CN102509804B - 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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- CN102509804B CN102509804B CN201110357814.7A CN201110357814A CN102509804B CN 102509804 B CN102509804 B CN 102509804B CN 201110357814 A CN201110357814 A CN 201110357814A CN 102509804 B CN102509804 B CN 102509804B
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- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910001352 Li3V2(PO4)3/C Inorganic materials 0.000 title claims abstract description 9
- 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 21
- 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
- 238000003756 stirring Methods 0.000 claims description 9
- 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
- 230000008020 evaporation Effects 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 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
- 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-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 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
- 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 description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 229920000858 Cyclodextrin Polymers 0.000 abstract 1
- 239000001116 FEMA 4028 Substances 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 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 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
- 238000000034 method Methods 0.000 description 13
- 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 8
- 239000000047 product Substances 0.000 description 7
- 238000001354 calcination Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910013553 LiNO Inorganic materials 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
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 108010022579 ATP dependent 26S protease Proteins 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
- -1 and in this method Chemical compound 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000008859 change Effects 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
- 239000007788 liquid Substances 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
- 239000012071 phase Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 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
Images
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
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 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 various portable type electronic products in the past few decades.In addition, these advantages of the high power capacity of lithium ion battery, high power and environmental protection become the power supply being most possibly applied in hybrid electric vehicle or 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 lithium ion battery for electric vehicle.Polyanion material has good thermal stability, is considered to very promising anode material for lithium-ion batteries.And monoclinic lithium vanadium phosphate (Li
3v
2(PO
4)
3) because having, lithium ion diffusion coefficient and specific capacity are high, discharge voltage and the advantage such as energy density is high, cycle performance and Heat stability is good become the most attractive lithium ion battery for electric vehicle positive electrode.
Solid phase method and liquid phase method are the main method of preparing monoclinic lithium vanadium phosphate.Liquid phase method can make raw material reach the mixing of molecular level level, and then can in lower calcining heat and shorter calcination time, synthesize the phosphoric acid vanadium lithium of pure phase.Utilize the material particle size of Liquid preparation methods little, be evenly distributed, chemical property is good.Sol-gal process is the common liquid phase method of preparing phosphoric acid vanadium lithium, and in this method, citric acid becomes main complexing agent.In addition, the electron conduction ability of monoclinic lithium vanadium phosphate, the composite material of preparing the coated phosphoric acid vanadium lithium of carbon is the effectively method of one that improves this material electronics conductance.In this composite material of preparation, much inorganic or organic carbon source is used.But multiplying power property and the cycle performance of the coated phosphoric acid vanadium lithium composite material of the carbon that utilizes sol-gal process to prepare are also undesirable, particularly the cycle performance under high magnification need to improve.
Summary of the invention
In order to address the above problem, one of object of the present 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 the method prepares
3v
2(PO
4)
3/ C composite material further improves multiplying power and the cycle performance of phosphoric acid vanadium lithium.
To achieve these goals, technical scheme of the present invention is as follows:
A kind of lithium ion battery Li
3v
2(PO
4)
3the preparation method of/C composite material, is characterized in that, comprises and is prepared as follows step:
A, lithium source, vanadium source, phosphoric acid root, oxalic acid and complexing agent I beta-schardinger dextrin-are dissolved in to deionized water under mechanical agitation, form solution I, wherein according to amount of substance, calculate n
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, by solution I stir 0.5～2h;
C, complexing agent II is dissolved in to deionized water under mechanical agitation, obtains solution II;
D, under vigorous stirring, solution II is slowly added drop-wise in solution I, obtain solution III;
E, gained solution III in steps d is obtained to solution IV prior to reacting 2～4h in 60～80 ℃ of water-baths;
F, gained solution IV in step e is continued to form colloidal sols 60～80 ℃ of stirred in water bath, moisture evaporation is obtained to gel;
G, gained gel dry 4～8h in 80～120 ℃ of baking ovens obtains xerogel;
H, first gained xerogel is ground to 5～15min, under nitrogen protection, in 300～400 ℃ of pre-burning 3～6h, then pre-burning gains are ground to 5～15min, compressing tablet, at 650～850 ℃, calcine 4～10h, finally obtain Li
3v
2(PO
4)
3/ C composite material.
Preferably, described lithium source is lithium hydroxide (LiOHH
2o), lithium nitrate (LiNO
3), lithium acetate (CH
3cOOLi2H
2the mixture of one or several O).
Preferably, described vanadium source is vanadic oxide (V
2o
5), ammonium metavanadate (NH
4vO
3) in a kind of or mixture of two kinds.
Preferably, described 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, described complexing agent II is the one or more combination thing in citric acid, glycine, ascorbic acid, tartaric acid.
The method first using beta-schardinger dextrin-as complexing agent and carbon source introduce phosphoric acid vanadium lithium system, the present invention can make raw material reach the mixing of molecular level, so can in lower sintering temperature and shorter sintering time, synthesize particle diameter little and be evenly distributed, the coated monoclinic lithium vanadium phosphate material of carbon of chemical property excellence.
On the one hand, beta-schardinger dextrin-is by 7 glucose molecule monomer compositions, and the wide end of shape mouth is narrow, a similar pyramid, and the inside is hollow volume, has special 26S Proteasome Structure and Function, can form complex compound with numerous metal ions, is a kind of good complexing agent; Because beta-schardinger dextrin-is organic substance, at high temperature pyrolysis can obtain preparing Li on the other hand
3v
2(PO
4)
3the carbon source of/C composite material.The present invention is by forming compound complex agent by beta-schardinger dextrin-and other complexing agents, utilize the mutual supplement with each other's advantages feature of two kinds of complexing agents to make the metal ion in system disperse more evenly, can reduce the temperature of synthetic material, shorten calcination time, so synthetic particle diameter little and be evenly distributed, the material of chemical property excellence.
Accompanying drawing explanation
Fig. 1 is the prepared Li of the present invention
3v
2(PO
4)
3the cycle performance figure of/C composite material under 20C charge-discharge magnification;
Fig. 2 is the prepared Li of the present invention
3v
2(PO
4)
3/ C composite material is the cycle performance figure under 35C discharging current under 0.7C charging current.
Embodiment
A kind of lithium ion battery Li
3v
2(PO
4)
3the preparation method of/C composite material, is characterized in that, comprises and is prepared as follows step:
A, by 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 400ml deionized water, form solution I, wherein according to amount of substance calculate, n
li: n
v: n
pO4-=3.0: 2: 3, n
v: n
oxalic acid=1: 3, m
beta-schardinger dextrin-: m
final products=0.25;
B, in 70 ℃ of water-baths, solution I is stirred to 1h;
C, complexing agent II citric acid is dissolved in to 50mL deionized water under mechanical agitation, obtains solution II;
D, under vigorous stirring, solution II is slowly added drop-wise in solution I, obtain solution III;
E, gained solution III in steps d is obtained to solution IV prior to reacting 4h in 70 ℃ of water-baths;
F, gained solution IV in step e is continued to form colloidal sols 70 ℃ of stirred in water bath, moisture evaporation is obtained to gel;
G, gained gel dry 6h in 100 ℃ of baking ovens obtains xerogel;
H, first gained xerogel is ground to 5min, under nitrogen protection, in 300 ℃ of pre-burning 5h, then pre-burning gains are ground to 5min, compressing tablet, at 750 ℃, calcine 4h, finally obtain Li
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 and is prepared as follows step:
A, by 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 450ml deionized water, form solution I, wherein according to amount of substance calculate, n
li: n
v: n
pO4-=3.05: 2: 3, n
v: n
oxalic acid=1: 3.5, m
beta-schardinger dextrin-: m
final products=0.3;
B, in 75 ℃ of water-baths, solution I is stirred to 1h;
C, complexing agent II glycine is dissolved in to 70mL deionized water under mechanical agitation, obtains solution II;
D, under vigorous stirring, solution II is slowly added drop-wise in solution I, obtain solution III;
E, gained solution III in steps d is obtained to solution IV prior to reacting 3h in 75 ℃ of water-baths;
F, gained solution IV in step e is continued to form colloidal sols 80 ℃ of stirred in water bath, moisture evaporation is obtained to gel;
G, gained gel dry 8h in 120 ℃ of baking ovens obtains xerogel;
H, first gained xerogel is ground to 10min, under nitrogen protection, in 350 ℃ of pre-burning 4h, then pre-burning gains are ground to 10min, compressing tablet, at 700 ℃, calcine 8h, finally obtain Li
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 and is prepared as follows step:
A, by 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 300ml deionized water, form solution I, wherein according to amount of substance calculate, n
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 to 0.5h;
C, complexing agent II ascorbic acid is dissolved in to 70mL deionized water under mechanical agitation, obtains solution II;
D, under vigorous stirring, solution II is slowly added drop-wise in solution I, obtain solution III;
E, gained solution III in steps d is obtained to solution IV prior to reacting 2h in 80 ℃ of water-baths;
F, gained solution IV in step e is continued to form colloidal sols 80 ℃ of stirred in water bath, moisture evaporation is obtained to gel;
G, gained gel dry 6h in 120 ℃ of baking ovens obtains xerogel;
H, first gained xerogel is ground to 10min, under nitrogen protection, in 350 ℃ of pre-burning 4h, then pre-burning gains are ground to 10min, compressing tablet, at 800 ℃, calcine 6h, finally obtain Li
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 and is prepared as follows step:
A, by 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 350ml deionized water, form solution I, wherein according to amount of substance calculate, n
li: n
v: n
pO4-=3.05: 2: 3, n
v: n
oxalic acid=1: 3.5, m
beta-schardinger dextrin-: m
final products=0.7;
B, in 70 ℃ of water-baths, solution I is stirred to 1h;
C, complexing agent II ascorbic acid is dissolved in to 65mL deionized water under mechanical agitation, obtains solution II;
D, under vigorous stirring, solution II is slowly added drop-wise in solution I, obtain solution III;
E, gained solution III in steps d is obtained to solution IV prior to reacting 2h in 80 ℃ of water-baths;
F, gained solution IV in step e is continued to form colloidal sols 80 ℃ of stirred in water bath, moisture evaporation is obtained to gel;
G, gained gel dry 6h in 120 ℃ of baking ovens obtains xerogel;
H, first gained xerogel is ground to 15min, under nitrogen protection, in 400 ℃ of pre-burning 3h, then pre-burning gains are ground to 15min, compressing tablet, at 800 ℃, calcine 4h, finally obtain Li
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 and is prepared as follows step:
A, by 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 400ml deionized water, form solution I, wherein according to amount of substance calculate, n
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 to 1h;
C, complexing agent II glycine is dissolved in to 70mL deionized water under mechanical agitation, obtains solution II;
D, under vigorous stirring, solution II is slowly added drop-wise in solution I, obtain solution III;
E, gained solution III in steps d is obtained to solution IV prior to reacting 4h in 75 ℃ of water-baths;
F, gained solution IV in step e is continued to form colloidal sols 80 ℃ of stirred in water bath, moisture evaporation is obtained to gel;
G, gained gel dry 8h in 120 ℃ of baking ovens obtains xerogel;
H, first gained xerogel is ground to 10min, under nitrogen protection, in 350 ℃ of pre-burning 4h, then pre-burning gains are ground to 10min, compressing tablet, at 800 ℃, calcine 6h, finally obtain Li
3v
2(PO
4)
3/ C composite material.
The above is only five embodiment of the present invention; should be understood that; for the person of ordinary skill of the art; do not departing under the prerequisite of principle of the present invention; can also make some modifications and improvement to the present invention, so all equivalences of doing according to method, feature and principle described in patent claim of the present invention change or improve; the complexing agent II for example choosing is malic acid or maleic acid, and these features belong to the scope of patent application protection of the present invention equally.
As seen from Figure 1, the coated phosphoric acid vanadium lithium composite material the highest specific discharge capacity under 20C charging and discharging currents of carbon that prepared by the present invention can reach 95.2mAh g
-1, 180 capacity are without obvious decay.The coated phosphoric acid vanadium lithium composite material of carbon that as shown in Figure 2 prepared by the present invention under 0.7C charging current under 35C discharging current capacity reach as high as 87.1mAh g
-1.The vanadium phosphate lithium/carbon composite material of being prepared by the present invention shows good cycle performance under high magnification, and the method that this sol-gal process based on compound complex agent is prepared monoclinic lithium vanadium phosphate is a kind of very promising synthetic method.
Claims (5)
1. a lithium ion battery Li
3v
2(PO
4)
3the preparation method of/C composite material, is characterized in that, comprises and is prepared as follows step:
A, lithium source, vanadium source, phosphoric acid root, oxalic acid and complexing agent I beta-schardinger dextrin-are dissolved in to deionized water under mechanical agitation, form solution I, wherein according to amount of substance, calculate n
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, by solution I stir 0.5～2h;
C, complexing agent II is dissolved in to deionized water under mechanical agitation, obtains solution II;
D, under vigorous stirring, solution II is slowly added drop-wise in solution I, obtain solution III;
E, gained solution III in steps d is obtained to solution IV prior to reacting 2～4h in 60～80 ℃ of water-baths;
F, gained solution IV in step e is continued to form colloidal sols 60～80 ℃ of stirred in water bath, moisture evaporation is obtained to gel;
G, gained gel dry 4～8h in 80～120 ℃ of baking ovens obtains xerogel;
H, first gained xerogel is ground to 5～15min, under nitrogen protection, in 300～400 ℃ of pre-burning 3～6h, then pre-burning gains are ground to 5～15min, compressing tablet, at 650～850 ℃, calcine 4～10h, finally obtain Li
3v
2(PO
4)
3/ C composite material.
2. Li according to claim 1
3v
2(PO
4)
3the preparation method of/C composite material, is characterized in that, described lithium source is one or several the mixture in lithium hydroxide, lithium nitrate, lithium acetate.
3. Li according to claim 1
3v
2(PO
4)
3the preparation method of/C composite material, is characterized in that, described vanadium source is the mixture of a kind of in vanadic oxide, ammonium metavanadate or two kinds.
4. Li according to claim 1
3v
2(PO
4)
3the preparation method of/C composite material, is characterized in that, described phosphoric acid root is one or several the mixture in phosphoric acid, ammonium dihydrogen phosphate, ammonium hydrogen phosphate.
5. Li according to claim 1
3v
2(PO
4)
3the preparation method of/C composite material, is characterized in that, described complexing agent II is the one or more combination thing in citric acid, glycine, ascorbic acid, tartaric acid.
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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 |
| 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 |
| 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 |
| 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 |
| 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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