CN103896239A - Carbon thermal reduction method for producing lithium vanadium phosphate by using polymer material - Google Patents
Carbon thermal reduction method for producing lithium vanadium phosphate by using polymer material Download PDFInfo
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- CN103896239A CN103896239A CN201410111590.5A CN201410111590A CN103896239A CN 103896239 A CN103896239 A CN 103896239A CN 201410111590 A CN201410111590 A CN 201410111590A CN 103896239 A CN103896239 A CN 103896239A
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Abstract
The invention discloses a carbon thermal reduction method for producing lithium vanadium phosphate by using a polymer material. A metal polyanion or mixed metal polyanion compound is prepared by a wet mixing method or a dry mixing method, then is heated to remove a solvent to form a dry mixture; the mixture is heated to a temperature higher than the melting point of the polymer; and finally the sintering product is calcined and ground to obtain a lithium ion battery anode material, namely lithium vanadium phosphate. According to the carbon thermal reduction method for producing lithium vanadium phosphate by using the polymer material, the polymer is used as a raw material; the polymer can be dissolved in the solvent to form a solution which functions as a phase separation inhibitor in the wet mixing or dry mixing synthesis method so as to form a conductive network in lithium vanadium phosphate; the produced material has high electrical conductivity, excellent cycle life and relatively high reversible capacity.
Description
Technical field
The scale operation that the present invention relates to a kind of electroactive material phosphoric acid vanadium lithium is synthetic, relates in particular to a kind of carbothermic reduction method that uses polymer materials to produce phosphoric acid vanadium lithium.
Background technology
Along with portable electric appts, the fast development in power and energy storage field, also constantly increases the demand of heavy body, high-durability, long-life batteries.Therefore alkali metal battery, particularly lithium ion battery have become desirable energy derive.
At present, by polyanion (SiO
4)
n-, (PO
4)
n-, (AsO
4)
n-three-dimensional structure compound Deng composition is considered to as LiM
xo
ythe desirable surrogate of oxide electrode material.A series of this materials are at United States Patent (USP) 6,528, and in 003 B1, (Barker et al.) obtained disclosure, and the method is by V
2o
5, Li
2cO
3, (NH
4)
2hPO
4ball milling together with carbon; Again ground powder is carried out to granulation; Add hot particle to remove CO at 300 DEG C
2and NH
3; New particle is heated and is incubated at 850 DEG C and within 8 hours, make electrochemical activity product.These compounds have general formula Li
amI
bmII
c(PO
4)
d, MI and MII can be the same or different.MI can be one or more metals in the group of Fe, Co, Ni, Mn, Cu, V, Sn, Ti, Cr composition.MII is one or more metals in the group of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be composition.This polyanion material more specifically example comprises olivine structural compound, as LiMPO
4, M is Mn, Fe, Co, Cr etc. here.The example of other polyanion material also has NASICON structural compounds, as Li
3m
2(PO
4)
3.At present, a series of polyanionic compounds with this crystal lattice structure, as transition metal and hybrid metal phosphoric acid salt are developed.These transition metal and hybrid metal phosphoric acid salt are intercalation compounds, and compared with lithium-transition metal composite oxide material, it is stable that phosphoric acid salt positive electrode material generally has crystalline structure, Heat stability is good, the outstanding advantages of safety performance excellence.
In these phosphate cathode materials, there is chemical general formula Li
3v
2(PO
4)
3phosphoric acid vanadium lithium be a kind of up-and-coming lithium ion battery material.It has Stability Analysis of Structures, and heavy body (197 mAh/g), the feature of high-voltage (4.3 V).Although this material can be used as electrochemical active material for the manufacture of electrode, the research to this material at present might not be most economical effective in large-scale industrial production.Laboratory scale synthetic method, is often difficult to implement in the production of mass-producing.
summary of the invention:
Technical problem to be solved by this invention is, a kind of carbothermic reduction method that uses polymer materials to produce phosphoric acid vanadium lithium is provided, and the material that the method is produced has high specific conductivity, remarkable cycle life and higher reversible capacity.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions: a kind of carbothermic reduction method that uses polymer materials to produce phosphoric acid vanadium lithium, comprises the following steps:
A, first by wet-mixed method, polymer materials is joined in solvent, and constantly stir until polymer dissolution, time is 10min to 5h, then add polyanionic compound material and constantly stir and form mixture, then mixture is proceeded to stir, time is 2min to 5h, subsequently metal ion materials is joined in mixture, and stirs 2min to 5h and obtain mixture paste; Or by being dry mixed method, polymer materials, solvent, polyanion source or alkali metal polysilicate negative ion source carbon source and at least one metal ion source are mixed into mixed slurry, mixing time is 4min～16h, preferably 30min～2h; Said mixture slurry is heated under the condition that is greater than solvent boiling point, solvent is volatilized completely, obtain dry mixture;
B, dry mixture is ground or milled, the time is 4～24h, further to obtain mixed uniformly fine particle;
C, to grind or mill after mixture under inert atmosphere, heat, the heating of described mixture can be divided into two steps, the first step Heating temperature is at 300～400 DEG C, be 1～4h heating period, temperature rise rate is 2 DEG C/min; Second step Heating temperature is at 800～1000 DEG C, and be 2～10h heat-up time, and temperature rise rate is 2～5 DEG C/min, generates cathode material for lithium ion battery phosphoric acid vanadium lithium, and its chemical general formula can be expressed as metal polyanionic compound L i
3v
2(PO
4)
3or hybrid metal polyanionic compound Li
3v
2-xm
x(PO
4)
3;
D, the metal polyanionic compound of above-mentioned production or hybrid metal polyanionic compound product are cooled to room temperature under given pace, the product obtaining is with hammer type crushing crusher machine, and screening, obtaining required powdered material, described rate of cooling is at 2～3 DEG C/min.
Preferably, the solvent in described steps A is a kind of or its mixture in water, deionized water, ethanol, acetone, ethylene glycol, Virahol, PC, BC, DMF, DME, THF, BL, NMP, DMSO, and the boiling point of this solvent is between 50～300 DEG C.
Preferably, the polymer materials in described steps A is by enough few elementary composition organic materialss of carbon, oxygen, hydrogen and other, the preferred PEO of this organic materials, PEG and EHEC, and the addition of described polymer materials accounts for 3～12% of total reactant weight.
Preferably, in mixture in described steps A, be added with carbon source, described carbon source is the mixture of inorganic carbon or organic precursor material or inorganic carbon and organic precursor material, described inorganic carbon is carbon black, graphite, acetylene black and gac, described organic precursor material includes but not limited to coke, organic carbon hydrogen compound, alcohol, ester class, ketone, carboxylic acid, sulfonate, ethers, carbohydrate, carbohydrate and polymkeric substance, and its add-on accounts for 1～12% of total reactant weight.
Preferably, in the mixture in described steps A, contain the compound of at least one basic metal Li, should from Quilonum Retard, lithium hydroxide, monometallic and composition thereof, choose containing the compound of Li.
Preferably, the polyanionic compound in described steps A is containing PO
4 3-compound, should be containing PO
4 3-compound from DAP, ammonium di-hydrogen phosphate, monometallic and composition thereof, choose.
Preferably, in described steps A, metal ion is the compound that comes from V, should be V containing the raw material of a metal ion species V
2o
3, V
2o
5, NH
4vO
3in a kind of or its mixture.
Preferably, be added with the second metal ion materials in described steps A, it is a kind of or its metallic compound in Fe, Co, Cr, Mn, Mg, Ti, Al, Ca.
Preferably, the type of heating in described steps A is that continuous spraying is dried with belt drying or step rake is dry and bipyramid combination drying.
Preferably, the inert atmosphere in described step C is nitrogen or argon gas.
Compared with prior art, usefulness of the present invention is: this use polymer materials is produced the carbothermic reduction method polymkeric substance of phosphoric acid vanadium lithium as raw material, this polymkeric substance can form solution with solvent, in wet mixing or the synthetic method that is dry mixed, play phase separation inhibitor, between phosphoric acid vanadium lithium, form conductive network, the material of its production has high specific conductivity, the cycle life of brilliance and higher reversible capacity.
brief description of the drawings:
Below in conjunction with accompanying drawing, the present invention is further described.
Fig. 1 is the size distribution curve of the embodiment of the present invention 1 prepared phosphoric acid vanadium lithium;
Fig. 2 is the XRD curve of the embodiment of the present invention 1 prepared phosphoric acid vanadium lithium;
Fig. 3 is the different multiplying charging and discharging curve of the embodiment of the present invention 1 prepared phosphoric acid vanadium lithium;
Fig. 4 is the cycle performance curve of the prepared phosphoric acid vanadium lithium of the embodiment of the present invention 1 at 2.5V～4.6V;
Fig. 5 is the SEM figure of the embodiment of the present invention 1 prepared phosphoric acid vanadium lithium.
embodiment:
Describe the present invention below in conjunction with the drawings and specific embodiments.
Embodiment 1:
Select polymer materials and conductive carbon black Super P is carbon source simultaneously, prepares chemical formula as Li taking wet-mixed
3v
2(PO
4)
3electrode active material.
Polyoxyethylene PEO (1.8Kg, molecular weight 20000) joins (100Kg) in deionized water, stirs, and obtains solution A.LiH
2pO
4(100Kg) join in solution A, obtain slurry B.V
2o
5(57.74Kg) join mix and blend in slurry B, obtain slurry C.Again conductive carbon black Super-P (4.8Kg) is joined in slurry C, obtain slurry D.Slurry D heats 12 hours at 110 DEG C, obtains drying composite.
Drying composite was milled after 12 hours, and ball milling 12 hours under nitrogen atmosphere (or argon atmospher) protection, is warmed up to 400 DEG C with the speed of 3 DEG C of per minutes, thermal treatment 2 hours subsequently; Be warmed up to 900 DEG C with the speed of 5 DEG C of per minutes again, thermal treatment 8 hours; Last cool to room temperature.The product obtaining is with hammer type crushing crusher machine, and screening, obtains the powdered material that particle size is less than 40 microns.
Embodiment 2:
It is Li that wet-mixed is prepared chemical formula
3v
2(PO
4)
3electrode active material.
Polyoxyethylene glycol (8Kg, molecular weight 1000), polyoxyethylene PEO (0.4Kg) and deionized water (72Kg) mix and blend, obtain solution A.LiH
2pO
4(80Kg) join mix and blend in solution A, obtain slurry B.V
2o
5(46.19Kg) join mix and blend in slurry B, obtain slurry C.Slurry C heats 12 hours at 110 DEG C, obtains drying composite.
Drying composite was milled after 12 hours, and ball milling 12 hours under nitrogen atmosphere (or argon atmospher) protection, is warmed up to 400 DEG C with the speed of 3 DEG C of per minutes, thermal treatment 2 hours subsequently; Be warmed up to 900 DEG C with the speed of 5 DEG C of per minutes again, thermal treatment 8 hours; Last cool to room temperature.The product obtaining is with hammer type crushing crusher machine, and screening, obtains the powdered material that particle size is less than 40 microns.
Embodiment 3:
It is Li that dry mix is prepared chemical formula
3v
2(PO
4)
3electrode active material.
LiH
2pO
4(100Kg) and V
2o
5(57.33Kg) mix, mix with polyoxyethylene PEO (20Kg, molecular weight 20000) subsequently.Mixture is with V-mixer and Norta mixing machine mix and blend, the fine particle being uniformly mixed.Mixture heats 12 hours at 110 DEG C, obtains drying composite.
Drying composite ball milling 4 hours, under nitrogen atmosphere (or argon atmospher) protection, is warmed up to 400 DEG C with the speed of 3 DEG C of per minutes, thermal treatment 2 hours subsequently; Be warmed up to 900 DEG C with the speed of 5 DEG C of per minutes again, thermal treatment 8 hours; Last cool to room temperature.The product obtaining is with hammer type crushing crusher machine, and screening, obtains the powdered material that particle size is less than 40 microns.
Embodiment 4:
Select polymer materials and conductive carbon black Super P is carbon source simultaneously, prepares chemical formula as Li taking dry mix
3v
2(PO
4)
3electrode active material
LiH
2pO
4(100Kg) and V
2o
5(57.33Kg) mix, subsequently with polyoxyethylene PEO (20Kg, molecular weight 20000) mix, then with conductive carbon black Super P(1.44Kg) mix.Mixture is with V-mixer and Norta mixing machine mix and blend, the fine particle being uniformly mixed.Mixture heats 12 hours at 110 DEG C, obtains drying composite.
Drying composite ball milling 4 hours, under nitrogen atmosphere (or argon atmospher) protection, is warmed up to 400 DEG C with the speed of 3 DEG C of per minutes, thermal treatment 2 hours subsequently; Be warmed up to 900 DEG C with the speed of 5 DEG C of per minutes again, thermal treatment 8 hours; Last cool to room temperature.The product obtaining is with hammer type crushing crusher machine, and screening, obtains the powdered material that particle size is less than 40 microns.
Embodiment 5:
Select polymer materials Type 3U EHEC, prepare chemical formula as Li taking wet-mixed
3v
2(PO
4)
3electrode active material
Type 3U EHEC (8Kg, molecular weight 1000) and deionized water (72Kg) mix and blend, obtain solution A.LiH
2pO
4(80Kg) join mix and blend in solution A, obtain slurry B.V
2o
5(46.89Kg) join mix and blend in slurry B, obtain slurry C.Slurry C heats 12 hours at 110 DEG C, obtains drying composite.
Drying composite was milled after 12 hours, and ball milling 12 hours under nitrogen atmosphere (or argon atmospher) protection, is warmed up to 400 DEG C with the speed of 3 DEG C of per minutes, thermal treatment 2 hours subsequently; Be warmed up to 900 DEG C with the speed of 5 DEG C of per minutes again, thermal treatment 8 hours; Last cool to room temperature.The product obtaining is with hammer type crushing crusher machine, and screening, obtains the powdered material that particle size is less than 40 microns.
Embodiment 6:
Select polymer materials polyoxyethylene glycol PEG, prepare chemical formula as Li taking wet-mixed
3v
2(PO
4)
3electrode active material
Polyoxyethylene glycol PEG (10Kg) and deionized water (90Kg) mix and blend, obtain solution A.LiH
2pO
4(100Kg) join mix and blend in solution A, obtain slurry B.V
2o
5(57.74Kg) join mix and blend in slurry B, obtain slurry C.Slurry C heats 12 hours at 110 DEG C, obtains drying composite.
Drying composite was milled after 12 hours, and ball milling 12 hours under nitrogen atmosphere (or argon atmospher) protection, is warmed up to 400 DEG C with the speed of 3 DEG C of per minutes, thermal treatment 2 hours subsequently; Be warmed up to 900 DEG C with the speed of 5 DEG C of per minutes again, thermal treatment 8 hours; Last cool to room temperature.The product obtaining is with hammer type crushing crusher machine, and screening, obtains the powdered material that particle size is less than 40 microns.
Embodiment 7:
Select polymer materials and conductive carbon black Super P is carbon source simultaneously, prepares chemical formula as Li taking wet-mixed
3v
2(PO
4)
3electrode active material
Polyoxyethylene PEO (1.8Kg, molecular weight 20000) joins (100Kg) in deionized water, stirs, and obtains solution A.LiH
2pO
4(100Kg) join in solution A, obtain slurry B.V
2o
3(47.58Kg) join mix and blend in slurry B, obtain slurry C.Again conductive carbon black Super-P (4.8Kg) is joined in slurry C, obtain slurry D.Slurry D heats 12 hours at 110 DEG C, obtains drying composite.
Drying composite was milled after 12 hours, and ball milling 12 hours under nitrogen atmosphere (or argon atmospher) protection, is warmed up to 400 DEG C with the speed of 3 DEG C of per minutes, thermal treatment 2 hours subsequently; Be warmed up to 900 DEG C with the speed of 5 DEG C of per minutes again, thermal treatment 8 hours; Last cool to room temperature.The product obtaining is with hammer type crushing crusher machine, and screening, obtains the powdered material that particle size is less than 40 microns.
Embodiment 8:
Select polymer materials and conductive carbon black Super P is carbon source simultaneously, prepares chemical formula as Li taking wet-mixed
3v
2(PO
4)
3electrode active material
Polyoxyethylene PEO (1.8Kg, molecular weight 20000) joins (100Kg) in deionized water, stirs, and obtains solution A.LiH
2pO
4(100Kg) join in solution A, obtain slurry B.NH
4vO
3(74.27Kg) join mix and blend in slurry B, obtain slurry C.Again conductive carbon black Super-P (4.8Kg) is joined in slurry C, obtain slurry D.Slurry D heats 12 hours at 110 DEG C, obtains drying composite.
Drying composite was milled after 12 hours, and ball milling 12 hours under nitrogen atmosphere (or argon atmospher) protection, is warmed up to 400 DEG C with the speed of 3 DEG C of per minutes, thermal treatment 2 hours subsequently; Be warmed up to 900 DEG C with the speed of 5 DEG C of per minutes again, thermal treatment 8 hours; Last cool to room temperature.The product obtaining is with hammer type crushing crusher machine, and screening, obtains the powdered material that particle size is less than 40 microns.
Embodiment 9:
Select polymer materials and conductive carbon black Super P is carbon source simultaneously, prepares chemical formula as Li taking wet-mixed
3v
1.98cr
0.02(PO
4)
3electrode active material
Polyoxyethylene PEO (1.8Kg, molecular weight 20000) joins (100Kg) in deionized water, stirs, and obtains solution A.LiH
2pO
4(100Kg) join in solution A, obtain slurry B.V
2o
5(57.16Kg) and Cr (CH
3cOO)
36H
2o (2.10Kg) joins mix and blend in slurry B, obtains slurry C.Again conductive carbon black Super-P (4.8Kg) is joined in slurry C, obtain slurry D.Slurry D heats 12 hours at 110 DEG C, obtains drying composite.
Drying composite was milled after 12 hours, and ball milling 12 hours under nitrogen atmosphere (or argon atmospher) protection, is warmed up to 400 DEG C with the speed of 3 DEG C of per minutes, thermal treatment 2 hours subsequently; Be warmed up to 900 DEG C with the speed of 5 DEG C of per minutes again, thermal treatment 8 hours; Last cool to room temperature.The product obtaining is with hammer type crushing crusher machine, and screening, obtains the powdered material that particle size is less than 40 microns.
As shown in Figures 1 to 5, this use polymer materials is produced the carbothermic reduction method polymkeric substance of phosphoric acid vanadium lithium as raw material, this polymkeric substance can form solution with solvent, in wet mixing or the synthetic method that is dry mixed, play phase separation inhibitor, between phosphoric acid vanadium lithium, form conductive network, the material of its production has high specific conductivity, the cycle life of brilliance and higher reversible capacity.
It is emphasized that: be only preferred embodiment of the present invention above, not the present invention is done to any pro forma restriction, any simple modification, equivalent variations and modification that every foundation technical spirit of the present invention is done above embodiment, all still belong in the scope of technical solution of the present invention.
Claims (10)
1. use polymer materials to produce a carbothermic reduction method for phosphoric acid vanadium lithium, it is characterized in that, comprise the following steps:
A, first by wet-mixed method, polymer materials is joined in solvent, and constantly stir until polymer dissolution, time is 10min to 5h, then add polyanionic compound material and constantly stir and form mixture, then mixture is proceeded to stir, time is 2min to 5h, subsequently metal ion materials is joined in mixture, and stirs 2min to 5h and obtain mixture paste; Or by being dry mixed method, polymer materials, solvent, polyanion source or alkali metal polysilicate negative ion source carbon source and at least one metal ion source are mixed into mixed slurry, mixing time is 4min～16h, preferably 30min～2h; Said mixture slurry is heated under the condition that is greater than solvent boiling point, solvent is volatilized completely, obtain dry mixture;
B, dry mixture is ground or milled, the time is 4～24h, further to obtain mixed uniformly fine particle;
C, to grind or mill after mixture under inert atmosphere, heat, the heating of described mixture can be divided into two steps, the first step Heating temperature is at 300～400 DEG C, be 1～4h heating period, temperature rise rate is 2 DEG C/min; Second step Heating temperature is at 800～1000 DEG C, and be 2～10h heat-up time, and temperature rise rate is 2～5 DEG C/min, generates cathode material for lithium ion battery phosphoric acid vanadium lithium, and its chemical general formula can be expressed as metal polyanionic compound L i
3v
2(PO
4)
3or hybrid metal polyanionic compound Li
3v
2-xm
x(PO
4)
3;
D, the metal polyanionic compound of above-mentioned production or hybrid metal polyanionic compound product are cooled to room temperature under given pace, the product obtaining is with hammer type crushing crusher machine, and screening, obtaining required powdered material, described rate of cooling is at 2～3 DEG C/min.
2. use polymer materials according to claim 1 is produced the carbothermic reduction method of phosphoric acid vanadium lithium, it is characterized in that, solvent in described steps A is a kind of or its mixture in water, deionized water, ethanol, acetone, ethylene glycol, Virahol, PC, BC, DMF, DME, THF, BL, NMP, DMSO, and the boiling point of this solvent is between 50～300 DEG C.
3. use polymer materials according to claim 1 is produced the carbothermic reduction method of phosphoric acid vanadium lithium, it is characterized in that, polymer materials in described steps A is by enough few elementary composition organic materialss of carbon, oxygen, hydrogen and other, the preferred PEO of this organic materials, PEG and EHEC, and the addition of described polymer materials accounts for 3～12% of total reactant weight.
4. use polymer materials according to claim 1 is produced the carbothermic reduction method of phosphoric acid vanadium lithium, it is characterized in that, in mixture in described steps A, be added with carbon source, described carbon source is the mixture of inorganic carbon or organic precursor material or inorganic carbon and organic precursor material, described inorganic carbon is carbon black, graphite, acetylene black and gac, described organic precursor material includes but not limited to coke, organic carbon hydrogen compound, alcohol, ester class, ketone, carboxylic acid, sulfonate, ethers, carbohydrate, carbohydrate and polymkeric substance, its add-on accounts for 1～12% of total reactant weight.
5. use polymer materials according to claim 1 is produced the carbothermic reduction method of phosphoric acid vanadium lithium, it is characterized in that, in mixture in described steps A, contain the compound of at least one basic metal Li, should from Quilonum Retard, lithium hydroxide, monometallic and composition thereof, choose containing the compound of Li.
6. use polymer materials according to claim 1 is produced the carbothermic reduction method of phosphoric acid vanadium lithium, it is characterized in that, the polyanionic compound in described steps A is containing PO
4 3-compound, should be containing PO
4 3-compound from DAP, ammonium di-hydrogen phosphate, monometallic and composition thereof, choose.
7. use polymer materials according to claim 1 is produced the carbothermic reduction method of phosphoric acid vanadium lithium, it is characterized in that, in described steps A, metal ion is the compound that comes from V, should be V containing the raw material of a metal ion species V
2o
3, V
2o
5, NH
4vO
3in a kind of or its mixture.
8. use polymer materials according to claim 1 is produced the carbothermic reduction method of phosphoric acid vanadium lithium, it is characterized in that, in described steps A, be added with the second metal ion materials, it is a kind of or its metallic compound in Fe, Co, Cr, Mn, Mg, Ti, Al, Ca.
9. use polymer materials according to claim 1 is produced the carbothermic reduction method of phosphoric acid vanadium lithium, it is characterized in that, the type of heating in described steps A is that continuous spraying is dried with belt drying or step rake is dry and bipyramid combination drying.
10. use polymer materials according to claim 1 is produced the carbothermic reduction method of phosphoric acid vanadium lithium, it is characterized in that, the inert atmosphere in described step C is nitrogen or argon gas.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105655567A (en) * | 2016-04-14 | 2016-06-08 | 天津巴莫科技股份有限公司 | Lithium vanadium phosphate/lithium cobalt oxide composite material and preparation method thereof |
| CN111742432A (en) * | 2018-02-27 | 2020-10-02 | Tdk株式会社 | Active material and all-solid-state secondary battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101803078A (en) * | 2007-08-01 | 2010-08-11 | 威伦斯技术公司 | Synthesis of cathode active materials |
-
2014
- 2014-03-25 CN CN201410111590.5A patent/CN103896239A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101803078A (en) * | 2007-08-01 | 2010-08-11 | 威伦斯技术公司 | Synthesis of cathode active materials |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105655567A (en) * | 2016-04-14 | 2016-06-08 | 天津巴莫科技股份有限公司 | Lithium vanadium phosphate/lithium cobalt oxide composite material and preparation method thereof |
| CN105655567B (en) * | 2016-04-14 | 2018-10-02 | 天津巴莫科技股份有限公司 | Phosphoric acid vanadium lithium/cobalt-lithium oxide composite material and preparation method |
| CN111742432A (en) * | 2018-02-27 | 2020-10-02 | Tdk株式会社 | Active material and all-solid-state secondary battery |
| CN111742432B (en) * | 2018-02-27 | 2024-04-16 | Tdk株式会社 | Active material and all-solid secondary battery |
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Application publication date: 20140702 |