative electrode separator is coated by a dispersion solution or a gel electrolyte for coating, the dispersion solution being prepared by uniformly dispersing calcium zincate powder, calcium hydroxide powder or a mixture thereof in a binder or a thickening agent, and the gel electrolyte containing 1~10 wt% of at least one gel polymer selected from the group consisting of polyethylene oxide (PEO), polyvinyl alcohol (PVA) and potassium poly(acrylic acid) (PAAK), and 90~99 wt% of 3~12M potassium hydroxide (KOH) solution.
  2. The secondary zinc alkaline battery according to claim 1, wherein the dispersion solution contains 1~5 wt% of the calcium zincate powder, the calcium hydroxide powder or the mixture thereof with reference to an average active material for each negative electrode plate.
  3. The secondary zinc alkaline battery according to claim 1, wherein the binder is selected from the group consisting of PTFE, PE, and SBR.
  4. The secondary zinc alkaline battery according to claim 1, wherein the thickening agent comprises at least one selected from the group consisting of CMC, HEC and acrylic ester.
  5. The secondary zinc alkaline battery according to claim 1, wherein the gel electrolyte solution further contains porous ceramic or silica and calcium zincate powder, calcium hydroxide powder or a mixture thereof in an amount of 1~10 parts by weight with reference to the gel polymer.
  6. The secondary zinc alkaline battery according to claim 1, wherein the battery comprises at least one negative electrode separator.
  7. The secondary zinc alkaline battery according to claim 1, wherein the zinc electrode is fabricated by mixing an anode active material and activated carbon using a ball-mill process to prepare a mixture; wetting the mixture, followed by adding a thickening agent to prepare a slurry; adding a binder to the slurry to prepare a composition for negative electrodes; coating the composition on a current collector; and drying the composition coated on the current collector.
  8. The secondary zinc alkaline battery according to claim 7, wherein the anode active material comprises at least one selected from the group consisting of zinc oxide, calcium zincate and zinc powders.
  9. The secondary zinc alkaline battery according to claim 7, wherein the activated carbon comprises at least one selected from the group consisting of acetylene black and Ketjen black.
  10. The secondary zinc alkaline battery according to claim 7, wherein the thickening agent comprises at least one selected from the group consisting of CMC, HEC, and acrylic ester.
  11. The secondary zinc alkaline battery according to claim 7, wherein the thickening agent is substituted Na+ with K+.
  12. The secondary zinc alkaline battery according to claim 7, wherein the binder comprises at least one selected from the group consisting of PTFE, PE and SBR.
  13. The secondary zinc alkaline battery according to claim 7, wherein the mixture comprises 95~99 wt% of the anode active material and 1~5 wt% of the activated carbon.
  14. The method according to claim 7, wherein additives comprising Ca(OH)2 and Bi2O3 are added to the mixture when mixing the anode active material and the activated carbon.
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CN101928036A (en) * 2010-09-08 2010-12-29 童孟良 Microwave preparation method of zinc-nickel battery anode material calcium zincate
CN103296319A (en) * 2013-06-08 2013-09-11 苏州诺信创新能源有限公司 Preparation method of electrolyte membrane for nickel-hydrogen battery
WO2015061403A1 (en) * 2013-10-23 2015-04-30 Bettergy Corp. Composite materials for rechargeable zinc electrodes
US20150214541A1 (en) * 2012-08-06 2015-07-30 Westfälische Wilhelms-Universität Münster Method for producing carbon-coated metal-doped zinc oxide articles and the use thereof
WO2015161188A1 (en) * 2014-04-17 2015-10-22 Aiping Yu Wearable battery charger
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US20030113630A1 (en) * 2001-12-06 2003-06-19 Kainthla Ramesh C. Anodic zinc electrode for use in an alkaline based electrochemical cell
US6953639B2 (en) * 2003-03-17 2005-10-11 Rechargeable Battery Corporation Heavy metal-free rechargeable zinc negative electrode for an alkaline storage cell

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CN101928036A (en) * 2010-09-08 2010-12-29 童孟良 Microwave preparation method of zinc-nickel battery anode material calcium zincate
US9620775B2 (en) * 2012-08-06 2017-04-11 Westfälische Wilhelms-Universität Münster Method for producing carbon-coated metal-doped zinc oxide articles and the use thereof
US20150214541A1 (en) * 2012-08-06 2015-07-30 Westfälische Wilhelms-Universität Münster Method for producing carbon-coated metal-doped zinc oxide articles and the use thereof
CN103296319A (en) * 2013-06-08 2013-09-11 苏州诺信创新能源有限公司 Preparation method of electrolyte membrane for nickel-hydrogen battery
WO2015061403A1 (en) * 2013-10-23 2015-04-30 Bettergy Corp. Composite materials for rechargeable zinc electrodes
CN105612635A (en) * 2013-10-23 2016-05-25 百特吉公司 Composite materials for rechargeable zinc electrodes
WO2015161188A1 (en) * 2014-04-17 2015-10-22 Aiping Yu Wearable battery charger
CN106410291A (en) * 2015-07-30 2017-02-15 株式会社杰士汤浅国际 Storage battery
CN106410291B (en) * 2015-07-30 2021-08-24 株式会社杰士汤浅国际 Electric storage element
WO2017062435A1 (en) * 2015-10-05 2017-04-13 Research Foundation Of The City University Of New York Rechargeable alkaline battery comprising metal hydroxide separator
CN105633482A (en) * 2015-12-30 2016-06-01 湖南格瑞普新能源有限公司 Wide-temperature range and high-power nickel-hydrogen battery and preparation technology thereof
CN111600025A (en) * 2020-04-23 2020-08-28 同济大学 Zinc cathode material with elastic protective layer and preparation and application thereof
US11817591B2 (en) 2020-05-22 2023-11-14 Duracell U.S. Operations, Inc. Seal assembly for a battery cell
CN112563446A (en) * 2020-11-22 2021-03-26 扬州大学 Electrode with biopolymer coating and method for making same
CN113054165A (en) * 2021-03-12 2021-06-29 国家纳米科学中心 Negative pole piece of zinc secondary battery and preparation method and application thereof
US11228032B1 (en) 2021-04-06 2022-01-18 ZAF Energy Systems, Incorporated Secondary electrode including styrene-butadiene rubber
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US11404696B1 (en) 2022-01-05 2022-08-02 ZAF Energy Systems, Incorporated Secondary aqueous battery electrodes including vinyl acetate-ethylene

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