CN108270004B - Lithium iron phosphate anode material and preparation method thereof - Google Patents
Lithium iron phosphate anode material and preparation method thereof Download PDFInfo
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- CN108270004B CN108270004B CN201810054891.7A CN201810054891A CN108270004B CN 108270004 B CN108270004 B CN 108270004B CN 201810054891 A CN201810054891 A CN 201810054891A CN 108270004 B CN108270004 B CN 108270004B
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- Prior art keywords
- iron phosphate
- lithium iron
- positive electrode
- electrode material
- resorcinol
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- 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 135
- 239000010405 anode material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 50
- 239000002243 precursor Substances 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- -1 phenolic aldehyde Chemical class 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 23
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000001694 spray drying Methods 0.000 claims abstract description 7
- 239000011258 core-shell material Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims description 25
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000002989 phenols Chemical class 0.000 claims description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 239000013538 functional additive Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 claims description 5
- 229910010951 LiH2 Inorganic materials 0.000 claims description 5
- VGMJYYDKPUPTID-UHFFFAOYSA-N 4-ethylbenzene-1,3-diol Chemical compound CCC1=CC=C(O)C=C1O VGMJYYDKPUPTID-UHFFFAOYSA-N 0.000 claims description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 4
- GHVHDYYKJYXFGU-UHFFFAOYSA-N Beta-Orcinol Chemical compound CC1=CC(O)=C(C)C(O)=C1 GHVHDYYKJYXFGU-UHFFFAOYSA-N 0.000 claims description 4
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 claims description 4
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 claims description 3
- LGYJSPMYALQHBL-UHFFFAOYSA-N pentanedihydrazide Chemical compound NNC(=O)CCCC(=O)NN LGYJSPMYALQHBL-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 claims description 2
- SNVRDQORMVVQBI-OWOJBTEDSA-N (e)-but-2-enedihydrazide Chemical compound NNC(=O)\C=C\C(=O)NN SNVRDQORMVVQBI-OWOJBTEDSA-N 0.000 claims description 2
- SNVRDQORMVVQBI-UPHRSURJSA-N (z)-but-2-enedihydrazide Chemical compound NNC(=O)\C=C/C(=O)NN SNVRDQORMVVQBI-UPHRSURJSA-N 0.000 claims description 2
- ZLCPKMIJYMHZMJ-UHFFFAOYSA-N 2-nitrobenzene-1,3-diol Chemical compound OC1=CC=CC(O)=C1[N+]([O-])=O ZLCPKMIJYMHZMJ-UHFFFAOYSA-N 0.000 claims description 2
- WFJIVOKAWHGMBH-UHFFFAOYSA-N 4-hexylbenzene-1,3-diol Chemical compound CCCCCCC1=CC=C(O)C=C1O WFJIVOKAWHGMBH-UHFFFAOYSA-N 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 229930182556 Polyacetal Natural products 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- IKWQWOFXRCUIFT-UHFFFAOYSA-N benzene-1,2-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C(=O)NN IKWQWOFXRCUIFT-UHFFFAOYSA-N 0.000 claims description 2
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 claims description 2
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 claims description 2
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 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
- 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
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000011247 coating layer Substances 0.000 abstract description 20
- 239000010410 layer Substances 0.000 abstract description 14
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 5
- 238000009833 condensation Methods 0.000 abstract description 4
- 230000005494 condensation Effects 0.000 abstract description 4
- 229920001568 phenolic resin Polymers 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
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000002245 particle 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
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 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 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- MPCCNXGZCOXPMG-UHFFFAOYSA-N 4-bromobenzene-1,3-diol Chemical compound OC1=CC=C(Br)C(O)=C1 MPCCNXGZCOXPMG-UHFFFAOYSA-N 0.000 description 1
- JQVAPEJNIZULEK-UHFFFAOYSA-N 4-chlorobenzene-1,3-diol Chemical compound OC1=CC=C(Cl)C(O)=C1 JQVAPEJNIZULEK-UHFFFAOYSA-N 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
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material 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
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- PSIKPHJLTVSQFO-UHFFFAOYSA-N propanedihydrazide Chemical compound NNC(=O)CC(=O)NN PSIKPHJLTVSQFO-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
Abstract
The invention discloses a preparation method of a lithium iron phosphate anode material, which comprises the steps of preparing a phenol/lithium iron phosphate precursor mixed solution, adding an aldehyde solution, carrying out a phenolic aldehyde condensation hydrothermal reaction under the condition of a high-pressure reaction kettle to obtain a first lithium iron phosphate coating layer formed by phenolic resin, coating polyvinylpyrrolidone on the surface of the first lithium iron phosphate coating layer to obtain a second lithium iron phosphate coating layer, and finally carrying out spray drying and sintering to obtain the lithium iron phosphate anode material. The lithium iron phosphate anode material obtained by the invention has a core-shell structure, and the surface of the core lithium iron phosphate is coated with a double-layer shell formed by a carbon/graphene compound and porous carbon, so that the tap density, the electric conductivity and the specific capacity of the material are obviously improved, the rate capability and the cycle performance of a lithium ion battery are also improved, and the lithium iron phosphate anode material is suitable for the lithium ion battery with high specific energy density.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a preparation method of a lithium iron phosphate anode material and the lithium iron phosphate anode material obtained by the preparation method.
Background
The lithium iron phosphate electrode material is a novel battery material developed in recent years, is mainly used for various lithium ion batteries, is favored by people due to the advantages of good cycle performance, environment friendliness, low price and the like, but has the same obvious defect that the lithium iron phosphate has poor ionic and electronic conductivity, so that the charging and discharging rate performance is poor, and the defect greatly limits the application of the lithium iron phosphate.
In order to improve the conductivity of lithium iron phosphate, sucrose, glucose and other substances are generally coated on the surface of lithium iron phosphate, and a carbon substance is formed after carbonization to improve the conductivity, or an organic substance is used as a reducing agent to reduce ferric iron or inhibit oxidation of ferrous iron, contact between lithium iron phosphate particles is prevented, growth of the particles is inhibited, and dissolution of the lithium iron phosphate in the charging and discharging processes is prevented. For example, chinese patent 201310323690.X discloses a preparation method of a lithium iron phosphate/carbon composite material, in which a carbon layer coated on the surface of lithium iron phosphate is formed by high-temperature carbonization and cracking of hydrocarbons such as sucrose, glucose, starch and the like, so as to improve the specific capacity, rate and cycle performance of the material; however, the carbon layer formed on the surface of the material has the problems of uneven coating layer, poor bonding force between layers, poor compatibility between the coating layer and electrolyte and the like, so that the cycle and rate performance improvement of the lithium iron phosphate material is limited.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a preparation method of a lithium iron phosphate anode material, which comprises the steps of carrying out phenolic aldehyde reaction on the surface of lithium iron phosphate through hydrothermal reaction to form a carbon layer serving as a first coating layer, and then combining a high-carbon-chain polymer with high specific surface area to coat and modify the surface of the first coating layer of the material to obtain a porous second coating layer with proper specific surface area, so that the lithium iron phosphate composite material with high tap density, high specific capacity, strong liquid absorption capacity, good rate capability and excellent cycle performance is obtained.
In order to achieve the purpose, the preparation method of the lithium iron phosphate anode material provided by the invention comprises the following steps:
a. obtaining a lithium iron phosphate precursor;
b. preparing an intermediate material: mixing a phenolic compound, a lithium iron phosphate precursor, a graphene oxide conductive liquid, a carbonate/bicarbonate compound and a functional additive, adding the obtained mixed solution into an aldehyde compound aqueous solution with the mass concentration of (1-5%), transferring the mixture into a high-pressure reaction kettle, reacting for 1-3 hours at the temperature of (100-200 ℃) and the pressure of (1-5) Mpa, and drying and crushing to obtain an intermediate material;
according to the mass ratio, the lithium iron phosphate precursor comprises a phenolic compound, an aldehyde compound, a graphene oxide solid, a carbonate/bicarbonate compound, a functional additive =500, (10-50), (50-100), (1-10) and (0.5-2);
the concentration of the graphene oxide conducting solution is (1-10) mg/mL;
the functional additive is at least one of hydrazide compounds, oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, phthalic acid dihydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, pyromellitic acid trihydrazide and 1,2, 4-benzene trihydrazide;
c. preparing a lithium iron phosphate positive electrode material: adding 100 parts of intermediate material into 1000ml of polyvinylpyrrolidone solution with mass concentration of 1-5%, uniformly dispersing, then adding 0.5-5 parts of catalyst, fully dispersing, performing spray drying, transferring to a tubular furnace, heating to 750-850 ℃ in a hydrogen atmosphere, sintering for 1-12 h, naturally cooling to room temperature, and crushing to obtain the lithium iron phosphate positive electrode material;
the catalyst is at least one of potassium hydroxide, sodium hydroxide and zinc chloride.
According to the lithium iron phosphate anode material, aldehyde substances are adsorbed on the surface of lithium iron phosphate, and then the hydrothermal reaction of phenolic aldehyde condensation is carried out under the condition of a high-pressure reaction kettle, so that a phenolic resin composite substance with long molecular weight and stable structure is formed on the surface of the lithium iron phosphate, and a net-shaped coating layer with high density and large specific surface area is formed and used as a first coating layer of the lithium iron phosphate, so that the conductivity and the electrochemical performance of the lithium iron phosphate are greatly improved, and the tap density and the gram volume are improved; meanwhile, the doped graphene material with high conductivity and large specific surface area is utilized to promote the phenolic substance to form an amorphous carbon layer with large interlayer spacing in the carbonization process, so that the insertion and extraction rate and the cycle performance of lithium ions in the charging and discharging process are improved. However, the lithium iron phosphate material formed by the hydrothermal reaction has the characteristic of large specific surface area and is not beneficial to the exertion of the first efficiency and gram volume of the material, so that polyvinylpyrrolidone (PVP) and a catalyst are combined for use, a second coating layer made of PVP is formed on the surface of the material to reduce the specific surface area of the material, appropriate nano/micro holes are formed under the action of the catalyst, the liquid absorption and retention capacity of the lithium iron phosphate material is improved, and the conductivity of the material is improvedMeanwhile, the cycle performance of the material is obviously improved. The lithium iron phosphate material obtained by the invention has a reversible specific capacity of 163mAh/g when discharged at a rate of 0.1C, a reversible specific capacity of more than 115mAh/g when discharged at a rate of 10C, and a tap density of 1.4g/cm3. Therefore, the lithium iron phosphate cathode material with high conductivity, high tap density, high specific capacity, good rate capability and excellent cycle performance can be prepared by the preparation method of the invention, and is suitable for the lithium ion battery with high specific energy density.
As a limitation to the above technical solution, the lithium iron phosphate precursor in step a may be prepared by the following steps:
10.4g of LiH2PO4、40.4gFe(NO3)3·9H2Dissolving O in 500ml of N, N-dimethylformamide, uniformly stirring to obtain a lithium iron phosphate precursor solution with the mass concentration of 10%, filtering, drying at 80 ℃ in vacuum, and sintering at 800 ℃ for 2h to obtain the lithium iron phosphate precursor.
As a limitation to the above technical scheme, the phenolic compound in the step b is at least one of resorcinol, 2-methylresorcinol, 5-methylresorcinol, 2, 5-dimethylresorcinol, 4-ethylresorcinol, 4-chlororesorcinol, 2-nitroresorcinol, 4-bromoresorcinol and 4-n-hexylresorcinol.
As a limitation to the above technical scheme, the phenolic compound is resorcinol and/or methyl resorcinol.
As a limitation to the above technical means, the aldehyde compound in step b is at least one of formaldehyde, paraformaldehyde, polyacetal, acetaldehyde, paraldehyde, crotonaldehyde, and acrolein.
As a limitation to the above technical means, the aldehyde compound is preferably formaldehyde and/or acetaldehyde.
As a limitation to the above technical solution, in the step b, the carbonate/bicarbonate compound is one of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
Further limits the preparation of the lithium iron phosphate precursor and the preferable substances of the raw materials of the phenolic compound, the aldehyde compound and the carbonate/bicarbonate compound, and is more beneficial to improving the electrochemical performance of the lithium iron phosphate material.
Meanwhile, the invention also provides a lithium iron phosphate anode material which is prepared by the preparation method of the lithium iron phosphate anode material.
As a limitation to the above technical scheme, the lithium iron phosphate positive electrode material has a core-shell structure, the core of the lithium iron phosphate positive electrode material is lithium iron phosphate, and the shell is a double-layer shell formed by a carbon/graphene composite and porous carbon which are coated on the surface of the lithium iron phosphate positive electrode material.
As a limitation to the above technical scheme, the coating amount of the shell is (1-5)%.
The lithium iron phosphate anode material obtained by the preparation method disclosed by the invention has a core-shell structure, and the surface of the core lithium iron phosphate is coated with a double-layer shell formed by the carbon/graphene compound and the porous carbon layer, so that the electrochemical performance, the tap density and the specific capacity of the lithium iron phosphate material are improved, and meanwhile, the rate capability and the cycle performance are improved, and the lithium iron phosphate anode material is suitable for a lithium ion battery with high specific energy density.
In summary, according to the preparation method of the lithium iron phosphate cathode material obtained by the technical scheme of the invention, the phenol/lithium iron phosphate precursor mixed solution is prepared, the aldehyde solution is added, then the hydrothermal reaction of phenol aldehyde condensation is performed under the condition of the high-pressure reaction kettle, the first lithium iron phosphate coating layer formed by the phenol aldehyde resin is obtained, the polyvinylpyrrolidone is coated on the surface of the first lithium iron phosphate coating layer to obtain the second lithium iron phosphate coating layer, and finally the spray drying and sintering are performed to obtain the lithium iron phosphate cathode material. The lithium iron phosphate anode material obtained by the invention has a core-shell structure, and the surface of the core lithium iron phosphate is coated with a double-layer shell formed by the carbon/graphene compound and the porous carbon layer, so that the electrochemical performance, the tap density and the specific capacity of the material are obviously improved, and simultaneously, the rate capability and the cycle performance are also improved, and the lithium iron phosphate anode material is suitable for a lithium ion battery with high specific energy density.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is an SEM image of a lithium iron phosphate positive electrode material obtained in a first embodiment of the present invention;
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
The embodiment relates to preparation of a lithium iron phosphate cathode material.
Example 1.1
The lithium iron phosphate anode material is prepared by the following steps:
a. obtaining a lithium iron phosphate precursor; the lithium iron phosphate precursor can be purchased directly or prepared by the following method: 10.4g of LiH2PO4、40.4gFe(NO3)3·9H2Dissolving O in 500ml of N, N-dimethylformamide, uniformly stirring to obtain a lithium iron phosphate precursor solution with the mass concentration of 10%, filtering, drying at 80 ℃ in vacuum, and sintering at 800 ℃ for 2h to obtain a lithium iron phosphate precursor;
b. preparing an intermediate material: uniformly mixing 30g of resorcinol, 500g of lithium iron phosphate precursor, 1000ml of graphene oxide conductive liquid with the concentration of 8mg/ml, 5g of sodium carbonate and 1g of oxalic dihydrazide to obtain a mixed solution, adding the mixed solution into 266ml of formaldehyde aqueous solution with the mass concentration of 3%, transferring the mixed solution into a high-pressure reaction kettle, reacting for 2 hours at the temperature of 150 ℃ and the pressure of 3Mpa, and drying and crushing to obtain an intermediate material;
c. preparing a lithium iron phosphate positive electrode material: adding 100g of the intermediate material into 1000ml of polyvinylpyrrolidone (PVP) solution with the mass concentration of 3%, uniformly dispersing, adding 50ml of potassium hydroxide solution with the mass concentration of 1% as a catalyst, fully dispersing, carrying out spray drying, transferring to a tubular furnace, heating to 800 ℃ in a hydrogen atmosphere, sintering for 6 hours, naturally cooling to room temperature, and crushing to obtain the lithium iron phosphate anode material.
Example 1.2
The lithium iron phosphate anode material is prepared by the following steps:
a. obtaining a lithium iron phosphate precursor; the lithium iron phosphate precursor can be purchased directly or prepared by the following method: 10.4g of LiH2PO4、40.4gFe(NO3)3·9H2Dissolving O in 500ml of N, N-dimethylformamide, uniformly stirring to obtain a lithium iron phosphate precursor solution with the concentration of 10%, filtering, drying in vacuum at 80 ℃, and sintering at high temperature of 800 ℃ for 2 hours to obtain a lithium iron phosphate precursor;
b. preparing an intermediate material: uniformly mixing 10g of 2-methylresorcinol, 500g of a lithium iron phosphate precursor, 1000ml of a graphene oxide conductive liquid with the concentration of 1mg/ml, 1g of potassium carbonate and 0.5g of malonic dihydrazide to obtain a mixed solution, adding the mixed solution into 500ml of an acetaldehyde aqueous solution with the mass concentration of 1%, transferring the acetaldehyde aqueous solution into a high-pressure reaction kettle, reacting for 1 hour at the temperature of 100 ℃ and the pressure of 5Mpa, and drying and crushing to obtain an intermediate material;
c. preparing a lithium iron phosphate positive electrode material: adding 100g of the intermediate material into 1000ml of 1% polyvinylpyrrolidone (PVP) solution, uniformly dispersing, adding 20ml of 0.5% sodium hydroxide solution serving as a catalyst, fully dispersing, performing spray drying, transferring to a tubular furnace, heating to 750 ℃ in a hydrogen atmosphere, sintering for 12 hours, naturally cooling to room temperature, and crushing to obtain the lithium iron phosphate cathode material.
Example 1.3
The lithium iron phosphate anode material is prepared by the following steps:
a. obtaining a lithium iron phosphate precursor; the lithium iron phosphate precursor can be purchased directly or prepared by the following method: 10.4g of LiH2PO4、40.4gFe(NO3)3·9H2Dissolving O in 500ml of N, N-dimethylformamide, uniformly stirring to obtain a lithium iron phosphate precursor solution with the concentration of 10%, filtering, drying in vacuum at 80 ℃, and sintering at high temperature of 800 ℃ for 2 hours to obtain a lithium iron phosphate precursor;
b. preparing an intermediate material: uniformly mixing 50g of 5-methylresorcinol, 500g of a lithium iron phosphate precursor, 1000ml of a graphene oxide conductive liquid with the concentration of 10mg/ml, 10g of sodium bicarbonate and 2g of glutaric dihydrazide to obtain a mixed solution, adding the mixed solution into 2000ml of a crotonaldehyde solution with the mass concentration of 5%, transferring the crotonaldehyde solution into a high-pressure reaction kettle, reacting for 3 hours at the temperature of 200 ℃ and the pressure of 1MPa, and drying and crushing to obtain an intermediate material;
c. preparing a lithium iron phosphate positive electrode material: adding 100g of the intermediate material into 1000ml of 5% polyvinylpyrrolidone (PVP) solution, uniformly dispersing, adding 20ml of 5% zinc chloride solution serving as a catalyst, fully dispersing, carrying out spray drying, transferring to a tubular furnace, heating to 850 ℃ in a hydrogen atmosphere, sintering for 1h, naturally cooling to room temperature, and crushing to obtain the lithium iron phosphate cathode material.
Comparative example
Comparative example 1
Adding 500g of lithium iron phosphate precursor into 2000ml of glucose solution with the mass concentration of 5%, stirring, filtering, transferring to a tubular furnace, heating to 750 ℃ in a hydrogen atmosphere, sintering for 12h, naturally cooling to room temperature, and crushing to obtain the lithium iron phosphate composite material.
Comparative example 2
Weighing 1.6g of resorcinol, dissolving the resorcinol in 250mL of deionized water, adding 3mL of formaldehyde solution with the mass fraction of 37%, adding 60g of lithium iron phosphate, and continuously stirring to uniformly disperse the lithium iron phosphate. Controlling the reaction temperature at 60 ℃, continuously reacting for 6 hours, stirring and evaporating the solution to dryness, and calcining the dried product at 600 ℃ for 2 hours under the protective atmosphere to obtain the lithium iron phosphate composite material.
Example two
The embodiment relates to performance detection of a lithium iron phosphate cathode material.
Example 2.1
And (3) performing SEM electron microscope test on the lithium iron phosphate cathode material prepared in the first embodiment, wherein as can be seen from fig. 1, the obtained lithium iron phosphate material is spherical, the size distribution is uniform, and the particle size is (1-5) mum.
Example 2.2
And (3) performing electrochemical performance test on the lithium iron phosphate positive electrode material samples prepared in the first embodiment and the comparative example.
Example 2.2.1
Button cell test
The test method comprises the following steps: weighing 2.0000g of each of five samples in examples 1.1-1.3 and comparative examples 1 and 2, respectively preparing each sample into a button cell, namely mixing 2.0000g of the sample with 0.1111g of conductive carbon black and 0.1111g of PVDF (according to the mass ratio of 0.9: 0.05), adding 2.5g of NMP (N-methyl pyrrolidone) as an organic solvent, fully and uniformly mixing, coating a film with the thickness of 140 micrometers on an aluminum foil, drying in vacuum at 120 ℃ for 2h, beating into a 5mm wafer by using a puncher, tabletting under 10Mpa by using a tabletting machine, keeping the vacuum at 120 ℃ for 12h, and weighing the weight of a positive plate. The button cell is assembled in an argon-protected glove box, a metal lithium sheet is taken as a negative electrode, an electrolyte is an EC (ethylene carbonate) and DMC (1, 2-dimethyl carbonate) mixed solvent with the volume ratio of 1:1, and an electrolyte LiPF is prepared6And the diaphragm is a Celgard2400 microporous polyethylene film. The assembled cell was tested for electrical performance on a blue tester. And in the voltage range of 2.5V-4.2V, charging/discharging at a constant current of 0.2C to test the specific capacity, and simultaneously carrying out charging at 0.2C and discharging at 10C to test the specific capacity. The results are shown in table 1, in which a1, a2, A3 and B1, B2 represent the button cells prepared by the five samples of examples 1.1 to 1.3 and comparative examples 1 and 2.
As can be seen from the results in table 1, the discharge capacity and the first efficiency of the lithium iron phosphate cathode material prepared in the first example are significantly higher than those of the lithium iron phosphate cathode material prepared in the comparative example 1, because the phenolic resin doped with the interlayer spacing on the surface of the material provides the transmission rate of lithium ions in the charge and discharge processes, the first efficiency and the gram capacity performance of the material are improved; meanwhile, the first coating layer with strong binding force and high density is generated through phenolic reaction, so that the tap density of the material is improved.
Example 2.2.2
Pouch cell testing
Respectively taking the samples of examples 1.1-1.3 and comparative examples 1 and 2 as positive electrode materials, taking artificial graphite as a negative electrode material, and adopting LiPF6A2.5 Ah cylindrical battery is prepared by using/EC + DEC (volume ratio of 1: 1) as an electrolyte, the concentration of the electrolyte is 1.3mol/L and a Celgard2400 membrane as a diaphragm, and the cycle performance of the material is tested.
Cycle performance test parameters: multiplying power charging and discharging multiplying power is 2.0C/2.0C, voltage range is 2.5-4.2V, temperature is 25 +/-3 ℃, cycle times are 500 times, and energy density of the battery is calculated.
The rate discharge performance of each sample was tested and the results are shown in table 2.
As can be seen from the results in table 2, the energy density of the battery prepared from the lithium iron phosphate positive electrode material of the first embodiment is significantly better than that of the batteries of the comparative examples 1 and 2, because the material of the first embodiment has higher specific capacity and tap density, and the energy density of the material is improved, and meanwhile, the lithium iron phosphate material has high density, strong structural stability and sufficient lithium ions, so that the cycle performance of the lithium iron phosphate material is improved.
Comparative example 2 a layer of compact coating layer was formed on the surface of lithium iron phosphate particles by the polymerization reaction of phenol-formaldehyde condensation to obtain modified lithium iron phosphate, so that the conductivity of the material and the electrochemical performance of the test were greatly improved, and the tap density and the gram volume were improved, but the material had a large rate performance deviation and a poor cycle performance under a large rate condition.
In conclusion, the lithium iron phosphate anode material obtained by the invention has a core-shell structure, the surface of the core lithium iron phosphate is coated with the double-layer shell, and the first coating layer is formed by the carbon/graphene compound, so that the conductivity and the electrochemical performance of the lithium iron phosphate are greatly improved, and the tap density and the gram volume are improved; meanwhile, the existence of graphene promotes the first coating layer to form an amorphous carbon layer with larger interlayer spacing along with the carbonization of phenolic substances in the forming process, so that the charging and discharging process is improvedThe intercalation and deintercalation rate of lithium ions, and the cycle performance; the porous carbon formed after PVP carbonization is used as the second coating layer, the defects caused by the first coating layer are overcome, the specific surface area of the material is reduced, suitable nanometer/micrometer holes are formed under the action of the catalyst, the liquid absorption and retention capacity of the lithium iron phosphate material is improved, and the conductivity of the material is improved while the cycle performance of the material is obviously improved. The lithium iron phosphate material obtained by the invention has a reversible specific capacity of 163mAh/g when discharged at a rate of 0.1C, a reversible specific capacity of more than 115mAh/g when discharged at a rate of 10C, and a tap density of 1.4g/cm3. Therefore, the lithium iron phosphate cathode material with high conductivity, high tap density, high specific capacity, good rate capability and excellent cycle performance can be prepared by the preparation method of the invention, and is suitable for the lithium ion battery with high specific energy density.
Claims (10)
1. A preparation method of a lithium iron phosphate positive electrode material is characterized by comprising the following steps:
a. obtaining a lithium iron phosphate precursor;
b. preparing an intermediate material: mixing a phenolic compound, a lithium iron phosphate precursor, a graphene oxide conductive liquid, a carbonate or bicarbonate compound and a functional additive, adding the obtained mixed solution into an aldehyde compound aqueous solution with the mass concentration of 1-5%, transferring the aldehyde compound aqueous solution into a high-pressure reaction kettle, reacting for 1-3 hours at the temperature of 100-200 ℃ and under the pressure of 1-5 Mpa, drying and crushing to obtain an intermediate material;
according to the mass ratio, the lithium iron phosphate precursor comprises a phenolic compound, an aldehyde compound, a graphene oxide solid, a carbonate or bicarbonate compound and a functional additive, wherein the functional additive is 500: 10-50: 50-100: 1-10: 0.5-2;
the concentration of the graphene oxide conducting solution is 1-10 mg/mL;
the functional additive is a hydrazide compound, and the hydrazide compound is at least one of oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, phthalic acid dihydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, pyromellitic acid trihydrazide and 1,2, 4-benzene trihydrazide;
c. preparing a lithium iron phosphate positive electrode material: adding 100 parts of intermediate material into 1000ml of polyvinylpyrrolidone solution with the mass concentration of 1-5%, uniformly dispersing, then adding 0.5-5 parts of catalyst, fully dispersing, performing spray drying, transferring to a tubular furnace, heating to 750-850 ℃ in a hydrogen atmosphere, sintering for 1-12 h, naturally cooling to room temperature, and crushing to obtain the lithium iron phosphate positive electrode material;
the catalyst is at least one of potassium hydroxide, sodium hydroxide and zinc chloride.
2. The method for preparing a lithium iron phosphate positive electrode material according to claim 1, characterized in that: the lithium iron phosphate precursor in the step a is prepared by the following steps:
10.4g of LiH2PO4、40.4gFe(NO3)3·9H2Dissolving O in 500ml of N, N-dimethylformamide, uniformly stirring to obtain a lithium iron phosphate precursor solution with the mass concentration of 10%, filtering, drying at 80 ℃ in vacuum, and sintering at 800 ℃ for 2h to obtain the lithium iron phosphate precursor.
3. The method for preparing a lithium iron phosphate positive electrode material according to claim 1, characterized in that: the phenolic compound in the step b is at least one of resorcinol, 2-methyl resorcinol, 5-methyl resorcinol, 2, 5-dimethyl resorcinol, 4-ethyl resorcinol, 4-chlorine resorcinol, 2-nitro resorcinol, 4-bromine resorcinol and 4-n-hexyl resorcinol.
4. The method for preparing a lithium iron phosphate positive electrode material according to claim 3, characterized in that: the phenolic compound is resorcinol and/or methyl resorcinol.
5. The method for preparing a lithium iron phosphate positive electrode material according to claim 1, characterized in that: in the step b, the aldehyde compound is at least one of formaldehyde, paraformaldehyde, polyacetal, acetaldehyde, paraldehyde, crotonaldehyde and acrolein.
6. The method for preparing a lithium iron phosphate positive electrode material according to claim 5, characterized in that: the aldehyde compound is formaldehyde and/or acetaldehyde.
7. The method for preparing a lithium iron phosphate positive electrode material according to claim 1, characterized in that: in the step b, the carbonate or bicarbonate compound is one of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
8. A lithium iron phosphate anode material is characterized in that: the lithium iron phosphate positive electrode material is prepared by the preparation method of the lithium iron phosphate positive electrode material as claimed in any one of claims 1 to 7.
9. The lithium iron phosphate positive electrode material according to claim 8, characterized in that: the lithium iron phosphate anode material has a core-shell structure, wherein the core is lithium iron phosphate, and the shell is a double-layer shell formed by a carbon-graphene compound and porous carbon which are coated on the surface.
10. The lithium iron phosphate positive electrode material according to claim 9, characterized in that: the mass fraction of the coating amount of the shell is 1-5%.
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