CN103050697B - Method for preparing micron-sized LiFePO4/C serving as high-rate lithium ion battery anode material - Google Patents

Method for preparing micron-sized LiFePO4/C serving as high-rate lithium ion battery anode material Download PDF

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CN103050697B
CN103050697B CN201210593750.5A CN201210593750A CN103050697B CN 103050697 B CN103050697 B CN 103050697B CN 201210593750 A CN201210593750 A CN 201210593750A CN 103050697 B CN103050697 B CN 103050697B
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ion battery
lithium ion
lifepo
battery anode
anode material
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CN103050697A (en
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李小玉
蒋建平
胡雯燕
谷雪贤
柳滢春
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Zhongshan Torch Polytechnic
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Abstract

The invention discloses a method for preparing micron-sized LiFePO4/C serving as a high-rate lithium ion battery anode material. The method comprises the steps as follows: firstly, preparing mono-disperse water-soluble Ag nano-particles, mixing the mono-disperse water-soluble Ag nano-particles and glucose, preparing a nano Ag-glucose organic compound carbon source, mixing lithium salt, iron salt, phosphate and doping metal M at a ratio, and then adding the nano Ag-glucose organic compound carbon source to prepare a LiFePO4/C precursor; and calcining the LiFePO4/C precursor to prepare the micron-sized LiFePO4/C serving as high-rate lithium ion battery anode materials under the protection of nitrogen in vacuum. According to the method, the process is simple, the repeatability is good, the cost is low, and the environment is protected. The processability and the rate capability of the lithium ion battery anode material are good, and the cyclic capacity retention ratio is high.

Description

A kind of high-rate lithium ion battery anode material micron order LiFePO 4the preparation method of/C
[technical field]
The present invention relates to a kind of preparation method of high-rate lithium ion battery anode material, particularly a kind of high-rate lithium ion battery anode material micron order LiFePO 4the preparation method of/C, belongs to electrochemical energy storage materials preparing technical field.
[background technology]
The desirable energy that lithium-ion-power cell developed as 21 century, has that operating voltage is high, energy density is high, has extended cycle life, self-discharge rate is low, the advantage such as pollution-free.Current lithium ion battery still based on low capacity, low battery power, middle Large Copacity, in the not yet large-scale production of high-power lithium ion battery.Fossil energy day by day in short supply will impel that lithium ion battery is extensive is applied to the fields such as electrokinetic cell, wind energy and solar energy deposit.
LiFePO4 (the LiFePO of olivine-type 4) have nontoxic, environmental friendliness, security performance is good, has stable high-temperature performance, and raw material sources are extensive, low price and higher operating voltage (3.45Vvs.Li +/ Li), the advantage such as higher theoretical specific capacity (close to 170mAh/g), preferably cyclical stability, be expected the positive electrode becoming middle Large Copacity, middle high power lithium ion cell first-selection.
At present, LiFePO 4deficiency as anode material for lithium-ion batteries is mainly manifested in the aspects such as tap density is low, poorly conductive.For improving conductivity, people mix conductive carbon material, significantly reduce again the bulk density of material, will be very huge, and be difficult to be applied to reality by the battery volume making to make.The electric conductivity and the practical tool of bulk density to LiFePO 4 that improve LiFePO 4 are marginal.The element composition of material and crystal structure are by chemical properties such as the conductivity of this LiFePO 4 of major effect, high and low temperatures.The granule-morphology of powder body material, particles size and distribution directly affect the bulk density of material.
[summary of the invention]
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, there is provided that a kind of conductivity is high, technique is simple, reproducible, cost is low and the preparation method of the high-rate lithium ion battery anode material of environmental protection, the obtained positive electrode of the method is applied in lithium ion battery and makes battery have good processing characteristics and high rate performance.
The present invention for solving the problems of the technologies described above, by the following technical solutions:
A preparation method of high-rate lithium ion battery anode material micron order LiFePO4/C, is characterized in that comprising the following steps:
A, prepare monodisperse water soluble Ag nano particle
Take silver salt and use water-soluble solution, under stirring condition, by Polymer-supported reducing reagents repetitive: Ag +the thing mass ratio of=2:1 ~ 10:1 adds Polymer-supported reducing reagents, then with distilled water diluting to Ag +molar concentration be 5 × 10 -3molL -1and be 10 ~ 11 by acetic acid or ammoniacal liquor adjust ph, be transferred in reactor after continuing to stir 0.5h and react 16 ~ 48h at 120 ~ 150 DEG C, room temperature is cooled to after reaction terminates, centrifuging and taking lower sediment adds water centrifugation again again, repeats to get precipitation 2 times, with absolute ethanol washing precipitation for several times, get precipitation after centrifugation, obtain monodisperse water soluble Ag nano particle (Ag NPs);
B, preparation LiFePO 4/ C presoma
The monodisperse water soluble Ag nano particle obtained by step a and glucose in mass ratio 1:1 mix, and obtain nanometer Ag-glucose organic mixture carbon source, lithium salts, molysite, phosphate and doping metals M are pressed Li:Fe:PO 4: the thing mass ratio of M=1:0.95 ~ 0.995:1:0.005 ~ 0.05 mixes, then by every mole of PO 4adding the nanometer Ag-glucose organic mixture carbon source of 20 ~ 40g, take absolute ethyl alcohol as ball-milling medium, with rotating speed 250rmin -1ball milling 10h, by the slurry 60 DEG C of dry 12h in baking oven obtained, then grinding is sieved, and obtains LiFePO 4/ C presoma;
C, prepare micron order LiFePO 4/ C positive electrode material
The LiFePO obtained by step b 4/ C presoma is warming up to 650 ~ 700 DEG C of calcining 12h calcine 5 ~ 8h at 350 ~ 450 DEG C in nitrogen protection vacuum tube furnace after, treat that stove is cooled to room temperature, take out grinding, crosses 400 mesh sieves and namely obtains high-rate lithium ion battery anode material micron order LiFePO 4/ C.
Silver salt in the present invention is silver nitrate (AgNO 3) and silver oxide (Ag 2o) one in, is preferably Ag 2o, such system, completely without the need to reprocessing, can simplify preparation flow.
Polymer-supported reducing reagents in the present invention is the one in kayexalate-co-sodium maleate (PSSMA) and polyvinylpyrrolidone (PVP).The gentle reducing agent of PSSMA, PVP class is used directly to prepare Ag NPs, whole process does not need additionally to add reducing agent, and chemical reagent used is more friendly to environment, simultaneously due to the feature of this body structure of Polymer-supported reducing reagents, can stabilizer be served as again, make whole system more stable.
The surface charge density of organic polymer reducing agent PSSMA or PVP can be changed by adjusted to ph during preparation Ag NPs and realize the functionalization of Ag NPs further.
Lithium salts in the present invention is the one in lithium carbonate, lithium hydroxide, lithium nitrate.
Molysite in the present invention is the one in ferrous oxalate, ferrous acetate, ferric oxide.
Phosphate in the present invention is the one in diammonium hydrogen phosphate, ammonium dihydrogen phosphate.
Doping metals M in the present invention is the one in magnesium acetate, magnesium oxide, chromium acetate, chromium oxide, zirconium nitrate, titanium oxide, cerium oxide, praseodymium oxide, samarium oxide.
The present invention is on the basis of containing transition metal or thulium ion modification, nanometer Ag-glucose organic mixture is selected to carry out coating modification as the material of coated carbon source and raising conductivity, and optimize the preparation technology such as solid phase reaction and roasting heat treatment conditions, prepare micron order LiFePO 4/ C particle.
Micron order LiFePO prepared by the present invention 4the particle D of/C 50be 1.80 μm ~ 2.0 μm, specific area is 11.0 ~ 13.0m 2/ g.
The present invention compared with prior art, has following advantage:
In the present invention with nanometer Ag-glucose organic mixture for carbon source and reducing agent, by lithium salts, molysite, phosphate and doping metals by certain amount of substance than mixing, adopt carbothermic method synthesis LiFePO 4/ C positive electrode material, carbon thermal reduction synthesis LiFePO in the present invention 4containing transition metal element or thulium modification during/C positive electrode material, prepare micron LiFePO by solid reaction process in conjunction with two sections of high-temperature roasting heat treatments 4/ C, preparation technology efficiently reduces LiFePO 4/ C material particle size, shortens the migration distance of electronics and lithium ion, thus improves the conductivity of material; In addition, contributing to the adding of Ag NPs improving material conductivity, efficiently solving as promoting conductivity and the mass density of material that a large amount of carbon coated is brought reduces the problem with the volumetric specific energy of battery greatly.
Present invention process is simple, reproducible, with low cost and environmental protection.The processing characteristics of anode material for lithium-ion batteries of the present invention and good rate capability, the capability retention of circulation is high.
[embodiment]
Describe the present invention below in conjunction with specific embodiment:
Embodiment 1:
A, take 0.136g silver nitrate obtain 2 × 10 by the water-soluble solution of 40mL -2molL -1liquor argenti nitratis ophthalmicus.Take out this solution of 1mL, and be diluted to 20mL, add 4 × 10 of 10mL under agitation afterwards -2molL -1kayexalate-co-sodium maleate (PSSMA) solution, redistilled water is diluted to 40mL, and be 10.4 by adjust ph, continue to stir to be transferred in reactor after 0.5h and reacts 18h at 120 DEG C, after reaction terminates, be cooled to room temperature, then centrifuging and taking lower sediment adds water centrifugation again, repeat to get precipitation 2 times, with absolute ethanol washing precipitation several, get precipitation after centrifugation, obtain Ag NPs;
B, the Ag NPs obtained by step a and glucose in mass ratio 1:1 mix, and obtain nanometer Ag-glucose organic mixture carbon source, lithium nitrate, ferrous oxalate, diammonium hydrogen phosphate and zirconium nitrate are pressed Li:Fe:PO 4: the thing mass ratio of Zr=1:0.95:1:0.05 mixes, then by every mole of PO 4adding the nanometer Ag-glucose organic mixture carbon source of 40g, take absolute ethyl alcohol as ball-milling medium, with rotating speed 250rmin -1ball milling 10h, by the slurry 60 DEG C of dry 12h in baking oven obtained, then grinding is sieved, and obtains LiFePO 4/ C presoma;
C, the LiFePO that step b is obtained 4/ C presoma is warming up to 650 DEG C of calcining 12h calcine 8h at 350 DEG C in nitrogen protection vacuum tube furnace after, treat that stove is cooled to room temperature, take out grinding, crosses 400 mesh sieves and namely obtains high-rate lithium ion battery anode material micron order LiFePO 4/ C.
The micron order LiFePO that embodiment 1 is obtained 4the particle D of/C positive electrode material 50be 1.92 μm, specific area is 11.5m 2/ g, when conductive agent acetylene black content is 4.0%, micron order LiFePO 4the coating density of/C is 2.8g/dm 2time, cell positive material has good processing characteristics and high rate performance.Surface temperature rise when 5.00C charging, 15.00C electric discharge is very little.In 2.0 ~ 3.8V discharge and recharge, 96.7%, 87.3%, 1.00C charging when 20.00C, 30.00C discharge capacity after optimization is respectively 1.00C, 10.00C electric discharge, the capability retention of the 400th circulation is 85.3%.
Embodiment 2:
A, take silver oxide and use water-soluble solution, under stirring condition, by Polymer-supported reducing reagents repetitive: Ag +the thing mass ratio of=5:1 adds polyvinylpyrrolidone, then with distilled water diluting to [Ag +]=5 × 10 -3molL -1and be 10.7 by acetic acid or ammoniacal liquor adjust ph, be transferred in reactor after continuing to stir 0.5h and react 24h at 150 DEG C, room temperature is cooled to after reaction terminates, centrifuging and taking lower sediment adds water centrifugation again again, repeats to get precipitation 2 times, with absolute ethanol washing precipitation for several times, get precipitation after centrifugation, obtain Ag NPs;
B, the Ag NPs obtained by step a and glucose in mass ratio 1:1 mix, and obtain nanometer Ag-glucose organic mixture carbon source, lithium carbonate, ferric oxide, ammonium dihydrogen phosphate and magnesium oxide are pressed Li:Fe:PO 4: the thing mass ratio of Mg=1:0.995:1:0.005 mixes, then by every mole of PO 4adding the nanometer Ag-glucose organic mixture carbon source of 30, take absolute ethyl alcohol as ball-milling medium, with rotating speed 250rmin -1ball milling 10h, by the slurry 60 DEG C of dry 12h in baking oven obtained, then grinding is sieved, and obtains LiFePO 4/ C presoma;
C, the LiFePO that step b is obtained 4/ C presoma is warming up to 700 DEG C of calcining 12h calcine 5h at 450 DEG C in nitrogen protection vacuum tube furnace after, treat that stove is cooled to room temperature, take out grinding, crosses 400 mesh sieves and namely obtains high-rate lithium ion battery anode material micron order LiFePO 4/ C.
The micron order LiFePO that embodiment 2 is obtained 4the particle D of/C positive electrode material 50be 1.81 μm, specific area is 12.7m 2/ g, when conductive agent acetylene black content is 4.0%, micron order LiFePO 4the coating density of/C is 2.95g/dm 2time, cell positive material has good processing characteristics and high rate performance; Surface temperature rise when 5.00C charging, 15.00C electric discharge is very little; In 2.0 ~ 3.8V discharge and recharge, 95.7%, 86.2%, 1.00C charging when 20.00C, 30.00C discharge capacity after optimization is respectively 1.00C, 10.00C electric discharge, the capability retention of the 400th circulation is 83.5%.
Embodiment 3:
A, take silver salt and use water-soluble solution, under stirring condition, by Polymer-supported reducing reagents repetitive: Ag +the thing mass ratio of=2:1 adds kayexalate-co-sodium maleate, then with distilled water diluting to [Ag +]=5 × 10 -3molL -1and be 11.0 by acetic acid or ammoniacal liquor adjust ph, be transferred in reactor after continuing to stir 0.5h and react 48h at 140 DEG C, room temperature is cooled to after reaction terminates, centrifuging and taking lower sediment adds water centrifugation again again, repeats to get precipitation 2 times, with absolute ethanol washing precipitation for several times, get precipitation after centrifugation, obtain Ag NPs;
B, the Ag NPs obtained by step a and glucose in mass ratio 1:1 mix, and obtain nanometer Ag-glucose organic mixture carbon source, lithium hydroxide, ferrous acetate, diammonium hydrogen phosphate and praseodymium oxide are pressed Li:Fe:PO 4: the thing mass ratio of Pr=1:0.995:1:0.005 mixes, then by every mole of PO 4adding the nanometer Ag-glucose organic mixture carbon source of 20g, take absolute ethyl alcohol as ball-milling medium, with rotating speed 250rmin -1ball milling 10h, by the slurry 60 DEG C of dry 12h in baking oven obtained, then grinding is sieved, and obtains LiFePO 4/ C presoma;
C, the LiFePO that step b is obtained 4/ C presoma is warming up to 700 DEG C of calcining 12h calcine 5h at 450 DEG C in nitrogen protection vacuum tube furnace after, treat that stove is cooled to room temperature, take out grinding, crosses 400 mesh sieves and namely obtains high-rate lithium ion battery anode material micron order LiFePO 4/ C.
The micron order LiFePO that embodiment 3 is obtained 4the particle D of/C positive electrode material 50be 1.87 μm, specific area is 12.1m 2/ g, when conductive agent acetylene black content is 4.0%, micron order LiFePO 4the coating density of/C is 2.89g/dm 2time, cell positive material has good processing characteristics and high rate performance; Surface temperature rise when 5.00C charging, 15.00C electric discharge is very little; In 2.0 ~ 3.8V discharge and recharge, 92.7%, 83.2%, 1.00C charging when 20.00C, 30.00C discharge capacity after optimization is respectively 1.00C, 10.00C electric discharge, the capability retention of the 400th circulation is 83.8%.
Embodiment 4:
A, take silver salt and use water-soluble solution, under stirring condition, by Polymer-supported reducing reagents repetitive: Ag +the thing mass ratio of=10:1 adds kayexalate-co-sodium maleate, then with distilled water diluting to [Ag +]=5 × 10 -3molL -1and be 10.7 by acetic acid or ammoniacal liquor adjust ph, be transferred in reactor after continuing to stir 0.5h and react 24h at 120 DEG C, room temperature is cooled to after reaction terminates, centrifuging and taking lower sediment adds water centrifugation again again, repeats to get precipitation 2 times, with absolute ethanol washing precipitation for several times, get precipitation after centrifugation, obtain Ag NPs;
B, the Ag NPs obtained by step a and glucose in mass ratio 1:1 mix, and obtain nanometer Ag-glucose organic mixture carbon source, lithium carbonate, ferrous oxalate, diammonium hydrogen phosphate and chromium oxide are pressed Li:Fe:PO 4: the thing mass ratio of Cr=1:0.98:1:0.02 mixes, then by every mole of PO 4adding the nanometer Ag-glucose organic mixture carbon source of 20g, take absolute ethyl alcohol as ball-milling medium, with rotating speed 250rmin -1ball milling 10h, by the slurry 60 DEG C of dry 12h in baking oven obtained, then grinding is sieved, and obtains LiFePO 4/ C presoma;
C, the LiFePO that step b is obtained 4/ C presoma is warming up to 700 DEG C of calcining 12h calcine 7h at 400 DEG C in nitrogen protection vacuum tube furnace after, treat that stove is cooled to room temperature, take out grinding, crosses 400 mesh sieves and namely obtains high-rate lithium ion battery anode material micron order LiFePO 4/ C.
The micron order LiFePO that embodiment 4 is obtained 4the particle D of/C positive electrode material 50be 1.95 μm, specific area is 11.2m 2/ g, when conductive agent acetylene black content is 4.0%, micron order LiFePO 4the coating density of/C is 2.76g/dm 2time, cell positive material has good processing characteristics and high rate performance; Surface temperature rise when 5.00C charging, 15.00C electric discharge is very little; In 2.0 ~ 3.8V discharge and recharge, 95.8%, 85.3%, 1.00C charging when 20.00C, 30.00C discharge capacity after optimization is respectively 1.00C, 10.00C electric discharge, the capability retention of the 400th circulation is 82.4%.
Embodiment 5:
A, take silver salt and use water-soluble solution, under stirring condition, pressing repetitive by Polymer-supported reducing reagents: Ag +the thing mass ratio of=10:1 adds polyvinylpyrrolidone, then with distilled water diluting to [Ag +]=5 × 10 -3molL -1and be 10.4 by acetic acid or ammoniacal liquor adjust ph, be transferred in reactor after continuing to stir 0.5h and react 24h at 120 DEG C, room temperature is cooled to after reaction terminates, centrifuging and taking lower sediment adds water centrifugation again again, repeats to get precipitation 2 times, with absolute ethanol washing precipitation for several times, get precipitation after centrifugation, obtain Ag NPs;
B, the Ag NPs obtained by step a and glucose in mass ratio 1:1 mix, and obtain nanometer Ag-glucose organic mixture carbon source, lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate and cerium oxide are pressed Li:Fe:PO 4: the thing mass ratio of Ce=1:0.98:1:0.02 mixes, then by every mole of PO 4adding the nanometer Ag-glucose organic mixture carbon source of 20g, take absolute ethyl alcohol as ball-milling medium, with rotating speed 250rmin -1ball milling 10h, by the slurry 60 DEG C of dry 12h in baking oven obtained, then grinding is sieved, and obtains LiFePO 4/ C presoma;
C, the LiFePO that step b is obtained 4/ C presoma is warming up to 700 DEG C of calcining 12h calcine 7h at 400 DEG C in nitrogen protection vacuum tube furnace after, treat that stove is cooled to room temperature, take out grinding, crosses 400 mesh sieves and namely obtains high-rate lithium ion battery anode material micron order LiFePO 4/ C.
The micron order LiFePO that embodiment 5 is obtained 4the particle D of/C positive electrode material 50be 1.95 μm, specific area is 11.2m 2/ g, when conductive agent acetylene black content is 4.0%, micron order LiFePO 4the coating density of/C is 2.76g/dm 2time, cell positive material has good processing characteristics and high rate performance; Surface temperature rise when 5.00C charging, 15.00C electric discharge is very little; In 2.0 ~ 3.8V discharge and recharge, 93.8%, 85.3%, 1.00C charging when 20.00C, 30.00C discharge capacity after optimization is respectively 1.00C, 10.00C electric discharge, the capability retention of the 400th circulation is 83.4%.

Claims (8)

1. a high-rate lithium ion battery anode material micron order LiFePO 4the preparation method of/C, is characterized in that comprising the following steps:
A, prepare monodisperse water soluble Ag nano particle
Take silver salt and use water-soluble solution, under stirring condition, by Polymer-supported reducing reagents repetitive: Ag +the amount of substance ratio of=2:1 ~ 10:1 adds Polymer-supported reducing reagents, then with distilled water diluting to Ag +molar concentration be 5 × 10 -3molL -1and be 10 ~ 11 by acetic acid or ammoniacal liquor adjust ph, be transferred in reactor after continuing to stir 0.5h and react 16 ~ 48h at 120 ~ 150 DEG C, room temperature is cooled to after reaction terminates, centrifuging and taking lower sediment adds water centrifugation again again, repeats to get precipitation 2 times, with absolute ethanol washing precipitation for several times, get precipitation after centrifugation, obtain monodisperse water soluble Ag nano particle;
B, preparation LiFePO 4/ C presoma
The Ag nano particle obtained by step a and glucose in mass ratio 1:1 mix, and obtain nanometer Ag-glucose organic mixture carbon source, lithium salts, molysite, phosphate and doping metals M are pressed Li:Fe:PO 4 3-: the amount of substance ratio of M=1:0.95 ~ 0.995:1:0.005 ~ 0.05 mixes, then by every mole of PO 4 3-adding the nanometer Ag-glucose organic mixture carbon source of 20 ~ 40g, take absolute ethyl alcohol as ball-milling medium, with rotating speed 250rmin -1ball milling 10h, by the slurry 60 DEG C of dry 12h in baking oven obtained, then grinding is sieved, and obtains LiFePO 4/ C presoma;
C, prepare micron order LiFePO 4/ C positive electrode material
The LiFePO obtained by step b 4/ C presoma is warming up to 650 ~ 700 DEG C of calcining 12h calcine 5 ~ 8h at 350 ~ 450 DEG C in nitrogen protection vacuum tube furnace after, treat that stove is cooled to room temperature, take out grinding, crosses 400 mesh sieves and namely obtains high-rate lithium ion battery anode material micron order LiFePO 4/ C.
2. a kind of high-rate lithium ion battery anode material micron order LiFePO according to claim 1 4the preparation method of/C, is characterized in that described silver salt is the one in silver nitrate and silver oxide.
3. a kind of high-rate lithium ion battery anode material micron order LiFePO according to claim 1 4the preparation method of/C, is characterized in that described Polymer-supported reducing reagents is the one in kayexalate-co-sodium maleate and polyvinylpyrrolidone.
4. a kind of high-rate lithium ion battery anode material micron order LiFePO according to claim 1 4the preparation method of/C, is characterized in that described lithium salts is the one in lithium carbonate, lithium hydroxide, lithium nitrate.
5. a kind of high-rate lithium ion battery anode material micron order LiFePO according to claim 1 4the preparation method of/C, is characterized in that described molysite is the one in ferrous oxalate, ferrous acetate, ferric oxide.
6. a kind of high-rate lithium ion battery anode material micron order LiFePO according to claim 1 4the preparation method of/C, is characterized in that described phosphate is the one in diammonium hydrogen phosphate, ammonium dihydrogen phosphate.
7. a kind of high-rate lithium ion battery anode material micron order LiFePO according to claim 1 4the preparation method of/C, is characterized in that described doping metals M is the one in magnesium acetate, magnesium oxide, chromium acetate, chromium oxide, zirconium nitrate, titanium oxide, cerium oxide, praseodymium oxide, samarium oxide.
8. a kind of high-rate lithium ion battery anode material micron order LiFePO according to any one of claim 1-7 4the preparation method of/C, is characterized in that described micron order LiFePO 4the particle D of/C 50be 1.80 μm ~ 2.0 μm, specific area is 11.0 ~ 13.0m 2/ g.
CN201210593750.5A 2012-12-31 2012-12-31 Method for preparing micron-sized LiFePO4/C serving as high-rate lithium ion battery anode material Expired - Fee Related CN103050697B (en)

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CN106103337A (en) * 2014-12-26 2016-11-09 恒耀能源股份有限公司 The manufacture method of nano-powder, the electrode comprising this nano-powder and comprise the battery of this electrode
CN105449206A (en) * 2015-12-23 2016-03-30 邬石根 LiFe1-xZrxPO4 electrode material and preparation method thereof
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CN115974102A (en) * 2022-12-26 2023-04-18 深圳华钠新材有限责任公司 Preparation method and application of silver-carbon coated Prussian blue material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1649189A (en) * 2004-12-29 2005-08-03 浙江大学 Method for preparing carbon coated lithium ferrous phosphate composite material including metal conductive agent
CN1721321A (en) * 2005-05-13 2006-01-18 中国科学院上海硅酸盐研究所 A kind of method for preparing the simple substance nano powder with the reductive agent reduced oxide
CN101635349A (en) * 2009-08-21 2010-01-27 广州市云通磁电有限公司 Method for preparing metal-silver-doped carbon-covering lithium iron phosphate of lithium-ion battery cathode material
CN101112979B (en) * 2007-06-27 2010-05-19 广州市鹏辉电池有限公司 Solid-phase method for preparation of high-density spherical-like ferric phosphate lithium

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1649189A (en) * 2004-12-29 2005-08-03 浙江大学 Method for preparing carbon coated lithium ferrous phosphate composite material including metal conductive agent
CN1721321A (en) * 2005-05-13 2006-01-18 中国科学院上海硅酸盐研究所 A kind of method for preparing the simple substance nano powder with the reductive agent reduced oxide
CN101112979B (en) * 2007-06-27 2010-05-19 广州市鹏辉电池有限公司 Solid-phase method for preparation of high-density spherical-like ferric phosphate lithium
CN101635349A (en) * 2009-08-21 2010-01-27 广州市云通磁电有限公司 Method for preparing metal-silver-doped carbon-covering lithium iron phosphate of lithium-ion battery cathode material

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