CN114613965A - Preparation method and application of lithium iron phosphate/carbon composite material - Google Patents
Preparation method and application of lithium iron phosphate/carbon composite material Download PDFInfo
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- CN114613965A CN114613965A CN202210281641.3A CN202210281641A CN114613965A CN 114613965 A CN114613965 A CN 114613965A CN 202210281641 A CN202210281641 A CN 202210281641A CN 114613965 A CN114613965 A CN 114613965A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 79
- 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 62
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 43
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 63
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 34
- 229910052742 iron Inorganic materials 0.000 claims description 30
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 claims description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims description 22
- 239000011574 phosphorus Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000005955 Ferric phosphate Substances 0.000 claims description 19
- 229940032958 ferric phosphate Drugs 0.000 claims description 19
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 19
- 239000012065 filter cake Substances 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 229930006000 Sucrose Natural products 0.000 claims description 7
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 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 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004537 pulping Methods 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims 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 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims 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 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 229940116007 ferrous phosphate Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 2
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052683 pyrite Inorganic materials 0.000 claims description 2
- 239000011028 pyrite Substances 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 239000002243 precursor Substances 0.000 abstract description 5
- 239000002344 surface layer Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 20
- 238000003756 stirring Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 241000190070 Sarracenia purpurea Species 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- -1 dihydrate ferric phosphate Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008570 general process Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000185 sucrose group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
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- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention belongs to the technical field of battery materials, and discloses a lithium iron phosphate/carbon composite material and a preparation method and application thereof. According to the carbon-containing iron phosphate precursor synthesized by the method, carbon is distributed in iron phosphate particles or between particles, and then the lithium iron phosphate material is further synthesized, so that conductive carbon bridges can be formed among the interior of the lithium iron phosphate particles, between the interior of the particles and the surface layer, and between the particles, and a transmission channel is provided for lithium ions and electrons, so that the electrochemical properties of the lithium iron phosphate such as conductivity and the like are improved.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a preparation method and application of a lithium iron phosphate/carbon composite material.
Background
The preparation method of the lithium iron phosphate is characterized in that iron phosphate is used as a precursor, lithium carbonate is used as a lithium source, glucose or other organic carbon is used as a carbon source, and the lithium iron phosphate is obtained through the working procedures of grinding, spray drying, sintering and the like. The common synthesis method of iron phosphate on the market is a precipitation method, namely, ferrous sulfate which is a byproduct of a titanium dioxide process is taken as an iron source, ammonium dihydrogen phosphate or phosphoric acid is taken as a phosphorus source, hydrogen peroxide is taken as an oxidant, and ammonia water or sodium hydroxide regulates and controls pH precipitation in the reaction process to obtain the iron phosphate. The dosage of the hydrogen peroxide is 1.2 to 1.5 times of the theoretical value generally, and the dosage of the hydrogen peroxide greatly improves the cost for synthesizing the iron phosphate.
Due to the structural characteristics of the lithium iron phosphate, the lithium iron phosphate has the defects of low lithium ion diffusion coefficient, low conductivity and the like. Aiming at the defects, the surface carbon coating can effectively improve the ionic and electronic conductivity of the surfaces and particles of the lithium iron phosphate particles; however, the problems of low lithium ion diffusion coefficient and low conductivity still exist between the internal particles and the surface layer of the internal lithium iron phosphate particles, and particularly, in order to improve the compaction density, a part of the internal particles are large particles.
In order to solve the above problems, there is a need to develop a method for preparing lithium iron phosphate that can improve the problems of low lithium ion diffusion coefficient and low electrical conductivity between the internal particles and the surface layer of the lithium iron phosphate.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a lithium iron phosphate/carbon composite material, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium iron phosphate/carbon composite material comprises carbon-doped lithium iron phosphate and a carbon layer coated on the surface of the carbon-doped lithium iron phosphate.
Preferably, the first discharge specific capacity of the lithium iron phosphate/carbon composite material is 156-162 mAh/g.
Preferably, the first charge-discharge efficiency of the lithium iron phosphate/carbon composite material is 97-99%.
A preparation method of a lithium iron phosphate/carbon composite material comprises the following steps:
(1) mixing an iron source solution and a phosphorus source, heating, adding a carbon source, continuously heating for reaction, adding an oxidant, continuously reacting, carrying out solid-liquid separation, and taking a solid phase to obtain a carbon-containing iron phosphate filter cake;
(2) pulping the carbon-containing iron phosphate filter cake, carrying out solid-liquid separation, washing and drying to obtain carbon-doped iron phosphate dihydrate;
(3) and mixing the carbon-doped iron phosphate dihydrate, a lithium source and a carbon source, and calcining to obtain the lithium iron phosphate/carbon composite material.
Preferably, in the step (1), the iron source in the iron source solution is at least one of elemental iron, ferrous chloride, ferrous sulfate, ferric nitrate, ferrous acetate, ferrous phosphate, pyrite, waste ferric phosphate, and phosphorous iron slag.
Further preferably, the elementary substance of iron is one of iron powder and iron sheet.
Preferably, in step (1), the phosphorus source is at least one of phosphoric acid, phosphorous acid, sodium hypophosphite, ammonium hydrogen phosphate, ammonium dihydrogen phosphate or ammonium phosphate.
Further preferably, the phosphorus source is at least one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, or ammonium phosphate.
Preferably, in the step (1), the molar ratio of iron to phosphorus after the iron source solution and the phosphorus source are mixed is (0.92-1.03): 1.
further preferably, the molar ratio of iron to phosphorus after the iron source solution and the phosphorus source are mixed is (0.97-1): 1.
preferably, in the step (1), the temperature is raised to 40-50 ℃.
Carbon can be used as a crystal nucleus point at the temperature of 40-50 ℃, and carbon-containing iron phosphate dihydrate can be gradually and slowly generated.
Preferably, in the step (1), the carbon source is at least one of graphite, carbon nanotubes, graphene, carbon powder or acetylene black.
Further preferably, the carbon source is at least one of graphite, carbon nanotubes or carbon powder.
Preferably, in the step (1), the temperature of the reaction is 70-100 ℃; further preferably, the temperature of the reaction is 80-95 ℃.
Preferably, in step (1), the reaction time is 1-2 h.
Preferably, in the step (1), the oxidant is at least one of hydrogen peroxide, oxygen, sodium peroxide or ammonium persulfate.
Further preferably, the oxidant is at least one of hydrogen peroxide and oxygen.
Preferably, in step (1), the temperature for the continued reaction is 70-100 ℃.
Preferably, in the step (1), the time for continuing the reaction is 2-10h, and further preferably, the time for continuing the reaction is 4-8 h.
Preferably, in the step (2), the carbon-containing iron phosphate filter cake and water are slurried according to a solid-to-liquid ratio of 1g (5-10) mL to obtain the carbon-containing iron phosphate slurry.
Preferably, in the step (2), the filtrate after solid-liquid separation is washed until the conductivity of the filtrate is less than or equal to 500 mu s/cm.
Further preferably, the washing is to wash the filtrate after the solid-liquid separation until the conductivity of the filtrate is less than or equal to 200 mus/cm.
Preferably, in the step (2), the drying temperature is 60-120 ℃, and further preferably, the drying temperature is 90-110 ℃.
Preferably, in the step (2), the specific surface area of the carbon-doped ferric phosphate dihydrate is 12-20m2G and Dv50 of 3.5-4.2 cm.
Preferably, in the step (3), the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium dihydrogen phosphate.
Preferably, in the step (3), the carbon source is at least one of glucose, sucrose, starch, carbon black or graphene.
Further preferably, the carbon source is sucrose.
Preferably, in the step (3), the temperature of the calcination is 650-.
Preferably, in the step (3), the calcination time is 6-16h, and further preferably, the calcination time is 6-10 h.
Preferably, in step (3), the atmosphere of the calcination is an inert atmosphere, and further preferably, the atmosphere of the calcination is a nitrogen atmosphere.
Preferably, step (3) further comprises sanding and spray drying before the calcining.
The invention also provides a battery which comprises the lithium iron phosphate/carbon composite material.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the carbon-containing iron phosphate precursor synthesized by the method, carbon is distributed in iron phosphate particles or between particles, and then the carbon-coated and carbon-doped lithium iron phosphate material is further synthesized, so that conductive carbon bridges can be formed among the interiors of the lithium iron phosphate particles, between the interiors of the particles and a surface layer, and between the particles, and a transmission channel is provided for lithium ions and electrons, so that the electrochemical properties such as the conductivity and the like of the lithium iron phosphate are improved.
2. According to the invention, an iron source solution and a phosphorus source are mixed, a carbon source is heated and added, then the temperature is continuously raised, part of ferrous ions in the iron source solution can participate in reaction, after the reaction is carried out for a period of time, an oxidant is added, and then the reaction is continuously carried out to generate a carbon-doped orthorhombic system ferric phosphate precursor, the use amount of the oxidant is greatly reduced in the process, the carbon-doped orthorhombic system ferric phosphate, the carbon source and the lithium source are calcined to prepare the lithium iron phosphate/carbon material, the precursor is the carbon-doped orthorhombic system ferric phosphate, lithium intercalation is facilitated in a sintering process, the diffusion coefficient of lithium ions between inner particles and a surface layer is improved, dehydration is not required, the cost is lower, and the lithium iron phosphate/carbon composite material with excellent electrochemical performance is prepared.
Drawings
FIG. 1 is an SEM photograph of carbon-doped ferric phosphate dihydrate prepared in example 1 of the present invention;
fig. 2 is a schematic diagram of carbon distribution in the lithium iron phosphate/carbon composite material prepared in embodiment 1 of the present invention;
FIG. 3 is an XRD pattern of carbon-doped iron phosphate dihydrate prepared according to example 1 of the present invention;
FIG. 4 is an SEM photograph of ferric phosphate dihydrate prepared in comparative example 1 of the present invention;
FIG. 5 is an XRD pattern of iron phosphate dihydrate prepared by comparative example 1 of the present invention;
fig. 6 is an SEM image of the lithium iron phosphate/carbon composite material prepared in example 1 of the present invention;
fig. 7 is an XRD pattern of the lithium iron phosphate/carbon composite material prepared in example 1 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The preparation method of the lithium iron phosphate/carbon composite material comprises the following specific steps:
(1) preparing mixed metal liquid: adding ferrous sulfate into a stirring tank to prepare a solution with the iron concentration of 35g/L, then adding phosphoric acid to prepare a solution with the phosphorus concentration of 20g/L, and uniformly stirring to obtain 70L of mixed metal liquid containing iron and phosphorus;
(2) pouring 70L of prepared iron-phosphorus-containing mixed liquid into a reaction container, stirring, starting to adjust to 450rpm, heating to 90 ℃, adding 82g of carbon nano tube, heating to 90 ℃, keeping the temperature at 90 ℃ for 2h, then dropwise adding hydrogen peroxide, wherein the dosage of hydrogen peroxide is 1.25kg, and after the reaction is finished, performing solid-liquid separation on filtrate by using a suction filtration bottle to obtain a carbon-containing iron phosphate filter cake;
(3) putting the carbon-containing iron phosphate filter cake obtained by separation into a pulping water cup, adding deionized water, uniformly stirring, filtering, repeatedly cleaning with the deionized water until the conductivity of the washing water is less than 500 mu s/cm, stopping washing, spreading the filter cake, and drying in a drying oven at 100 ℃ to obtain carbon-doped iron phosphate dihydrate;
(4) weighing 9.42kg of carbon-doped iron phosphate dihydrate, 1.88kg of lithium carbonate and 580g of sucrose, mixing, sanding and spraying to obtain powder, placing the powder into a box furnace, and calcining at 700 ℃ for 6 hours in a nitrogen atmosphere to obtain the lithium iron phosphate/carbon composite material.
Example 2
The preparation method of the lithium iron phosphate/carbon composite material comprises the following specific steps:
(1) preparing mixed metal liquid: adding ferrous sulfate into a stirring tank to prepare a solution with the iron concentration of 39g/L, then adding phosphoric acid to prepare a solution with the phosphorus concentration of 22.3g/L, and uniformly stirring to obtain a mixed metal liquid containing iron and phosphorus;
(2) pouring 70L of prepared iron-phosphorus-containing mixed liquid into a reaction container, stirring, starting to adjust to 450rpm, heating to 90 ℃, adding 457g of graphite, heating to 90 ℃, keeping the temperature at 90 ℃ for 2h, introducing oxygen, oxidizing for 2h, and after the reaction is finished, separating solid and filtrate by using a suction filtration bottle to obtain a carbon-containing iron phosphate filter cake;
(3) putting the carbon-containing iron phosphate filter cake obtained by separation into a pulping water cup, adding deionized water, uniformly stirring, filtering, repeatedly cleaning with the deionized water until the conductivity of the washing water is less than 500 mu s/cm, stopping washing, spreading the filter cake, and drying in a drying oven at 100 ℃ to obtain carbon-doped iron phosphate dihydrate;
(4) weighing 9.42kg of carbon-doped ferric phosphate dihydrate, 1.88kg of lithium carbonate and 580 kg of sucrose, mixing, sanding and spraying to obtain powder, placing the powder into a box furnace, and calcining at 710 ℃ for 6 hours in a nitrogen atmosphere to obtain the lithium iron phosphate/carbon composite material.
Example 3
The preparation method of the lithium iron phosphate/carbon composite material comprises the following specific steps:
(1) preparing mixed metal liquid: adding ferrous sulfate into a stirring tank to prepare a solution with the iron concentration of 38.4g/L, then adding phosphoric acid to prepare a solution with the phosphorus concentration of 21.9g/L, and uniformly stirring to obtain a mixed metal solution containing iron and phosphorus;
(2) pouring 70L of prepared iron-phosphorus-containing mixed liquid into a reaction container, stirring, starting to adjust to 450rpm, heating to 90 ℃, adding 457g of graphite, heating to 90 ℃, keeping the temperature at 90 ℃ for 2 hours, then dropwise adding hydrogen peroxide, wherein the dosage of hydrogen peroxide is 1.36kg, and after the reaction is finished, performing solid-liquid separation on filtrate by using a suction filtration bottle to obtain a carbon-containing iron phosphate filter cake;
(3) putting the carbon-containing iron phosphate filter cake obtained by separation into a pulping water cup, adding deionized water, uniformly stirring, filtering, repeatedly cleaning with the deionized water until the conductivity of the washing water is less than 500 mu s/cm, stopping washing, spreading the filter cake, and drying in a drying oven at 100 ℃ to obtain carbon-doped iron phosphate dihydrate;
(4) 9.42kg of carbon-doped iron phosphate dihydrate, 1.88kg of lithium carbonate and 580g of sucrose are weighed, mixed, sanded and sprayed to obtain powder, and then the powder is placed into a box furnace and is calcined at 710 ℃ for 6 hours in a nitrogen atmosphere to obtain the lithium iron phosphate/carbon composite material.
Comparative example 1 (addition of oxidizing agent before formation of iron phosphate dihydrate)
The preparation method of the lithium iron phosphate/carbon composite material comprises the following specific steps:
(1) preparing mixed metal liquid: adding ferrous sulfate into a stirring tank to prepare a solution with the iron concentration of 35g/L, then adding phosphoric acid to prepare a solution with the phosphorus concentration of 20g/L, and uniformly stirring to obtain a mixed metal liquid containing iron and phosphorus;
(2) pouring 70L of prepared mixed metal liquid containing iron and phosphorus into a reaction container, adding 3.7kg of hydrogen peroxide for fully oxidizing ferrous iron, stirring and turning on to adjust to 450rpm after oxidation is finished, adding alkali liquor to adjust the pH to 2.0, heating to 90 ℃, aging for 4 hours, and separating solid and filtrate by using a filter flask to obtain an iron phosphate filter cake;
(3) putting the iron phosphate filter cake obtained by separation into a pulping water cup, adding deionized water, uniformly stirring, filtering, repeatedly cleaning with the deionized water until the conductivity of the washing water is less than 500 mu s/cm, stopping washing, spreading the filter cake, and drying in an oven at 100 ℃ to obtain ferric phosphate dihydrate;
(4) weighing 7.54kg of ferric phosphate dihydrate, 1.88kg of lithium carbonate and sucrose, mixing, sanding and spraying to obtain powder, then placing the powder into a box furnace, and calcining the powder at 700 ℃ for 6 hours in a nitrogen atmosphere to obtain the lithium iron phosphate/carbon composite material.
And (3) physicochemical results:
table 1 shows the results of physicochemical analyses of iron phosphate dihydrate products prepared in examples 1, 2 and 3 and comparative example 1. As can be seen from table 1, the C contents of the iron phosphate dihydrate products prepared in the examples were 1.024%, 4.981%, and 5.149%, respectively.
FIG. 1 is an SEM photograph of carbon-doped ferric phosphate dihydrate prepared according to example 1 of the present invention; it can be seen from the figure that the iron phosphate of example 1 consists of prismatic, polygonal particles.
Fig. 2 is a schematic diagram of the distribution of carbon in lithium iron phosphate prepared in embodiment 1 of the present invention; fig. 2 can obtain the distribution of carbon in lithium iron phosphate, with the carbon distributed within the iron phosphate particles or between particles.
FIG. 3 is an XRD pattern of carbon-doped iron phosphate dihydrate prepared according to example 1 of the present invention; it can be seen from the figure that the product obtained in example 1 is orthorhombic dihydrate ferric phosphate, which is different from monoclinic dihydrate ferric phosphate obtained by the general process; the bottom map is a ferric phosphate dihydrate standard card map.
FIG. 4 is an SEM photograph of ferric phosphate dihydrate prepared by comparative example 1 of the present invention; it can be seen from the figure that the iron phosphate dihydrate of comparative example 1 is formed by agglomeration of flake primary particles.
FIG. 5 is an XRD pattern of iron phosphate dihydrate prepared by comparative example 1 of the present invention. It can be seen from the figure that the product obtained in comparative example 1 is monoclinic ferric phosphate dihydrate; the bottom map is a ferric phosphate dihydrate standard card map.
Fig. 6 is an SEM of lithium iron phosphate/carbon prepared in example 1 of the present invention. It can be seen from the figure that the lithium iron phosphate of example 1 is composed of spherical particles having a rounded surface.
Fig. 7 is an XRD pattern of lithium iron phosphate/carbon prepared in example 1 of the present invention. It can be seen from the figure that the lithium iron phosphate obtained in example 1 is a pure-phase orthorhombic lithium iron phosphate.
And (3) physicochemical results:
table 1 shows the results of physicochemical analyses of iron phosphate dihydrate products prepared in examples 1, 2 and 3 and comparative example 1. As can be seen from table 1, the C contents of the iron phosphate dihydrate products prepared in the examples were 1.024%, 4.981%, and 5.149%, respectively. Fig. 2 is an SEM image of the iron phosphate of example 1, and it can be seen from the figure that the iron phosphate of example 1 is composed of prismatic, polygonal particles. Fig. 3 is an XRD pattern of the iron phosphate dihydrate of example 1, and it can be seen from the XRD pattern that the product obtained in example 1 is orthorhombic iron phosphate dihydrate, which is different from monoclinic iron phosphate dihydrate obtained by a general process. FIG. 4 is an SEM photograph of the iron phosphate dihydrate of comparative example 1, from which it can be seen that the iron phosphate dihydrate of comparative example 1 is formed by agglomeration of flaky primary particles. Fig. 5 is an XRD pattern of the iron phosphate dihydrate of comparative example 1, and it can be seen that the product obtained in comparative example 1 is monoclinic iron phosphate dihydrate.
TABLE 1 physicochemical results in iron phosphate dihydrate product
| Example 1 | Example 2 | Example 3 | Comparative example 1 | |
| Fe/％ | 29.3 | 29.05 | 29.16 | 29.13 |
| P/％ | 16.6 | 16.29 | 16.44 | 16.51 |
| Fe/P | 0.978 | 0.988 | 0.983 | 0.978 |
| C/％ | 1.257 | 4.981 | 5.149 | 0 |
| Dv50 | 3.99 | 3.57 | 4.05 | 2.79 |
| BET | 13 | 17.5 | 15 | 45.8 |
Table 2 shows the comparison between the hydrogen peroxide used in example 1 and the hydrogen peroxide used in the comparative example, and it can be seen from the table that the hydrogen peroxide used in the comparative example is almost 3 times the hydrogen peroxide used in the example in the same volume of the metal liquid with the same iron concentration. The embodiment 1 greatly reduces the consumption of hydrogen peroxide, reduces the cost, obtains the ferric phosphate dihydrate of an orthorhombic system and is beneficial to the intercalation of lithium.
Table 2 comparison of hydrogen peroxide amounts for example 1 and comparative example 2
Electrochemical performance:
fig. 1 is a schematic diagram of carbon distribution of lithium iron phosphate particles, a carbon bridge is arranged inside the particles, and a carbon coating layer is arranged on the surface of the particles, so that the carbon distribution can connect crystal grains inside the particles with crystal grains, the crystal grains with the surfaces of the particles, and the particles with one another, and provides a lithium ion and electron transmission channel, thereby improving the electrochemical performance of the lithium iron phosphate.
Table 3 shows the electrochemical performance of the lithium iron phosphate batteries prepared in examples 1, 2, and 3 and the comparative example, and the specific data is obtained by testing the devices such as an electrochemical workstation. As can be seen from table 2, the electrochemical performance of the lithium iron phosphate product prepared in the example is obviously better than that of comparative example 1, especially example 1.
TABLE 3 comparison of electrochemical Performance of lithium iron phosphate batteries
| Electrochemical performance | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| Specific capacity of first discharge (mAh/g) | 159.2 | 157.8 | 156.4 | 153.4 |
| First charge-discharge efficiency (%) | 98.7 | 97.6 | 97.2 | 95.6 |
| 0.5C specific discharge capacity (mAh/g) | 153 | 151.7 | 150.9 | 140 |
| 1C specific discharge capacity (mAh/g) | 147.7 | 145.2 | 144.8 | 132.1 |
| Specific volume of 2C dischargeQuantity (mAh/g) | 139.4 | 136 | 135.1 | 116.4 |
| 5C specific discharge capacity (mAh/g) | 129.6 | 123 | 121 | 98.5 |
| 10C specific discharge capacity (mAh/g) | 118.9 | 111.7 | 108.3 | 80.5 |
The present invention is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A lithium iron phosphate/carbon composite material is characterized by comprising carbon-doped lithium iron phosphate and a carbon layer coated on the surface of the carbon-doped lithium iron phosphate.
2. The lithium iron phosphate/carbon composite material as claimed in claim 1, wherein the first discharge specific capacity of the lithium iron phosphate/carbon composite material is 156-162 mAh/g.
3. The lithium iron phosphate/carbon composite material according to claim 1, wherein the lithium iron phosphate/carbon composite material has a first charge-discharge efficiency of 97 to 99%.
4. The method for preparing a lithium iron phosphate/carbon composite material according to any one of claims 1 to 3, comprising the steps of:
(1) mixing an iron source solution and a phosphorus source, heating, adding a carbon source, continuously heating for reaction, adding an oxidant, continuously reacting, carrying out solid-liquid separation, and taking a solid phase to obtain a carbon-containing iron phosphate filter cake;
(2) pulping the carbon-containing iron phosphate filter cake, carrying out solid-liquid separation, washing and drying to obtain carbon-doped iron phosphate dihydrate;
(3) and mixing the carbon-doped iron phosphate dihydrate, a lithium source and a carbon source, and calcining to obtain the lithium iron phosphate/carbon composite material.
5. The preparation method according to claim 4, wherein in the step (1), the iron source in the iron source solution is at least one of elemental iron, ferrous chloride, ferrous sulfate, ferric nitrate, ferrous acetate, ferrous phosphate, pyrite, waste ferric phosphate and phosphorus-iron slag; the phosphorus source is at least one of phosphoric acid, phosphorous acid, sodium hypophosphite, ammonium hydrogen phosphate, ammonium dihydrogen phosphate or ammonium phosphate.
6. The method according to claim 4, wherein in the step (1), the molar ratio of iron to phosphorus in the mixture of the iron source solution and the phosphorus source is (0.92-1.03): 1; the temperature of the continuous reaction is 70-100 ℃, and the time of the continuous reaction is 2-10 h.
7. The preparation method according to claim 4, wherein in the step (1), the carbon source is at least one of graphite, carbon nanotubes, graphene, carbon powder or acetylene black; the oxidant is at least one of hydrogen peroxide, oxygen, sodium peroxide or ammonium persulfate.
8. The production method according to claim 4, wherein in step (3), the lithium source is at least one of lithium carbonate, lithium hydroxide, or lithium dihydrogen phosphate.
9. The method according to claim 4, wherein in the step (3), the carbon source is at least one of glucose, sucrose, starch, carbon black, and graphene.
10. A battery comprising the lithium iron phosphate/carbon composite material according to any one of claims 1 to 3.
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| WO2023179046A1 (en) * | 2022-03-22 | 2023-09-28 | 宜昌邦普循环科技有限公司 | Preparation method for lithium iron phosphate/carbon composite material and use thereof |
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