CN102443882A - Method for preparing microporous LiFePO4/C type fiber by applying supercritical fluid melt-spraying spinning - Google Patents
Method for preparing microporous LiFePO4/C type fiber by applying supercritical fluid melt-spraying spinning Download PDFInfo
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- CN102443882A CN102443882A CN2011103339625A CN201110333962A CN102443882A CN 102443882 A CN102443882 A CN 102443882A CN 2011103339625 A CN2011103339625 A CN 2011103339625A CN 201110333962 A CN201110333962 A CN 201110333962A CN 102443882 A CN102443882 A CN 102443882A
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- supercritical fluid
- lifepo
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Abstract
The invention discloses a method for preparing microporous LiFePO4/C type fiber by applying supercritical fluid melt-spraying spinning. The method comprises the following steps of: introducing an iron source, a lithium source, a reducing agent, a carbon source and a complexing agent into a high-pressure reaction kettle for uniformly stirring; introducing supercritical fluid into the high-pressure reaction kettle to be uniformly mixed with the blend, and further reacting and synthesizing for 24 hours in the supercritical fluid; (3) feeding the uniformly-mixed materials into a screw quantitatively, compacting by a screw compression section and gradually forming a homogeneous body; (4) leading the homogeneous body to pass through a filter medium at a filter part; (5) after the homogeneous body passes through an inlet zone, an orifice flow zone and an expanding zone of a melt spraying die head, extruding the homogeneous body from spinneret orifices of the die head to form superfine microporous fiber; and (6) after naturally cooling, putting the obtained fiber into a quartz glass tube, then putting the quartz glass tube with the obtained fiber into a tube furnace, presintering for 4-6 hours at the temperature of 250-400 DEG C in the atmosphere of mixed gas flow with 5% H2 and 95% N2 according to volume percentage, then roasting for 9-11 hours at the temperature of 600 DEG C in the atmosphere of the mixed gas flow, cooling to room temperature along with the furnace, and obtaining the LiFePO4/C type superfine microporous fiber.
Description
Technical field
The present invention relates to a kind of supercritical fluid of using and melt and spray the method that spinning prepares micropore LiFePO4/C fibrid.
Background technology
LiFePO 4 LiFePO
4Can embed reversiblely and deviate from lithium ion, Fe
2+/ Fe
3+The voltage of lithium metal is 3.4 V relatively, and the theoretical specific capacity of this material is 170 mAh/g.Because LiFePO
4Have that nontoxic, environmental friendliness, raw material source are abundant and cheap, advantages such as cyclicity and Heat stability is good, thereby obtain the application on lithium battery very soon.But LiFePO
4Electrical conductivity be merely 10
-9The S/cm order of magnitude, simultaneously lithium ion is owing to receive that oxygen atom is closely packed closely influences, to lithium ion in charge and discharge process diffusion and transmit unfavorable.At present, to LiFePO
4The research of positive electrode mainly concentrates on the conductance of improving its electronics and ion, is included in the outside good conductive agents such as carbon, metal or conducting polymer of dispersive property that evenly coat of particle, improves the apparent electrical conductivity between particle surface and the particle; Adopt metal ion mixing in granule interior, reduce the conduction level of solid material or cause the ion vacancy, improve the intrinsic conductivity nano materials of material, reduce the electronics of material or the diffusion length of ion.LiFePO
4Common synthetic method high-temperature solid phase reaction method, sol-gel process, solvent-thermal method etc. are arranged.Commercial production adopts high temperature solid phase synthesis more, and still, this method quality stability in building-up process is not easy control, and product need carry out multistep calcination and grinding in order to obtain uniformly.
The development of meltblown fibers production technology and the expansion of product applications have promoted the use of high-performance polymer; To satisfy the special demands of fabrics for industrial use; Little like fibre fineness, high temperature resistant, chemical resistance, good intensity and elasticity, medical product comfort, with the requirements such as security of Food Contact.
Supercritical fluid; Be meant that certain material is in the critical point critical-temperature; More than the critical pressure, have the fluid of the unique rerum natura that is different from liquid or gas, not only have the characteristic of gas but also have the characteristic of liquid; Therefore we can say that supercritical fluid is the 3rd fluid that is present in beyond gas, these two kinds of fluid states of liquid.Supercritical fluid has the density close with liquid, thereby very strong solvent strength is arranged, and has the viscosity close with gas simultaneously, and mobile more much better than liquid, mass tranfer coefficient is also much bigger than liquid.And performances such as the density of fluid, solvent strength and viscosity all can be regulated through the variation of pressure and temperature easily, thereby have wide practical use.Adopt supercritical CO
2Extract and obtain broad research and commercial Application.In Polymer Processing, adopt supercritical CO
2Though few, obtained suitable attention and extensive studies, like supercritical CO
2Polymerisation, employing supercritical CO for medium
2In polymer, add additive, supercritical CO
2Swollen-state polymerization obtains blend and composite, polymer classification, extraction oligomer and solvent, microballoon and fento preparation, crystallization etc.
In the microporous polymer preparation, use supercritical fluid to have the following advantages:
(1) mass tranfer coefficient is high, can reach equilibrium concentration in the short period of time, thereby shorten process time, makes the commercial Application of microporous polymer preparation become possibility.
(2) under uniform temp, use supercritical CO
2Higher equilibrium concentration can be reached, thereby higher cell density and littler cell diameter can be obtained.
(3) can reduce the viscosity of polymer greatly owing to supercritical fluid dissolves in polymer, thereby reduce the flowability that melts and sprays pressure and improve melt.
Through changing the temperature or the pressure of supercritical fluid, can obtain being in the arbitrary density between gaseous state and the liquid state; Near critical point, the minor variations of pressure and temperature can cause the great variety of density.Because viscosity, dielectric constant, diffusion coefficient are all relevant with density with solvability, therefore can regulate the physicochemical properties that pressure and temperature is controlled supercritical fluid easily.The preparation of microporous polymer is mainly based on gas supersaturation method.Basic process is: at first make gases at high pressure (CO
2And N
2) be dissolved in and form the saturated system of polymer/gas in the polymer; Then through pressure drop with (or) temperature rises sharply and makes it to get into hypersaturated state, thereby a large amount of gas nuclear causes simultaneously and increases; Make the microcellular structure typing through methods such as quenchings at last.The improvement of conventional foam plastics physical blowing is technological parameters such as strict control temperature, pressure, time, makes a large amount of gas nuclear energy cause enough simultaneously, and not merger becomes bulla, thereby obtains microcellular structure.Adopt the supersaturation principle to prepare the process of microporous polymer, according to the continuous degree difference of operation mainly contain the method for fractional steps, semi-continuous process and extrude, continuity methods such as injection moulding, rotational moulding.The method of fractional steps and semi-continuous process are determined by the diffusion velocity of gas to polymeric matrix owing to forming the saturated system required time of polymer/gas, thereby length consuming time, can't satisfy industrial needs, are mainly used in theoretical research.And with the actual appearance that melts and sprays the corresponding to continuity method of processing, make micropore LiFePO
4The practical application of/C fibrid becomes possibility.Micropore LiFePO
4The mechanical property of/C fibrid mainly depends on and microcellular structure (comprising: hole dimension, hole density, pore size distribution and hole orientation) and molecular chain orientation.And through optimizing technology, control microcellular structure and molecular chain orientation can obtain the micropore LiFePO of function admirable
4/ C fibrid.
Summary of the invention
The purpose of this invention is to provide a kind of application supercritical fluid melts and sprays spinning and prepares micropore LiFePO
4The method of/C superfine fibre is to satisfy the demand of association areas such as weaving that lithium battery is the basis, electric, electronics, machinery, medical treatment, chemical industry, food and Aero-Space.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is following:
Application supercritical fluid of the present invention melts and sprays spinning and prepares micropore LiFePO
4The method of/C fibrid is characterized in that: comprise the steps:
(1) with source of iron: lithium source: reductant: carbon source: complexing agent is 0.8 ~ 1.2: 0.8 ~ 1.2: 0.8 ~ 1.2: 0.4 ~ 0.6 in molar ratio: 0.1 ~ 0.3 ratio takes by weighing, and imports evenly to mix in the autoclave that liner is housed to obtain blend;
(2) supercritical fluid is imported in the autoclave mix with above-mentioned blend and keep certain pressure (7-17 MPa), under certain holding temperature, stir and make raw materials mix even, simultaneously reaction Synthetic 24 hours in supercritical fluid.
(3) above-mentioned even composite material is quantitatively fed screw rod, be transferred and evenly blend, also become the homogeneous phase body gradually through the compacting of screw compression section then in the screw feed section;
(4) in the filter part, the homogeneous phase body is through filter medium, residual catalyst after elimination impurity and the polymerisation;
(5) in the measuring pump part, the homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, with the accurate controlling fiber fineness and the uniformity;
(6) the homogeneous phase body through the meltblown beam inlet region, orifice flow district and fluffing zone extrude from the die head spinneret orifice;
When the homogeneous phase body body thread of (7) extruding from the die head spinneret orifice because of environmental pressure reduces suddenly expanded swelling is taken place, receive the drawing-off of both sides high velocity, hot air stream, the melt thread that is in viscous state is by drawing-down rapidly; Simultaneously, the air at room temperature of both sides mixes the drawing-off thermal air current, and melt thread cooling curing is shaped, and forms ultra-fine micropore fibrid.
(8) after cooling off naturally, obtaining fiber and put into quartz glass tube and place tube furnace, is 5% H in volume fraction
2Gas and 95% N
2Under the mixed airflow of gas in 300-400 ℃ of temperature pre-burning 4-6 hour, under above-mentioned gaseous mixture in 500-700 ℃ of temperature roasting 9-11 hour again, cool to room temperature with the furnace, promptly get LiFePO
4The ultra-fine micropore fibrid of/C.
Wherein source of iron is FePO
42H
2O, Fe (NO
3)
39H
2O, ferrous oxalate, ferrous acetate, Fe2O3 etc., but be not limited to this; The Li source is LiH2PO4, Li2CO3, LiNO3 etc., but is not limited to this; Carbon source is polypropylene, sucrose, PVA or PVP etc., but is not limited to this; Complexing agent is NH4 H2 PO4, glycine etc., but is not limited to this.
Said supercritical fluid is overcritical N
2,H
2O or supercritical CO
2
Said supercritical fluid is overcritical N
2The time, its temperature is 50 ~ 380 ℃, pressure is 7 ~ 40MPa, overcritical N
2With the mass ratio of blend be 1:400-1:10.
Said supercritical fluid is overcritical H
2During O, its temperature is 330 ~ 380 ℃, and pressure is 19 ~ 24MPa, overcritical H
2The mass ratio of O and blend is 1:X-1:X.
Said supercritical fluid is a supercritical CO
2The time, its temperature is 50 ~ 380 ℃, critical pressure is 7 ~ 40MPa, supercritical CO
2With the mass ratio of blend be 1:100 ~ 1:10.
Said homogeneous phase body is 7 ~ 40MPa with extraneous pressure differential, and melting and spraying speed is 10 ~ 2000cm
3/ s.
Advantage of the present invention is remarkable, adopts of the present inventionly to melt and spray spinning with supercritical fluid and prepare polymer micro LiFePO
4The method of/C fibrid can make the micropore LiFePO of ultra-fine (200-90000nm)
4/ C fibrid.
Description of drawings
Fig. 1 uses supercritical fluid and melts and sprays spinning and prepare micropore LiFePO
4The method principle schematic of/C fibrid.
The specific embodiment
Embodiment 1
With Fe (NO
3)
39H
2O:LiNO
3: NH
4H
2PO
4: sucrose: PVA (PVP) 0.8: 0.8: 0.8 in molar ratio ~ 1.2: 0.4:0.1 takes by weighing, and imports in the autoclave that liner is housed evenly to mix.With temperature is 50-380 ℃, and pressure is the supercritical CO of 7-40MPa
2Import in the autoclave and evenly mix supercritical CO with above-mentioned material
2With the mass ratio of blend be 1:100 ~ 1:10.Stirring makes raw materials mix even under above-mentioned holding temperature, and the reaction generated time is 24 hours in the supercritical fluid.Above-mentioned even composite material is quantitatively fed screw rod, be transferred and evenly blend, then through compacting of screw compression section and homogeneous phase body gradually in the screw feed section.The homogeneous phase body should pass through filter medium, residual catalyst after elimination impurity and the polymerisation.The homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, with the accurate controlling fiber fineness and the uniformity.As shown in Figure 1, arrow A is represented the injection direction of homogeneous mixture melt among the figure, and arrow B is represented drawing-off with the mobile direction of hot-air, and arrow C is represented the flow of cold air direction.The homogeneous phase body through meltblown beam inlet region 1, orifice flow district 2 and fluffing zone 3 extrude from the die head spinneret orifice, melting and spraying speed is 10-2000 cm
3/ s.When the homogeneous phase body body thread of extruding from the die head spinneret orifice because of environmental pressure reduces suddenly expanded swelling is taken place, receive the drawing-off of both sides 290-320 ℃ of high velocity, hot air stream, the melt thread that is in viscous state is by drawing-down rapidly.Simultaneously, the air at room temperature of both sides mixes the drawing-off thermal air current, and melt thread cooling curing is shaped, and forms ultra-fine micropore fibrid.Above fiber obtains LiFePO through roasting
4/ C fiber, fibre fineness 200nm can directly use this LiFePO
4/ C fiber is done anode material of lithium battery.
Embodiment 2
With Fe (NO
3)
39H
2O: LiNO
3: NH
4H
2PO
4: sucrose: PVA (PVP) 1.2: 1.2: 1.2 in molar ratio: take by weighing at 0.6: 0.3, import in the autoclave that liner is housed and evenly mix.With 80 ℃, 16 MPa supercritical COs
2Import in the autoclave and evenly mix with above-mentioned material.Stirring makes raw materials mix even under above-mentioned holding temperature, and the reaction generated time is 24 hours in the supercritical fluid.The above-mentioned even composite material of autoclave quantitatively feeds screw rod, is transferred and evenly blend in the screw feed section, then through compacting of screw compression section and homogeneous phase body gradually; The homogeneous phase body should pass through filter medium, residual catalyst after elimination impurity and the polymerisation; The homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, with the accurate controlling fiber fineness and the uniformity; The homogeneous phase body through the meltblown beam inlet region, orifice flow district and fluffing zone extrude from the die head spinneret orifice; When the homogeneous phase body body thread of extruding from the die head spinneret orifice because of environmental pressure reduces suddenly expanded swelling is taken place, receive the drawing-off of both sides high velocity, hot air stream, the melt thread that is in viscous state is by drawing-down rapidly.Simultaneously, the air at room temperature of both sides mixes the drawing-off thermal air current, and melt thread cooling curing is shaped, and forms ultra-fine micropore fibrid; Above fiber obtains LiFePO through roasting
4/ C fiber, fibre fineness 300nm can directly use this LiFePO
4/ C fiber is done anode material of lithium battery.
Embodiment 3
With Fe (NO
3)
39H
2O:LiNO
3: NH
4H
2PO
4: sucrose: PVA (PVP) 0.8: 0.8: 0.8 in molar ratio ~ 1.2: 0.4:0.1 takes by weighing, and imports in the autoclave that liner is housed evenly to mix.With 50 ℃, the overcritical N of 7MPa
2Import in the autoclave and evenly mix with above-mentioned material.Stirring makes raw materials mix even under above-mentioned holding temperature, and the reaction generated time is 24 hours in the supercritical fluid.The above-mentioned even composite material of autoclave quantitatively feeds screw rod, is transferred and evenly blend in the screw feed section, then through compacting of screw compression section and homogeneous phase body gradually.The homogeneous phase body should pass through filter medium, residual catalyst after elimination impurity and the polymerisation.The homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, with the accurate controlling fiber fineness and the uniformity.The homogeneous phase body through the meltblown beam inlet region, orifice flow district and fluffing zone extrude from the die head spinneret orifice.When the homogeneous phase body body thread of extruding from the die head spinneret orifice because of environmental pressure reduces suddenly expanded swelling is taken place, receive the drawing-off of the 290 ℃ of high velocity, hot airs streams in both sides, the melt thread that is in viscous state is by drawing-down rapidly.Simultaneously, the air at room temperature of both sides mixes the drawing-off thermal air current, and melt thread cooling curing is shaped, and forms ultra-fine micropore fibrid.Above fiber obtains LiFePO through roasting
4/ C target product, fibre fineness 800nm can directly use this LiFePO
4/ C does anode material of lithium battery.
Embodiment 4
With Fe (NO
3)
39H
2O: LiNO
3: NH
4H
2PO
4: sucrose: PVA (PVP) 1.2: 1.2: 1.2 in molar ratio: take by weighing at 0.6: 0.3, import in the autoclave that liner is housed and evenly mix.With 80 ℃, the overcritical N of 16 MPa
2Import in the autoclave and evenly mix with above-mentioned material.Stirring makes raw materials mix even under above-mentioned holding temperature, and the reaction generated time is 24 hours in the supercritical fluid.The above-mentioned even composite material of autoclave quantitatively feeds screw rod, is transferred and evenly blend in the screw feed section, then through compacting of screw compression section and homogeneous phase body gradually; The homogeneous phase body should pass through filter medium, residual catalyst after elimination impurity and the polymerisation; The homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, with the accurate controlling fiber fineness and the uniformity; The homogeneous phase body through the meltblown beam inlet region, orifice flow district and fluffing zone extrude from the die head spinneret orifice; When the homogeneous phase body body thread of extruding from the die head spinneret orifice because of environmental pressure reduces suddenly expanded swelling is taken place, receive the drawing-off of both sides high velocity, hot air stream, the melt thread that is in viscous state is by drawing-down rapidly.Simultaneously, the air at room temperature of both sides mixes the drawing-off thermal air current, and melt thread cooling curing is shaped, and forms ultra-fine micropore fibrid; Above fiber obtains LiFePO through roasting
4/ C superfine fibre, fibre fineness 1000nm can directly use this LiFePO
4/ C superfine fibre is done anode material of lithium battery.
Claims (7)
1. use supercritical fluid and melt and spray spinning and prepare micropore LiFePO for one kind
4The method of/C fibrid is characterized in that: comprise the steps:
(1) with source of iron: lithium source: reductant: carbon source: complexing agent is 0.8 ~ 1.2: 0.8 ~ 1.2: 0.8 ~ 1.2: 0.4 ~ 0.6 in molar ratio: 0.1 ~ 0.3 ratio takes by weighing, and imports evenly to mix in the autoclave that liner is housed to obtain blend;
(2) supercritical fluid is imported in the autoclave mix with above-mentioned blend and keep certain pressure (7-17 MPa), under certain holding temperature, stir and make raw materials mix even, simultaneously reaction Synthetic 24 hours in supercritical fluid;
(3) above-mentioned even composite material is quantitatively fed screw rod, be transferred and evenly blend, also become the homogeneous phase body gradually through the compacting of screw compression section then in the screw feed section;
(4) in the filter part, the homogeneous phase body is through filter medium, residual catalyst after elimination impurity and the polymerisation;
(5) in the measuring pump part, the homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, with the accurate controlling fiber fineness and the uniformity;
(6) the homogeneous phase body through the meltblown beam inlet region, orifice flow district and fluffing zone extrude from the die head spinneret orifice;
When the homogeneous phase body body thread of (7) extruding from the die head spinneret orifice because of environmental pressure reduces suddenly expanded swelling is taken place, receive the drawing-off of both sides high velocity, hot air stream, the melt thread that is in viscous state is by drawing-down rapidly; Simultaneously, the air at room temperature of both sides mixes the drawing-off thermal air current, and melt thread cooling curing is shaped, and forms ultra-fine micropore fibrid;
(8) after cooling off naturally, obtaining fiber and put into quartz glass tube and place tube furnace, is 5% H in volume fraction
2Gas and 95% N
2In the mixed airflow atmosphere of gas,, in above-mentioned mixed airflow atmosphere,, cool to room temperature with the furnace again, promptly get LiFePO in 600 ℃ of roasting temperature 9-11 hours in 250-400 ℃ of temperature pre-burning 4-6 hour
4The ultra-fine micropore fibrid of/C.
2. application supercritical fluid according to claim 1 melts and sprays spinning and prepares micropore LiFePO
4The method of/C fibrid is characterized in that: described source of iron is FePO
42H
2O, Fe (NO
3)
39H
2O, ferrous oxalate, ferrous acetate or Fe
2O
3In any one; The Li source is LiH
2PO
4, Li
2CO
3Or LiNO
3In any one, carbon source is any one among polypropylene, sucrose, PVA or the PVP, complexing agent is NH
4H
2PO
4Or glycine.
3. application supercritical fluid according to claim 1 melts and sprays spinning and prepares micropore LiFePO
4The method of/C fibrid is characterized in that: said supercritical fluid is overcritical N
2,Overcritical H
2O or supercritical CO
2
4. application supercritical fluid according to claim 3 melts and sprays spinning and prepares micropore LiFePO
4The method of/C fibrid is characterized in that: said supercritical fluid is overcritical N
2The time, its temperature is 50 ~ 380 ℃, pressure is 7 ~ 40MPa, overcritical N
2With the mass ratio of blend be 1:400-1:10.
5. application supercritical fluid according to claim 3 melts and sprays spinning and prepares micropore LiFePO
4The method of/C fibrid is characterized in that: said supercritical fluid is overcritical H
2During O, its temperature is 330 ~ 380 ℃, and pressure is 19 ~ 24MPa, overcritical H
2The mass ratio of O and blend is 1:X-1:X.
6. application supercritical fluid according to claim 3 melts and sprays spinning and prepares micropore LiFePO
4The method of/C fibrid is characterized in that: said supercritical fluid is a supercritical CO
2The time, its temperature is 50 ~ 380 ℃, critical pressure is 7 ~ 40MPa, supercritical CO
2With the mass ratio of blend be 1:100 ~ 1:10.
7. application supercritical fluid according to claim 3 melts and sprays spinning and prepares micropore LiFePO
4The method of/C fibrid is characterized in that: described homogeneous phase body is 7 ~ 40MPa with extraneous pressure differential, and melting and spraying speed is 10 ~ 2000cm
3/ s.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103339625A CN102443882B (en) | 2011-10-28 | 2011-10-28 | Method for preparing microporous LiFePO4/C type fiber by applying supercritical fluid melt-spraying spinning |
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| CN102443882A true CN102443882A (en) | 2012-05-09 |
| CN102443882B CN102443882B (en) | 2013-12-11 |
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ID=46006803
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104357956A (en) * | 2014-11-19 | 2015-02-18 | 国网河南省电力公司濮阳供电公司 | Preparation method of bacterial cellulose based carbon nanofiber for piezoelectric generator |
| CN113299872A (en) * | 2021-05-24 | 2021-08-24 | 天津森特新材料科技有限责任公司 | Preparation method of lithium iron phosphate anode of lithium ion battery |
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| WO2005016612A2 (en) * | 2003-08-06 | 2005-02-24 | Milliken & Company | Method of forming light dispersing fiber and fiber formed thereby |
| CN1705776A (en) * | 2002-10-18 | 2005-12-07 | 可隆株式会社 | A microcellular foamed fiber, and a process of preparing for the same |
| CN1908053A (en) * | 2006-08-14 | 2007-02-07 | 华东理工大学 | Method of preparing siliceous polypropylene nano foaming material using supercritical carbon dioxide technique |
| CN101475156A (en) * | 2008-12-31 | 2009-07-08 | 郑州市联合能源电子有限公司 | Preparation of lithium iron phosphate precursor and charging battery electrode thereof |
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Patent Citations (5)
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| US5866053A (en) * | 1993-11-04 | 1999-02-02 | Massachusetts Institute Of Technology | Method for providing continuous processing of microcellular and supermicrocellular foamed materials |
| CN1705776A (en) * | 2002-10-18 | 2005-12-07 | 可隆株式会社 | A microcellular foamed fiber, and a process of preparing for the same |
| WO2005016612A2 (en) * | 2003-08-06 | 2005-02-24 | Milliken & Company | Method of forming light dispersing fiber and fiber formed thereby |
| CN1908053A (en) * | 2006-08-14 | 2007-02-07 | 华东理工大学 | Method of preparing siliceous polypropylene nano foaming material using supercritical carbon dioxide technique |
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| CN104357956A (en) * | 2014-11-19 | 2015-02-18 | 国网河南省电力公司濮阳供电公司 | Preparation method of bacterial cellulose based carbon nanofiber for piezoelectric generator |
| CN113299872A (en) * | 2021-05-24 | 2021-08-24 | 天津森特新材料科技有限责任公司 | Preparation method of lithium iron phosphate anode of lithium ion battery |
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|---|---|
| CN102443882B (en) | 2013-12-11 |
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