CN102509804A - Preparation method for lithium ion battery Li3V2 (Po4)3/C composite material - Google Patents
Preparation method for lithium ion battery Li3V2 (Po4)3/C composite material Download PDFInfo
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- CN102509804A CN102509804A CN2011103578147A CN201110357814A CN102509804A CN 102509804 A CN102509804 A CN 102509804A CN 2011103578147 A CN2011103578147 A CN 2011103578147A CN 201110357814 A CN201110357814 A CN 201110357814A CN 102509804 A CN102509804 A CN 102509804A
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- gained
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Links
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 229910001352 Li3V2(PO4)3/C Inorganic materials 0.000 title abstract 2
- 239000008139 complexing agent Substances 0.000 claims abstract description 23
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- 239000004471 Glycine Substances 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 4
- 239000001116 FEMA 4028 Substances 0.000 abstract description 3
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 229920000858 Cyclodextrin Polymers 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 abstract 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 abstract 1
- 229960004853 betadex Drugs 0.000 abstract 1
- 230000005518 electrochemistry Effects 0.000 abstract 1
- DMEJJWCBIYKVSB-UHFFFAOYSA-N lithium vanadium Chemical compound [Li].[V] DMEJJWCBIYKVSB-UHFFFAOYSA-N 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- ZVKRVGZVXQYLPZ-UHFFFAOYSA-N [Li].[V].P(O)(O)(O)=O Chemical compound [Li].[V].P(O)(O)(O)=O ZVKRVGZVXQYLPZ-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910013553 LiNO Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of battery material and particularly discloses a preparation method for a lithium ion battery Li3V2 (Po4) 3/C composite material. According to the invention, Beta cyclodextrin serving as a complexing agent and a silicon source is introduced in a sphoric acid vanadium Lithium system at first time; and the material adopted by the invention is mixed at the molecule level, so that the carbon-coated monocline phosphate vanadium lithium material with the advantages of small particle size, uniform distribution, and excellent electrochemistry property, can be compounded at a lower sintering temperature and a shorter sintering time.
Description
Technical field
The present invention relates to the battery material technical field, particularly relate to a kind of lithium ion battery Li
3V
2(PO
4)
3The preparation method of/C composite material.
Background technology
Lithium ion battery relies on the advantage of himself to be widely used in the various portable type electronic products in decades in the past.In addition, these advantages of the high power capacity of lithium ion battery, high power and environmental protection make it become the power supply that most possibly is applied in hybrid electric vehicle or the electric motor car.Fail safe is a vital factor of electric vehicle power supply.And the cobalt of lithium ion battery first generation positive electrode stratiform acid lithium (LiCoO
2) poor heat stability, be not suitable for the electric vehicle lithium ion battery.The polyanion material has good thermal stability, is considered to very promising anode material for lithium-ion batteries.And monocline phosphoric acid vanadium lithium (Li
3V
2(PO
4)
3) become the most attractive electric vehicle anode material for lithium-ion batteries because of having lithium ion diffusion coefficient and specific capacity height, discharge voltage and advantages such as energy density height, cycle performance and Heat stability is good.
Solid phase method and liquid phase method are the main method of preparation monocline phosphoric acid vanadium lithium.Liquid phase method can make raw material reach the mixing of molecular level level, and then can in lower calcining heat and short calcination time, synthesize pure phosphoric acid vanadium lithium mutually.Utilize the material particle size of liquid phase method preparation little, be evenly distributed, chemical property is good.Sol-gal process is the common liquid phase method of preparation phosphoric acid vanadium lithium, and citric acid becomes main complexing agent in this method.In addition, the electron conduction ability of monocline phosphoric acid vanadium lithium, the composite material that preparation carbon coats phosphoric acid vanadium lithium is a kind of efficient and simple method that improves this material electronics conductance.Much inorganic or organic carbon source is used in this composite material of preparation.But the multiplying power property and the cycle performance of the phosphoric acid vanadium lithium composite material that the carbon that utilizes Prepared by Sol Gel Method coats are also undesirable, and particularly the cycle performance under high magnification is still waiting to improve.
Summary of the invention
In order to address the above problem, one of the object of the invention is, a kind of lithium ion battery Li is provided
3V
2(PO
4)
3The preparation method of/C composite material, the Li that this method prepares
3V
2(PO
4)
3/ C composite material further improves the multiplying power and the cycle performance of phosphoric acid vanadium lithium.
To achieve these goals, technical scheme of the present invention is following:
A kind of lithium ion battery Li
3V
2(PO
4)
3The preparation method of/C composite material is characterized in that, comprises being prepared as follows step:
A, lithium source, vanadium source, phosphoric acid root, oxalic acid and complexing agent I beta-schardinger dextrin-are dissolved in deionized water under mechanical agitation, form solution I, wherein calculate n according to amount of substance
Li: n
V: n
PO4-=3.0～3.1: 2: 3, n
V: n
Oxalic acid=1: 3～4, m
Beta-schardinger dextrin-: m
Final products=0.25～0.80;
B, in 60～80 ℃ of water-baths, solution I is stirred 0.5～2h;
C, complexing agent II is dissolved in deionized water under mechanical agitation, obtains solution II;
D, under vigorous stirring, solution II slowly is added drop-wise in the solution I, obtain solution III;
E, gained solution III in the steps d is obtained solution IV prior to reacting 2～4h in 60～80 ℃ of water-baths;
F, gained solution IV among the step e is continued to form colloidal sols 60～80 ℃ of stirred in water bath, water evaporates is obtained gel;
G, gained gel dry 4～8h in 80～120 ℃ of baking ovens obtains xerogel;
5～15min grinds with the gained xerogel in h, elder generation, under nitrogen protection, in 300～400 ℃ of pre-burning 3～6h, again the pre-burning gains is ground 5～15min, compressing tablet, and calcining 4～10h obtains Li at last under 650～850 ℃
3V
2(PO
4)
3/ C composite material.
Preferably, said lithium source is lithium hydroxide (LiOHH
2O), lithium nitrate (LiNO
3), lithium acetate (CH
3COOLi2H
2The mixture of one or several O).
Preferably, said vanadium source is vanadic oxide (V
2O
5), ammonium metavanadate (NH
4VO
3) in a kind of or two kinds mixture.
Preferably, said phosphoric acid root is phosphoric acid (H
3PO
4), ammonium dihydrogen phosphate (NH
4H
2PO
4), ammonium hydrogen phosphate ((NH
4)
2HPO
4) in one or several mixture.
Preferably, said complexing agent II is the one or more combination thing in citric acid, glycine, ascorbic acid, the tartaric acid.
This method is introduced the phosphoric acid vanadium lithium system with beta-schardinger dextrin-as complexing agent and carbon source first; The present invention can make raw material reach the mixing of molecular level, so can in lower sintering temperature and short sintering time, synthesize particle diameter little and be evenly distributed, carbon that chemical property is excellent coats monocline phosphoric acid vanadium lithium material.
On the one hand, beta-schardinger dextrin-is made up of 7 glucose molecule monomers, and the wide end of shape mouth is narrow, a similar pyramid, and the inside is the hollow volume, has particular structural and function, can form complex compound with numerous metal ions, is a kind of good complexing agent; Because beta-schardinger dextrin-is an organic substance, pyrolysis at high temperature can obtain preparing Li on the other hand
3V
2(PO
4)
3The carbon source of/C composite material.The present invention is through forming compound complex agent with beta-schardinger dextrin-and other complexing agents; Utilize the mutual supplement with each other's advantages characteristics of two kinds of complexing agents to make the metal ion in the system disperse more evenly; Can reduce the temperature of synthetic material; Shorten calcination time, so synthetic particle diameter little and be evenly distributed, material that chemical property is excellent.
Description of drawings
Fig. 1 is the prepared Li of the present invention
3V
2(PO
4)
3The cycle performance figure of/C composite material under the 20C charge-discharge magnification;
Fig. 2 is the prepared Li of the present invention
3V
2(PO
4)
3The cycle performance figure of/C composite material under 35C discharging current under the 0.7C charging current.
Embodiment
Embodiment 1
A kind of lithium ion battery Li
3V
2(PO
4)
3The preparation method of/C composite material is characterized in that, comprises being prepared as follows step:
A, with lithium hydroxide (LiOHH
2O), ammonium metavanadate (NH
4VO
3), ammonium dihydrogen phosphate (NH
4H
2PO
4), oxalic acid (H
2C
2O
42H
2O) and complexing agent I beta-schardinger dextrin-under mechanical agitation, be dissolved in the 400ml deionized water, form solution I, wherein calculate n according to amount of substance
Li: n
V: n
PO4-=3.0: 2: 3, n
V: n
Oxalic acid=1: 3, m
β-ring is stuck with paste Smart: m
Final products=0.25;
B, in 70 ℃ of water-baths, solution I is stirred 1h;
C, complexing agent II citric acid is dissolved in the 50mL deionized water under mechanical agitation, obtains solution II;
D, under vigorous stirring, solution II slowly is added drop-wise in the solution I, obtain solution III;
E, with gained solution III in the steps d prior in 70 ℃ of water-baths the reaction 4h obtain solution IV;
F, gained solution IV among the step e is continued to form colloidal sols 70 ℃ of stirred in water bath, water evaporates is obtained gel;
G, gained gel dry 6h in 100 ℃ of baking ovens obtains xerogel;
5min grinds with the gained xerogel in h, elder generation, under nitrogen protection, in 300 ℃ of pre-burning 5h, again the pre-burning gains is ground 5min, compressing tablet, and calcining 4h obtains Li at last under 750 ℃
3V
2(PO
4)
3/ C composite material.
Embodiment 2
A kind of lithium ion battery Li
3V
2(PO
4)
3The preparation method of/C composite material is characterized in that, comprises being prepared as follows step:
A, with lithium hydroxide (LiOHH
2O), ammonium metavanadate (NH
4VO
3), ammonium dihydrogen phosphate (NH
4H
2PO
4), oxalic acid (H
2C
2O
42H
2O) and complexing agent I beta-schardinger dextrin-under mechanical agitation, be dissolved in the 450ml deionized water, form solution I, wherein calculate n according to amount of substance
Li: n
V: n
PO4-=3.05: 2: 3, n
V: n
Oxalic acid=1: 3.5, m
β -cyclodextrin: m
Final products=0.3;
B, in 75 ℃ of water-baths, solution I is stirred 1h;
C, complexing agent II glycine is dissolved in the 70mL deionized water under mechanical agitation, obtains solution II;
D, under vigorous stirring, solution II slowly is added drop-wise in the solution I, obtain solution III;
E, with gained solution III in the steps d prior in 75 ℃ of water-baths the reaction 3h obtain solution IV;
F, gained solution IV among the step e is continued to form colloidal sols 80 ℃ of stirred in water bath, water evaporates is obtained gel;
G, gained gel dry 8h in 120 ℃ of baking ovens obtains xerogel;
10min grinds with the gained xerogel in h, elder generation, under nitrogen protection, in 350 ℃ of pre-burning 4h, again the pre-burning gains is ground 10min, compressing tablet, and calcining 8h obtains Li at last under 700 ℃
3V
2(PO
4)
3/ C composite material.
Embodiment 3
A kind of lithium ion battery Li
3V
2(PO
4)
3The preparation method of/C composite material is characterized in that, comprises being prepared as follows step:
A, with lithium acetate (CH
3COOLi2H
2O), vanadic oxide (V
2O
5), ammonium dihydrogen phosphate (NH
4H
2PO
4), oxalic acid (H
2C
2O
42H
2O) and complexing agent I beta-schardinger dextrin-under mechanical agitation, be dissolved in the 300ml deionized water, form solution I, wherein calculate n according to amount of substance
Li: n
V: n
PO4-=3.1: 2: 3, n
V: n
Oxalic acid=1: 4, m
Beta-schardinger dextrin-: m
Final products=0.5;
B, in 80 ℃ of water-baths, solution I is stirred 0.5h;
C, complexing agent II ascorbic acid is dissolved in the 70mL deionized water under mechanical agitation, obtains solution II;
D, under vigorous stirring, solution II slowly is added drop-wise in the solution I, obtain solution III;
E, with gained solution III in the steps d prior in 80 ℃ of water-baths the reaction 2h obtain solution IV;
F, gained solution IV among the step e is continued to form colloidal sols 80 ℃ of stirred in water bath, water evaporates is obtained gel;
G, gained gel dry 6h in 120 ℃ of baking ovens obtains xerogel;
10min grinds with the gained xerogel in h, elder generation, under nitrogen protection, in 350 ℃ of pre-burning 4h, again the pre-burning gains is ground 10min, compressing tablet, and calcining 6h obtains Li at last under 800 ℃
3V
2(PO
4)
3/ C composite material.
Embodiment 4
A kind of lithium ion battery Li
3V
2(PO
4)
3The preparation method of/C composite material is characterized in that, comprises being prepared as follows step:
A, with lithium acetate (CH
3COOLi2H
2O), vanadic oxide (V
2O
5), phosphoric acid (H
3PO
4), oxalic acid (H
2C
2O
42H
2O) and complexing agent I beta-schardinger dextrin-under mechanical agitation, be dissolved in the 350ml deionized water, form solution I, wherein calculate n according to amount of substance
Li: n
V: n
PO4-=3.05: 2: 3, n
V: n
Oxalic acid=1: 3.5, m
β -cyclodextrin: m
Final products=0.7;
B, in 70 ℃ of water-baths, solution I is stirred 1h;
C, complexing agent II ascorbic acid is dissolved in the 65mL deionized water under mechanical agitation, obtains solution II;
D, under vigorous stirring, solution II slowly is added drop-wise in the solution I, obtain solution III;
E, with gained solution III in the steps d prior in 80 ℃ of water-baths the reaction 2h obtain solution IV;
F, gained solution IV among the step e is continued to form colloidal sols 80 ℃ of stirred in water bath, water evaporates is obtained gel;
G, gained gel dry 6h in 120 ℃ of baking ovens obtains xerogel;
15min grinds with the gained xerogel in h, elder generation, under nitrogen protection, in 400 ℃ of pre-burning 3h, again the pre-burning gains is ground 15min, compressing tablet, and calcining 4h obtains Li at last under 800 ℃
3V
2(PO
4)
3/ C composite material.
A kind of lithium ion battery Li
3V
2(PO
4)
3The preparation method of/C composite material is characterized in that, comprises being prepared as follows step:
A, with lithium nitrate (LiNO
3), vanadic oxide (V
2O
5), phosphoric acid (H
3PO
4), oxalic acid (H
2C
2O
42H
2O) and complexing agent I beta-schardinger dextrin-under mechanical agitation, be dissolved in the 400ml deionized water, form solution I, wherein calculate n according to amount of substance
Li: n
V: n
PO4-=3.0: 2: 3, n
V: n
Oxalic acid=1: 3, m
Beta-schardinger dextrin-: m
Final products=0.8;
B, in 75 ℃ of water-baths, solution I is stirred 1h;
C, complexing agent II glycine is dissolved in the 70mL deionized water under mechanical agitation, obtains solution II;
D, under vigorous stirring, solution II slowly is added drop-wise in the solution I, obtain solution III;
E, with gained solution III in the steps d prior in 75 ℃ of water-baths the reaction 4h obtain solution IV;
F, gained solution IV among the step e is continued to form colloidal sols 80 ℃ of stirred in water bath, water evaporates is obtained gel;
G, gained gel dry 8h in 120 ℃ of baking ovens obtains xerogel;
10min grinds with the gained xerogel in h, elder generation, under nitrogen protection, in 350 ℃ of pre-burning 4h, again the pre-burning gains is ground 10min, compressing tablet, and calcining 6h obtains Li at last under 800 ℃
3V
2(PO
4)
3/ C composite material.
The above only is five embodiment of the present invention, should be understood that, for the person of ordinary skill of the art; Under the prerequisite that does not break away from principle of the present invention; Can also make some modifications and improvement to the present invention, so all equivalences of doing according to the described method of patent claim of the present invention, characteristic and principle change or improve; The complexing agent II that for example chooses is malic acid or maleic acid, and these characteristics belong to the scope of patent application protection of the present invention equally.
Can find out that by Fig. 1 the carbon of the present invention's preparation coats phosphoric acid vanadium lithium composite material the highest specific discharge capacity under the 20C charging and discharging currents can reach 95.2mAh g
-1, 180 times capacity does not have obvious decay.But the carbon coating phosphoric acid vanadium lithium composite material capacity under 35C discharging current under the 0.7C charging current by Fig. 2 knowledge capital invention preparation reaches as high as 87.1mAh g
-1Phosphoric acid vanadium lithium/carbon composite by the present invention preparation shows excellent cycle performance under high magnification, the method for this Prepared by Sol Gel Method monocline phosphoric acid vanadium lithium based on compound complex agent is a kind of very promising synthetic method.
Claims (5)
1. lithium ion battery Li
3V
2(PO
4)
3The preparation method of/C composite material is characterized in that, comprises being prepared as follows step:
A, lithium source, vanadium source, phosphoric acid root, oxalic acid and complexing agent I beta-schardinger dextrin-are dissolved in deionized water under mechanical agitation, form solution I, wherein calculate n according to amount of substance
Li: n
V: n
PO4-=3.0～3.1: 2: 3, n
V: n
Oxalic acid=1: 3～4, m
Beta-schardinger dextrin-: m
Final products=0.25～0.80;
B, in 60～80 ℃ of water-baths, solution I is stirred 0.5～2h;
C, complexing agent II is dissolved in deionized water under mechanical agitation, obtains solution II;
D, under vigorous stirring, solution II slowly is added drop-wise in the solution I, obtain solution III;
E, gained solution III in the steps d is obtained solution IV prior to reacting 2～4h in 60～80 ℃ of water-baths;
F, gained solution IV among the step e is continued to form colloidal sols 60～80 ℃ of stirred in water bath, water evaporates is obtained gel;
G, gained gel dry 4～8h in 80～120 ℃ of baking ovens obtains xerogel;
5～15min grinds with the gained xerogel in h, elder generation, under nitrogen protection, in 300～400 ℃ of pre-burning 3～6h, again the pre-burning gains is ground 5～15min, compressing tablet, and calcining 4～10h obtains Li at last under 650～850 ℃
3V
2(PO
4)
3/ C composite material.
2. according to the said Li of claim 1
3V
2(PO
4)
3The preparation method of/C composite material is characterized in that, said lithium source is one or several the mixture in lithium hydroxide, lithium nitrate, the lithium acetate.
3. according to the said Li of claim 1
3V
2(PO
4)
3The preparation method of/C composite material is characterized in that, said vanadium source is the mixture of a kind of in vanadic oxide, the ammonium metavanadate or two kinds.
4. according to the said Li of claim 1
3V
2(PO
4)
3The preparation method of/C composite material is characterized in that, said phosphoric acid root is one or several the mixture in phosphoric acid, ammonium dihydrogen phosphate, the ammonium hydrogen phosphate.
5. according to the said Li of claim 1
3V
2(PO
4)
3The preparation method of/C composite material is characterized in that, said complexing agent II is the one or more combination thing in citric acid, glycine, ascorbic acid, the tartaric acid.
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| CN103682275A (en) * | 2013-12-24 | 2014-03-26 | 中南大学 | Preparation method for LiVOPO4-Li3V2(PO4 )3 composite cathode material of lithium ion battery |
| CN104167548A (en) * | 2014-06-04 | 2014-11-26 | 上海电力学院 | Positive electrode material of lithium ion battery, and preparation method thereof |
| CN104638228A (en) * | 2015-02-04 | 2015-05-20 | 武汉理工大学 | Coaxial carbon-coated bunchy vanadium potassium phosphate nanowire, as well as preparation method and application of nanowire |
| CN105655582A (en) * | 2016-02-05 | 2016-06-08 | 北京理工大学 | Method for coating and modifying lithium vanadium phosphate positive pole material with novel carbon source |
| CN108598473A (en) * | 2018-04-24 | 2018-09-28 | 电子科技大学 | Anion doped high-voltage charge and discharge vanadium phosphate cathode material and preparation method thereof |
| CN110504422A (en) * | 2019-07-29 | 2019-11-26 | 全球能源互联网研究院有限公司 | A kind of cell positive material and preparation method thereof |
| CN113328071A (en) * | 2021-05-14 | 2021-08-31 | 昆明理工大学 | Lithium vanadium phosphate/carbon battery positive electrode material and preparation method thereof |
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| CN103682275B (en) * | 2013-12-24 | 2016-03-02 | 中南大学 | Lithium ion battery composite cathode material vanadyl phosphate lithium-phosphoric acid vanadium lithium preparation method |
| CN104167548B (en) * | 2014-06-04 | 2017-02-15 | 上海电力学院 | Positive electrode material of lithium ion battery, and preparation method thereof |
| CN104167548A (en) * | 2014-06-04 | 2014-11-26 | 上海电力学院 | Positive electrode material of lithium ion battery, and preparation method thereof |
| CN104638228B (en) * | 2015-02-04 | 2017-03-22 | 武汉理工大学 | Coaxial carbon-coated bunchy vanadium potassium phosphate nanowire, as well as preparation method and application of nanowire |
| CN104638228A (en) * | 2015-02-04 | 2015-05-20 | 武汉理工大学 | Coaxial carbon-coated bunchy vanadium potassium phosphate nanowire, as well as preparation method and application of nanowire |
| CN105655582A (en) * | 2016-02-05 | 2016-06-08 | 北京理工大学 | Method for coating and modifying lithium vanadium phosphate positive pole material with novel carbon source |
| CN108598473A (en) * | 2018-04-24 | 2018-09-28 | 电子科技大学 | Anion doped high-voltage charge and discharge vanadium phosphate cathode material and preparation method thereof |
| CN110504422A (en) * | 2019-07-29 | 2019-11-26 | 全球能源互联网研究院有限公司 | A kind of cell positive material and preparation method thereof |
| CN110504422B (en) * | 2019-07-29 | 2021-10-15 | 全球能源互联网研究院有限公司 | Battery positive electrode material and preparation method thereof |
| CN113328071A (en) * | 2021-05-14 | 2021-08-31 | 昆明理工大学 | Lithium vanadium phosphate/carbon battery positive electrode material and preparation method thereof |
| CN113328071B (en) * | 2021-05-14 | 2023-04-18 | 昆明理工大学 | Lithium vanadium phosphate/carbon battery positive electrode material and preparation method thereof |
| CN113845152A (en) * | 2021-08-30 | 2021-12-28 | 蜂巢能源科技有限公司 | Lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery |
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