CN108270004A - Lithium iron phosphate positive material and preparation method - Google Patents
Lithium iron phosphate positive material and preparation method Download PDFInfo
- Publication number
- CN108270004A CN108270004A CN201810054891.7A CN201810054891A CN108270004A CN 108270004 A CN108270004 A CN 108270004A CN 201810054891 A CN201810054891 A CN 201810054891A CN 108270004 A CN108270004 A CN 108270004A
- Authority
- CN
- China
- Prior art keywords
- iron phosphate
- lithium iron
- lithium
- positive material
- phosphate positive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 106
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 24
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 24
- -1 carbon graphite alkene compound Chemical class 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052493 LiFePO4 Inorganic materials 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 150000002989 phenols Chemical class 0.000 claims abstract description 10
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 6
- 239000010439 graphite Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 11
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000013538 functional additive Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical class CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 229910010951 LiH2 Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 claims description 3
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- JQVAPEJNIZULEK-UHFFFAOYSA-N 4-chlorobenzene-1,3-diol Chemical class OC1=CC=C(Cl)C(O)=C1 JQVAPEJNIZULEK-UHFFFAOYSA-N 0.000 claims description 2
- WFJIVOKAWHGMBH-UHFFFAOYSA-N 4-hexylbenzene-1,3-diol Chemical class CCCCCCC1=CC=C(O)C=C1O WFJIVOKAWHGMBH-UHFFFAOYSA-N 0.000 claims description 2
- GHVHDYYKJYXFGU-UHFFFAOYSA-N Beta-Orcinol Chemical class CC1=CC(O)=C(C)C(O)=C1 GHVHDYYKJYXFGU-UHFFFAOYSA-N 0.000 claims description 2
- QSBINWBNXWAVAK-PSXMRANNSA-N PE-NMe(16:0/16:0) Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(=O)OCCNC)OC(=O)CCCCCCCCCCCCCCC QSBINWBNXWAVAK-PSXMRANNSA-N 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- ASHGTJPOSUFTGB-UHFFFAOYSA-N methyl resorcinol Natural products COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920002866 paraformaldehyde Polymers 0.000 claims description 2
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 claims description 2
- 229960003868 paraldehyde Drugs 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- ZLCPKMIJYMHZMJ-UHFFFAOYSA-N 2-nitrobenzene-1,3-diol Chemical class OC1=CC=CC(O)=C1[N+]([O-])=O ZLCPKMIJYMHZMJ-UHFFFAOYSA-N 0.000 claims 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 229920001568 phenolic resin Polymers 0.000 abstract description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 abstract description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 abstract description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005253 cladding Methods 0.000 abstract description 4
- 238000009833 condensation Methods 0.000 abstract description 4
- 230000005494 condensation Effects 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005011 phenolic resin Substances 0.000 abstract description 3
- 238000001694 spray drying Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 238000007599 discharging Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 238000005213 imbibition Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- VGMJYYDKPUPTID-UHFFFAOYSA-N 4-ethylbenzene-1,3-diol Chemical class CCC1=CC=C(O)C=C1O VGMJYYDKPUPTID-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- ZSYNKHJUSDFTCQ-UHFFFAOYSA-N [Li].[Fe].P(O)(O)(O)=O Chemical compound [Li].[Fe].P(O)(O)(O)=O ZSYNKHJUSDFTCQ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 125000005588 carbonic acid salt group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of preparation methods of lithium iron phosphate positive material, phenols/ferric lithium phosphate precursor mixed liquor is first configured in this method, aldehydes solution is added again, the hydro-thermal reaction of phenol formaldehyde condensation is carried out under the conditions of autoclave later, obtain the first clad of LiFePO4 of phenolic resin formation, on its surface, cladding polyvinylpyrrolidone obtains the second clad later, and lithium iron phosphate positive material finally is prepared by spray drying, sintering.The lithium iron phosphate positive material that the present invention obtains, with nucleocapsid, the double casing that cladding is formed by carbon graphite alkene compound, porous carbon on interior phosphocarnic acid iron lithium surface, while the tap density, conductivity and its specific capacity for significantly improving material, the high rate performance and cycle performance of lithium ion battery are also improved, suitable for the lithium ion battery of high-energy-density density.
Description
Technical field
The present invention relates to lithium ion battery material technical field more particularly to a kind of preparation sides of lithium iron phosphate positive material
Method and the lithium iron phosphate positive material obtained by the preparation method.
Background technology
Lithium iron phosphate electrode material is a kind of novel battery material to grow up in recent years, is mainly used for various lithium ions
Battery, because its have many advantages, such as good cycle, it is environmental-friendly, cheap due to have been favored by people, but LiFePO4
The shortcomings that it is equally apparent, ion and electron conduction are poor, so that its charge-discharge magnification performance is bad, and the shortcoming greatly limits
The application of LiFePO4 is made.
To improve the electric conductivity of LiFePO4, usually in substances such as LiFePO4 surface coated saccharose, glucose sugar, after carbonization
Carbonizable substance is formed to improve electric conductivity or using organic matter as reducing agent by ferric iron back or the ferrous oxidation of inhibition,
And contact between lithium iron phosphate particles is prevented, growing up for particle is hindered, while prevent LiFePO4 in charge and discharge process
Dissolving.If Chinese patent 201310323690.X discloses a kind of preparation method of lithium iron phosphate/carbon composite material, sugarcane is utilized
The high temperature cabonization of the hydrocarbons such as sugar, glucose sugar, starch cracks the carbon-coating to be formed and be coated on LiFePO4 surface, to improve material
Specific capacity, multiplying power and its cycle performance of material；But in the carbon-coating that material surface is formed, there are clad is uneven, layer and layer it
Between the problems such as combining the poor compatibility of force difference, clad and electrolyte, the cycle of LiFePO 4 material, high rate performance is caused to improve
It is limited.
Invention content
To solve the shortcomings of the prior art, the present invention provides a kind of preparation method of lithium iron phosphate positive material,
This method carries out phenol-formaldehyde reaction by hydro-thermal reaction on LiFePO4 surface, forms the carbon-coating as the first clad, in conjunction with
The high carbon chain polymer of high-specific surface area carries out coating modification to the first cover surface of material, and it is suitably more to obtain specific surface area
The second clad of permeability, so as to obtain, tap density is high, specific capacity is high, imbibition ability is strong, high rate performance is good, cycle performance is excellent
Composite ferric lithium phosphate material.
To achieve the above object, the preparation method of lithium iron phosphate positive material provided by the invention, includes the following steps：
A, ferric lithium phosphate precursor is obtained；
B, intermediary material is prepared：By phenolic compound, ferric lithium phosphate precursor, graphene oxide conduction liquid, carbonate/
Obtained mixed solution is added to the aldehyde that mass concentration is (1~5) % by bicarbonate compound and functional additive mixing
In class compound water solution, it is then transferred in autoclave, it is anti-under temperature (100~200) DEG C, pressure (1~5) Mpa
(1~3) h is answered, through drying, crushes, obtains intermediary material；
By quality proportioning, ferric lithium phosphate precursor:Phenolic compound:Aldehyde compound:Graphene oxide solid:Carbonic acid
Salt/bicarbonate compound:Functional additive=500:(10~50):(50~100):(1~10):(1~10):(0.5~
2)；
A concentration of (1~10) mg/mL of the graphene oxide conduction liquid；
The functional additive be hydrazide compound, careless acid dihydrazide, acid dihydrazide, glutaric, amber glass
Acid dihydrazide, adipic dihydrazide, Malaysia acid dihydrazide, two hydrazides of fumaric acid, O-phthalic acid dihydrazide, terephthalic acid (TPA) two
At least one in hydrazides, isophthalic dihydrazide, two hydrazides of pyromellitic acid, three hydrazides of pyromellitic acid, 1,2,4- benzene, three hydrazides
Kind；
C, lithium iron phosphate positive material is prepared：100 parts of intermediary materials are added to 1000ml mass concentrations (1~5) %
Polyvinylpyrrolidonesolution solution in, be uniformly dispersed, then add (0.5~5) part catalyst, spray after fully dispersed
It is dry, it is transferred in tube furnace, after in a hydrogen atmosphere, being warming up to (750~850) DEG C sintering (1~12) h, drops naturally later
It warms to room temperature, crushing obtains lithium iron phosphate positive material；
The catalyst is at least one of potassium hydroxide, sodium hydroxide, zinc chloride.
The lithium iron phosphate positive material of the present invention, it is anti-in high pressure later by LiFePO4 adsorption aldehyde material
The hydro-thermal reaction that phenol formaldehyde condensation is carried out under the conditions of kettle is answered, obtains the molecular weight formed on LiFePO4 surface length, stable structure
Phenolic resin class compound substance, forms that consistency is high, netted clad of large specific surface area, the first cladding as LiFePO4
Layer, makes the electric conductivity of LiFePO4, chemical property be greatly improved, is improved in terms of tap density, gram volume；
Meanwhile using the conductivity height of admixture, the grapheme material of large specific surface area, phenolic substance carbonisation is promoted to form interlayer
Away from big amorphous carbon layer, so as to improve lithium ion in charge and discharge process it is embedding go out rate and cycle performance.But since hydro-thermal is anti-
The LiFePO 4 material that should be formed has the characteristic of large specific surface area, does not utilize the first charge discharge efficiency of material and the performance of gram volume,
Therefore polyvinylpyrrolidone (PVP) and catalyst is used in combination, the second clad being made of PVP is formed in material surface,
To reduce material specific surface area, while suitable Nano/micron hole is formed by the effect of catalyst, improve LiFePO4 material
The imbibition of material, liquid-keeping property while materials conductive rate is improved, significantly improve the cycle performance of material.What the present invention obtained
LiFePO 4 material reaches 163mAh/g with reversible specific capacity during 0.1C multiplying power dischargings, with reversible specific capacity during 10C multiplying power dischargings
Reach more than 115mAh/g, while tap density reaches 1.4g/cm3.Therefore, conduction can be prepared by the preparation method of the present invention
The lithium iron phosphate positive material that rate is high, tap density is high, specific capacity is high, high rate performance is good, cycle performance is excellent, suitable for high ratio
Energy density lithium ion battery.
As the restriction to above-mentioned technical proposal, ferric lithium phosphate precursor can be prepared according to the following steps described in step a：
By 10.4g LiH2PO4、40.4gFe(NO3)3·9H2O is dissolved in 500ml n,N-Dimethylformamide, stirs evenly,
Obtain the lithium iron phosphate precursor solution that mass concentration is 10%, filtered later, 80 DEG C of vacuum drying, 800 DEG C of high temperature sinterings
2h obtains ferric lithium phosphate precursor.
As the restriction to above-mentioned technical proposal, phenolic compound described in step b is resorcinol, 2- methylresorcinols two
Phenol, oreinol diphenol, 2,5- dimethyl resorcinols, 4- ethyl resorcinols, 4- chloro resorcinols, 2- nitros isophthalic two
At least one of phenol, 4- bromines resorcinol, 4- n-hexyl resorcinols.
As the restriction to above-mentioned technical proposal, the phenolic compound is resorcinol and/or methyl resorcinol.
As the restriction to above-mentioned technical proposal, aldehyde compound described in step b for formaldehyde, paraformaldehyde, polyacetals,
At least one of acetaldehyde, para-acetaldehyde, crotonaldehyde, methacrylaldehyde.
As the restriction to above-mentioned technical proposal, the preferred formaldehyde of the aldehyde compound and/or acetaldehyde.
As the restriction to above-mentioned technical proposal, carbonate/bicarbonate compound described in step b is sodium carbonate, carbon
One kind in sour potassium, sodium bicarbonate, saleratus.
Further limit ferric lithium phosphate precursor preparation and raw material phenolic compound, aldehyde compound, carbonate/
The preferred substance of bicarbonate compound more conducively improves the chemical property of LiFePO 4 material.
Meanwhile the present invention also provides a kind of lithium iron phosphate positive material, by lithium iron phosphate positive material as described above
Preparation method be made.
As the restriction to above-mentioned technical proposal, the lithium iron phosphate positive material has nucleocapsid, and kernel is phosphorus
Sour iron lithium, shell are the carbon graphite alkene compound for being coated on surface and the double casing of porous carbon formation.
As the restriction to above-mentioned technical proposal, the covering amount of the shell is (1~5) %.
Nucleocapsid is presented in the lithium iron phosphate positive material obtained by the preparation method of the present invention, in interior phosphocarnic acid iron lithium table
Bread covers the double casing formed by carbon graphite alkene compound, porous carbon layer, improve LiFePO 4 material chemical property,
While tap density, specific capacity, high rate performance and cycle performance are improved, to be suitable for the lithium-ion electric of high-energy-density density
Pond.
In conclusion technical solution using the present invention, the preparation method of the lithium iron phosphate positive material of acquisition, are first configured
Phenols/ferric lithium phosphate precursor mixed liquor, then aldehydes solution is added, phenol formaldehyde condensation is carried out under the conditions of autoclave later
Hydro-thermal reaction obtains the first clad of LiFePO4 of phenolic resin formation, coats polyvinylpyrrolidone on its surface later
The second clad is obtained, lithium iron phosphate positive material finally is prepared by spray drying, sintering.The phosphoric acid that the present invention obtains
Iron lithium anode material has nucleocapsid, is coated on interior phosphocarnic acid iron lithium surface by carbon graphite alkene compound, porous carbon layer shape
Into double casing, while significantly improving the chemical property of material, tap density, specific capacity, also improve high rate performance
And cycle performance, to be suitable for the lithium ion battery of high-energy-density density.
Description of the drawings
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the SEM figures for the lithium iron phosphate positive material that the embodiment of the present invention one obtains；
Specific embodiment
Below in conjunction with embodiment, technical scheme of the present invention is clearly and completely described, it is clear that described
Embodiment is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field
Those of ordinary skill's all other embodiments obtained without making creative work, belong to protection of the present invention
Range.
Embodiment one
The present embodiment is related to a kind of preparation of lithium iron phosphate positive material.
Embodiment 1.1
Lithium iron phosphate positive material is prepared according to the following steps：
A, ferric lithium phosphate precursor is obtained；Ferric lithium phosphate precursor can be directly bought, can be also prepared as follows：It will
10.4g LiH2PO4、40.4gFe(NO3)3·9H2O is dissolved in 500ml n,N-Dimethylformamide, stirs evenly, and it is dense to obtain quality
The lithium iron phosphate precursor solution for 10% is spent, filtered later, 80 DEG C of vacuum drying, 800 DEG C of high temperature sintering 2h obtain phosphoric acid
Iron lithium presoma；
B, intermediary material is prepared：By 30g resorcinols, 500g ferric lithium phosphate precursors, a concentration of 8mg/ml of 1000ml
Graphene oxide conduction liquid, 5g sodium carbonate and 1g grass acid dihydrazides be uniformly mixed, obtained mixed solution is added to 266ml matter
In the formalin for measuring concentration 3%, it is then transferred in autoclave, reacts 2h under 150 DEG C of temperature, pressure 3Mpa,
It through drying, crushes, obtains intermediary material；
C, lithium iron phosphate positive material is prepared：100g intermediary materials are added to the poly- second of 1000ml mass concentrations 3%
It in alkene pyrrolidone (PVP) solution, is uniformly dispersed, then adds the potassium hydroxide solution of 50ml mass concentrations 1% as catalysis
Agent is spray-dried after fully dispersed, is transferred in tube furnace later, in a hydrogen atmosphere, is warming up to 800 DEG C of sintering 6h
Afterwards, room temperature is naturally cooling to, crushing obtains lithium iron phosphate positive material.
Embodiment 1.2
Lithium iron phosphate positive material is prepared according to the following steps：
A, ferric lithium phosphate precursor is obtained；Ferric lithium phosphate precursor can be directly bought, can be also prepared as follows：It will
10.4g LiH2PO4、40.4gFe(NO3)3·9H2O is dissolved in 500ml n,N-Dimethylformamide, stirs evenly, and obtains a concentration of
10% lithium iron phosphate precursor solution, filtered later, 80 DEG C of vacuum drying, 800 DEG C of high temperature sintering 2h, obtains LiFePO4
Presoma；
B, intermediary material is prepared：10g 2- methyl resorcinols, 500g ferric lithium phosphate precursors, 1000ml is a concentration of
Graphene oxide conduction liquid, 1g potassium carbonate and the 0.5g acid dihydrazides of 1mg/ml is uniformly mixed, and obtained mixed solution adds
Enter into the acetaldehyde solution of 500ml mass concentrations 1%, be then transferred in autoclave, in 100 DEG C of temperature, pressure
1h is reacted under 5Mpa, through drying, crushes, obtains intermediary material；
C, lithium iron phosphate positive material is prepared：100g intermediary materials are added to the poly- second of 1000ml mass concentrations 1%
It in alkene pyrrolidone (PVP) solution, is uniformly dispersed, then the sodium hydroxide solution of addition 20ml mass concentrations 0.5%, which is used as, urges
Agent is spray-dried after fully dispersed, is transferred in tube furnace later, in a hydrogen atmosphere, is warming up to 750 DEG C of sintering
After 12h, room temperature is naturally cooling to, crushing obtains lithium iron phosphate positive material.
Embodiment 1.3
Lithium iron phosphate positive material is prepared according to the following steps：
A, ferric lithium phosphate precursor is obtained；Ferric lithium phosphate precursor can be directly bought, can be also prepared as follows：It will
10.4g LiH2PO4、40.4gFe(NO3)3·9H2O is dissolved in 500ml n,N-Dimethylformamide, stirs evenly, and obtains a concentration of
10% lithium iron phosphate precursor solution, filtered later, 80 DEG C of vacuum drying, 800 DEG C of high temperature sintering 2h, obtains LiFePO4
Presoma；
B, intermediary material is prepared：50g oreinols diphenol, 500g ferric lithium phosphate precursors, 1000ml is a concentration of
Graphene oxide conduction liquid, 10g sodium bicarbonates and the 2g glutarics of 10mg/ml is uniformly mixed, obtained mixed solution
It is added in the crotonaldehyde solution that 2000ml mass concentrations are 5%, is then transferred in autoclave, in 200 DEG C of temperature, pressure
3h is reacted under strong 1Mpa, through drying, crushes, obtains intermediary material；
C, lithium iron phosphate positive material is prepared：100g intermediary materials are added to the polyethylene of 1000ml a concentration of 5%
It in pyrrolidones (PVP) solution, is uniformly dispersed, then adds the liquor zinci chloridi of 20ml a concentration of 5% as catalyst, fully
It is spray-dried after dispersion, is transferred in tube furnace later, in a hydrogen atmosphere, after being warming up to 850 DEG C of sintering 1h, dropped naturally
It warms to room temperature, crushing obtains lithium iron phosphate positive material.
Comparative example
Comparative example 1
500g ferric lithium phosphate precursors are added to 2000ml, mass concentration is agitation and filtration in 5% glucose solution
After be transferred in tube furnace, and in a hydrogen atmosphere, be warming up to 750 DEG C and be sintered 12h, Temperature fall is to room temperature later, and
Crushing obtains composite ferric lithium phosphate material.
Comparative example 2
It weighs 1.6g resorcinols to be dissolved in 250mL deionized waters, then adds in the formaldehyde that 3mL mass fractions are 37%
Solution adds 60g LiFePO4s, while being stirred continuously makes it be uniformly dispersed.Controlling reaction temperature is at 60 DEG C, sustained response 6
After hour, solution stirring is evaporated, desciccate is calcined 2 hours for 600 DEG C under protective atmosphere, has obtained LiFePO4 composite wood
Material.
Embodiment two
The present embodiment is related to the lithium iron phosphate positive material performance detection of the present invention.
Embodiment 2.1
The lithium iron phosphate positive material that embodiment one is prepared carries out SEM Electronic Speculum tests, as seen from Figure 1, acquisition
Ball-type is presented in LiFePO 4 material, and size distribution is uniform, and grain size is between (1~5) μm.
Embodiment 2.2
The lithium iron phosphate positive material sample that embodiment one and comparative example are prepared carries out electrochemical property test.
Embodiment 2.2.1
Button cell is tested
Test method：1,2 five embodiment 1.1~1.3, comparative example each 2.0000g of sample are weighed, respectively by each sample system
Into button cell, i.e., mix 2.0000g samples with 0.1111g conductive blacks, 0.1111gPVDF (in mass ratio 0.9: 0.05:
0.05) 2.5g organic solvents NMP (N-Methyl pyrrolidone), is added, after being sufficiently mixed uniformly, on aluminium foil painting thickness is
140 microns of film, 120 DEG C of vacuum drying 2h are broken into the disk of 5mm using card punch, are pushed using tablet press machine in 10Mpa
Piece, 120 DEG C of vacuum heat-preserving 12h, weighs anode sheet weight.Button cell is assembled into the glove box of argon gas protection, with metal
Lithium piece is cathode, and electrolyte is volume ratio 1:1 EC (ethylene carbonate), DMC (1,2- dimethyl carbonate) mixed solvent, electricity
Solve matter LiPF6, diaphragm is Celgard2400 microporous polyethylene films.The battery installed is tested into electrical property on blue electric tester.
In 2.5V~4.2V voltage ranges, with 0.2C constant current charge/discharge, specific capacity is tested, is carried out at the same time 0.2C chargings, 10C electric discharges
Test its specific capacity.The results are shown in Table 1, and the embodiment 1.1~1.3, comparative example are represented with A1, A2, A3 and B1, B2 in table
1st, the button cell that 2 five samples are prepared respectively.
By 1 result of table as it can be seen that the lithium iron phosphate positive material that embodiment one is prepared, discharge capacity and first charge discharge efficiency are apparent
Higher than comparative example 1, the reason for this is that the phenolic resin that material surface doping has interlamellar spacing provides the biography of lithium ion in charge and discharge process
Defeated rate plays so as to improve the first charge discharge efficiency of its material and gram volume；It is strong by phenol-formaldehyde reaction generation binding force simultaneously, it is fine and close
The first high clad is spent, improves the tap density of its material.
Embodiment 2.2.2
Soft-package battery is tested
Respectively using the sample of embodiment 1.1~1.3 and comparative example 1,2 as positive electrode, using Delanium as cathode material
Material, using LiPF6/ EC+DEC (volume ratios 1:1) it is electrolyte, 2400 film of a concentration of 1.3mol/L, Celgard is diaphragm, is made
It is standby go out 2.5Ah cylindrical batteries, and the cycle performance of test material.
Cycle performance test parameter：Multiplying power is charged and discharged multiplying power 2.0C/2.0C, 2.5~4.2V of voltage range, temperature 25
± 3 DEG C, cycle-index 500 times, while calculate the energy density of battery.
The multiplying power discharging property of each sample is tested, the results are shown in Table 2.
By 2 result of table as it can be seen that battery its energy density prepared by the lithium iron phosphate positive material of embodiment one is apparent
Better than comparative example 1,2, the reason for this is that there is one material of embodiment higher specific capacity and its tap density to improve the energy of its material
Metric density, while LiFePO 4 material has the lithium ion that consistency is high, structural stability is strong and its sufficient, is followed so as to improve it
Ring performance.
Comparative example 2 forms one layer of fine and close clad by the polymerisation of phenol formaldehyde condensation on lithium iron phosphate particles surface,
Modified LiFePO4 is obtained, the electric conductivity of material and the chemical property of test is made to be greatly improved, while in jolt ramming
Density is improved in terms of gram volume, but the high rate performance deviation of material is larger, the cycle performance under the conditions of big multiplying power compared with
Difference.
In conclusion the lithium iron phosphate positive material that the present invention obtains, is presented nucleocapsid, on interior phosphocarnic acid iron lithium surface
Double casing is coated, the first clad formed by carbon graphite alkene compound makes electric conductivity, the chemical property of LiFePO4
It is greatly improved, is improved in terms of tap density, gram volume；Meanwhile because the presence of graphene promotes the first cladding
Layer forms the amorphous carbon layer of larger interlamellar spacing in forming process with the carbonization of phenolic substance, so as to improve charge and discharge process
Middle lithium ion it is embedding go out rate and cycle performance；The porous carbon formed after being carbonized by PVP is solved as the second clad
The drawbacks of first clad is brought, reduces material specific surface area, while forms suitable nanometer/micro- by the effect of catalyst
Imbibition, the liquid-keeping property of LiFePO 4 material are improved in metre hole hole, while materials conductive rate is improved, significantly improve material
Cycle performance.The LiFePO 4 material that the present invention obtains reaches 163mAh/g with reversible specific capacity during 0.1C multiplying power dischargings, with 10C
Reversible specific capacity reaches more than 115mAh/g during multiplying power discharging, while tap density reaches 1.4g/cm3.Therefore, by the present invention's
Preparation method can prepare the ferric phosphate that conductivity is high, tap density is high, specific capacity is high, high rate performance is good, cycle performance is excellent
Lithium anode material, suitable for high-energy-density density lithium ion battery.
Claims (10)
1. a kind of preparation method of lithium iron phosphate positive material, which is characterized in that the preparation method includes the following steps：
A, ferric lithium phosphate precursor is obtained；
B, intermediary material is prepared：By phenolic compound, ferric lithium phosphate precursor, graphene oxide conduction liquid, carbonate/carbonic acid
Obtained mixed solution is added to the aldehydes that mass concentration is (1~5) % by hydrogen salt compound and functional additive mixing
It closes in object aqueous solution, is then transferred in autoclave, (1 is reacted under temperature (100~200) DEG C, pressure (1~5) Mpa
~3) h through drying, crushes, obtains intermediary material；
By quality proportioning, ferric lithium phosphate precursor:Phenolic compound:Aldehyde compound:Graphene oxide solid:Carbonate/carbon
Sour hydrogen salt compound:Functional additive=500:(10~50):(50~100):(1~10):(1~10):(0.5~2)；
A concentration of (1~10) mg/mL of the graphene oxide conduction liquid；
The functional additive be hydrazide compound, careless acid dihydrazide, acid dihydrazide, glutaric, amber glass acid two
Hydrazides, adipic dihydrazide, Malaysia acid dihydrazide, two hydrazides of fumaric acid, O-phthalic acid dihydrazide, two acyl of terephthalic acid (TPA)
At least one of hydrazine, isophthalic dihydrazide, two hydrazides of pyromellitic acid, three hydrazides of pyromellitic acid, 1,2,4- benzene, three hydrazides；
C, lithium iron phosphate positive material is prepared：100 parts of intermediary materials are added to the poly- of 1000ml mass concentrations (1~5) %
It in vinylpyrrolidone solution, is uniformly dispersed, then adds the catalyst of (0.5~5) part, it is dry that spraying is carried out after fully dispersed
It is dry, it is transferred in tube furnace later, after in a hydrogen atmosphere, being warming up to (750~850) DEG C sintering (1~12) h, Temperature fall
To room temperature, crushing obtains lithium iron phosphate positive material；
The catalyst is at least one of potassium hydroxide, sodium hydroxide, zinc chloride.
2. the preparation method of lithium iron phosphate positive material according to claim 1, it is characterised in that：Phosphoric acid described in step a
Iron lithium presoma can be prepared according to the following steps：
By 10.4g LiH2PO4、40.4gFe(NO3)3·9H2O is dissolved in 500ml n,N-Dimethylformamide, stirs evenly, and obtains
Mass concentration is 10% lithium iron phosphate precursor solution, and filtered later, 80 DEG C of vacuum drying, 800 DEG C of high temperature sintering 2h are obtained
To ferric lithium phosphate precursor.
3. the preparation method of lithium iron phosphate positive material according to claim 1, it is characterised in that：Phenol described in step b
Class compound is resorcinol, between 2- methyl resorcinols, oreinol diphenol, 2,5- dimethyl resorcinols, 4- ethyls
At least one of benzenediol, 4- chloro resorcinols, 2- nitro-resorcinols, 4- bromines resorcinol, 4- n-hexyl resorcinols.
4. the preparation method of lithium iron phosphate positive material according to claim 3, it is characterised in that：The phenolic compound
For resorcinol and/or methyl resorcinol.
5. the preparation method of lithium iron phosphate positive material according to claim 1, it is characterised in that：Aldehyde described in step b
Class compound is at least one of formaldehyde, paraformaldehyde, polyacetals, acetaldehyde, para-acetaldehyde, crotonaldehyde, methacrylaldehyde.
6. the preparation method of lithium iron phosphate positive material according to claim 5, it is characterised in that：The aldehyde compound
It is preferred that formaldehyde and/or acetaldehyde.
7. the preparation method of lithium iron phosphate positive material according to claim 1, it is characterised in that：Carbon described in step b
Hydrochlorate/bicarbonate compound is sodium carbonate, one kind in potassium carbonate, sodium bicarbonate, saleratus.
8. a kind of lithium iron phosphate positive material, it is characterised in that：By LiFePO4 according to any one of claims 1 to 7 just
The preparation method of pole material is made.
9. lithium iron phosphate positive material according to claim 8, it is characterised in that：The lithium iron phosphate positive material has
Nucleocapsid, kernel are LiFePO4, and shell is the carbon graphite alkene compound for being coated on surface and the bilayer of porous carbon formation
Shell.
10. lithium iron phosphate positive material according to claim 9, it is characterised in that：The covering amount of the shell for (1~
5) %.
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| CN110265652A (en) * | 2019-07-19 | 2019-09-20 | 河南师范大学 | A kind of preparation method for lithium ion/sodium-ion battery cathode nano-sheet Sb/C composite material |
| CN110265652B (en) * | 2019-07-19 | 2022-09-27 | 河南师范大学 | Preparation method of nano flaky Sb/C composite material for lithium ion/sodium ion battery cathode |
| CN111799446A (en) * | 2020-05-27 | 2020-10-20 | 广西华政新能源科技有限公司 | Fast-charging type explosion-proof lithium ion battery |
| CN115364041A (en) * | 2022-08-19 | 2022-11-22 | 辽宁大学 | Three-dimensional graphene oxide electric field sensitive drug-loading system and three-dimensional graphene oxide electric field sensitive drug-loading hydrogel |
| CN115364041B (en) * | 2022-08-19 | 2024-05-31 | 辽宁大学 | Three-dimensional graphene oxide electric field sensitive medicine carrying system and three-dimensional graphene oxide electric field sensitive medicine carrying hydrogel |
| CN116240574A (en) * | 2023-03-21 | 2023-06-09 | 四川捷途环保服务有限公司 | Electrocatalytic material and preparation method and application thereof |
| CN116600888A (en) * | 2023-03-27 | 2023-08-15 | 广东邦普循环科技有限公司 | Carbon-coated lithium ion sieve for extracting lithium by electrochemical deintercalation method, and preparation method and application thereof |
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