CN105552340B - A kind of anode material for lithium-ion batteries and preparation method thereof - Google Patents
A kind of anode material for lithium-ion batteries and preparation method thereof Download PDFInfo
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- CN105552340B CN105552340B CN201610074046.7A CN201610074046A CN105552340B CN 105552340 B CN105552340 B CN 105552340B CN 201610074046 A CN201610074046 A CN 201610074046A CN 105552340 B CN105552340 B CN 105552340B
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000010405 anode material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 229910010931 LiFexMnyPO4 Inorganic materials 0.000 claims abstract description 11
- 239000011368 organic material Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 5
- 239000011247 coating layer Substances 0.000 claims abstract description 4
- 239000011572 manganese Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 239000013049 sediment Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 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 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims 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 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- 239000002131 composite material Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 12
- 150000001722 carbon compounds Chemical class 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 16
- 229910052744 lithium Inorganic materials 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 229910019142 PO4 Inorganic materials 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000001694 spray drying Methods 0.000 description 7
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000011656 manganese carbonate Substances 0.000 description 6
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 6
- 229910052603 melanterite Inorganic materials 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910011844 LiFe0.25Mn0.75PO4 Inorganic materials 0.000 description 3
- 229910011990 LiFe0.5Mn0.5PO4 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910000901 LiFePO4/C Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 229910000904 FeC2O4 Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 229910009891 LiAc Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of anode material for lithium-ion batteries and preparation method thereof, anode material for lithium-ion batteries LiFexMnyPO4/ C is spherical structure, and outer surface is carbon coating layer, and inside includes LiFexMnyPO4Nano-particle, the particle diameter of the anode material for lithium-ion batteries are 5 15 μm, and carbon content is 0.5% 10%, and tap density is 1.3 1.6g/cm3, wherein 0 ＜ x≤0.5,0.5≤y ＜ 1, x+y=1.The present invention is prepared for nanoscale LiFe by hydro-thermal solvent-thermal method firstxMnyPO4Material, then by carbonaceous organic material and nanoscale LiFexMnyPO4After material mixing, it is spray-dried, then the carbon compound of material surface is transformed into High-conductivity carbon material after high-temperature calcination.Composite positive pole produced by the present invention has excellent chemical property, has good application value for power lithium-ion battery.
Description
Technical field
The present invention relates to technical field of lithium-ion battery, and in particular to a kind of anode material for lithium-ion batteries and its system
Preparation Method.
Background technology
Extensively should with lack of energy and to environmental protection requirement, lithium ion battery as a kind of cleaning, green battery
With, and anode material for lithium-ion batteries is limiting lithium ion cell extensive use in terms of power, current commercialized positive pole material
LiFePO4 has good security, environment-friendly, rate charge-discharge characteristic and good cycling stability, abundant raw materials cheap in material
The advantages that, but its discharge voltage plateau is relatively low (3.4V), is played so as to have impact on its energy density.And lithium manganese phosphate has equally
Olivine structural, theoretical gram volume is close to 170mAh/g, and its discharge voltage plateau is higher (4.1V), and theoretical energy density reaches
697Whkg-1, than the energy density (578Whkg of LiFePO4-1) 20% is higher by, but because it has Mn in charge and discharge process3 +Jahn-Teller effects cause the distortion of lattice, Mn3+Dissolving and lower lithium ion diffusion rate and electronic conductance
The unfavorable factors such as rate, so as to cause electrical property effectively to play, it is possible to reference to the advantage of the two, Reasonable Regulation And Control Mn and Fe
Ratio, by a part Mn substitute Fe to prepare the lithium ferric manganese phosphate positive pole material with high-energy-density and high conductance
Material.
Preparation method existing many on the synthetic method of lithium ferric manganese phosphate at present, early in 2005, publication No. was
CN1632970A patent document discloses a kind of preparation method of high-density spherical ferric lithium phosphate and iron manganese phosphate for lithium, its method
It is first to add ferrous sulfate, phosphorus source, complexing agent or wherein manganese sulfate, mixture aqueous solution is made into after mixing in proportion,
Synthesis ferrous ammonium phosphate or manganese phosphate ferrous ammonium presoma are reacted with ammonia spirit again, with lithium carbonate with mol ratio after washing is dry
1:1 uniformly mixing, nitrogen atmosphere protection under, by 600~900 DEG C of high-temperature heat treatments obtain within 8~48 hours LiFePO4 or
Iron manganese phosphate for lithium.But have in the above method using ammoniacal liquor, cause that preparation condition is sometimes uncontrolled, operating environment is poor,
It is not easy industrialized production.
Publication No. is that CN 103280579A patent document discloses a kind of high performance lithium ion battery anode material phosphoric acid
Ferrimanganic lithium and preparation method thereof.It will be prepared using solid phase method after single source of iron, manganese source, lithium source, phosphorus source and carbon source ball milling mixing
Go out lithium ferric manganese phosphate/carbon matrix precursor, then prepare Fe/Mn=4 by double sintering:6 lithium ferric manganese phosphate/carbon composite.
But iron reaches with manganese that molecular level is other to be mixed simply by ball grinding method in the lithium ferric manganese phosphate prepared using this method, it is difficult to
Reach iron to mix with the uniform of manganese atom rank, cause the uniformity of material poor.
It is that a kind of spray drying process prepares high-performance that publication No. discloses for the A of CN 104701536 patent document
The technique of LiFePO4/C anode material of lithium battery.Its technical scheme is：By toward adding polyvinyl alcohol in precursor solution
(PVA) additive is as auxiliary template, is successfully prepared for high performance having two level using organic matter assistant spray seasoning
The spherical LiFePO4/C anode material of lithium battery of structure.Optimize PVA addition and presoma sintering temperature simultaneously, improve work
Skill, adapt to the needs of industrialization large-scale production.The characteristics of invention is：The sample material prepared using PVA as organic additive
Material is not only with beautiful pattern but also with very excellent chemical property.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of anode material for lithium-ion batteries LiFexMnyPO4/ C and its system
Preparation Method, the chemical property of material is not only increased using the preparation method of the present invention, while also improve the jolt ramming of material
Density, there is good application value for power lithium-ion battery.
A kind of anode material for lithium-ion batteries, it is spherical structure, outer surface is carbon coating layer, and inside includes LiFexMnyPO4
Nano-particle, the particle diameter of the anode material for lithium-ion batteries is 5-15 μm, carbon content 0.5%-10%, and tap density is
1.3-1.6g/cm3, wherein 0 ＜ x≤0.5,0.5≤y ＜ 1, x+y=1.
Preferably, the particle diameter of the anode material for lithium-ion batteries is 11.8-14.2 μm, carbon content 1.9-3.2%,
Tap density is 1.32-1.54g/cm3。
LiFe provided by the inventionxMnyPO4/ C composite positive pole material with carbon-coated surface is uniform, has higher specific capacity,
It can reach more than 150mAh/g；Coulombic efficiency is more than 95% first；100 conservation rates are circulated under 0.5C more than 94%.
Preferably, the LiFexMnyPO4The particle diameter 200-300nm of nano-particle.
Present invention also offers a kind of preparation method of anode material for lithium-ion batteries, comprise the following steps：
(1) hydro-thermal solvent heat is carried out as raw material using Li source compound, Fe source compound, manganese source compound, P source compound
Reaction, after the sediment washing of generation, drying, it is well mixed with the carbonaceous organic material aqueous solution, is spray-dried and powder is made；
(2) under gas shield, the powder is calcined, after the carbonaceous organic material carbonization, naturally cools to room
Temperature, then by grinding, sieving, the anode material for lithium-ion batteries is made.
The preparation method of the present invention is prepared for nanoscale LiFe by hydro-thermal solvent-thermal method firstxMnyPO4Material, then will
Carbonaceous organic material and nanoscale LiFexMnyPO4After material carries out mixed at high speed, it is spray-dried, spray drying can not only
By nanoscale LiFexMnyPO4Material is gathered into micron-sized ball-type second particle, at the same time effectively can will contain carbon geochemistry
Thing evenly spreads to nanoscale LiFexMnyPO4The surface of material, the carbon compound transformation of material surface after high-temperature calcination
Into High-conductivity carbon material.
Preferably, in step (1), Li source compound, Fe source compound, manganese source compound, P source compound are according to Li：
Fe：Mn：P mol ratios are 3.0：x：y：1.0 mixing, wherein 0 ＜ x≤0.5,0.5≤y ＜ 1, x+y=1.It is more highly preferred to, x is
0.5 or 0.25.
The Li source compound is Li2CO3、LiNO3, one or several kinds in LiOH or LiAc.
The Fe source compound is FeC2O4、Fe(Ac)2、FeSO4、FeCl2Or Fe (NO3)2In one or several kinds.
The manganese source compound is MnSO4、MnCl2、MnCO3In one or several kinds.
Phosphorus source compound is H3PO4、NH4H2PO4、(NH4)2HPO4In one or several kinds.
Preferably, the hydro-thermal solvent thermal reaction is using the mixture of organic solvent and water as reaction medium, wherein having
Solvent and the volume ratio of water are 1：1-10.In this reaction medium, it can not only effectively shorten the migration distance of lithium ion, and
And Fe and Mn mixing reaches the mixing of atomic level in this method, make final product dispersiveness and uniformity good.It is described organic
Solvent is the one or several kinds in methanol, ethanol, glycerine, polyethylene glycol.More preferably, the volume ratio of glycerine and water is
1：1.
PH value in reaction adjusted between 6.0~12.0 by inorganic acid after raw material mixing, finally by reactor seal to
Reacted 5~24 hours at 140~240 DEG C.Preferably, pH value is 8.0~10.0, more preferably, pH value is 8.0.It is described
Inorganic acid is HCl, H2SO4、H3PO4、HAc、H2C2O4In one or several kinds.
In step (1), it is neutral that the sediment that reacts to obtain, which need to be cleaned with deionized water to the pH value of solution, then will cleaning
It is nanoscale LiFe that sediment afterwards obtains pale solid powder in 2~12 hours in 60~120 DEG C of vacuum dryingxMnyPO4
Material.
Preferably, the carbonaceous organic material is one kind in glucose, sucrose, ascorbic acid, polyvinyl alcohol or starch
It is or several.
Preferably, in step (1), the mass ratio of sediment and carbonaceous organic material is 100：1-20.More preferably, precipitation
The mass ratio of thing and glucose is 100：10.
Preferably, in step (2), the gas is N2、Ar、Ar/H2Mixed gas or N2/H2Mixed gas.
Preferably, in step (2), the condition of calcining is to be heat-treated 1~24 hour at 400~800 DEG C.
The beneficial effect that the present invention possesses：(1) present invention prepares nanometer LiFe using hydro-thermal solvent-thermal methodxMnyPO4, wherein
Fe and Mn mixing reaches the mixing of atomic level, makes final product dispersiveness and uniformity good；(2) improved by being spray-dried
Composite tap density, while carbon compound is dispersed in second particle surface, be advantageous to subsequent calcination and formed
Whole carbon coating layer, improve electric conductivity；(3) preparation method technical process of the invention is simple and easy, cheap, beneficial to reality
Apply, be very suitable for being commercialized popularization and application.
Brief description of the drawings
Fig. 1 is lithium ion anode material preparation principle schematic diagram of the present invention.
Fig. 2 is ball-type LiFe of the present invention0.5Mn0.5PO4The SEM figures of/C composite positive poles.
Fig. 3 is Fig. 2 LiFe0.5Mn0.5PO4The enlarged drawing of/C composite positive pole SEM figures.
Fig. 4 is the XRD elementary analysis figures that composite is made in embodiment 3.
Embodiment
With reference to embodiment, the invention will be further described, it is necessary to it is pointed out here that be that following examples can only be used
In the further explanation for the present invention, it is impossible to be interpreted as being defined protection scope of the present invention, on this basis non-
The modifications and adaptations of essence still belong to protection scope of the present invention.
In order to reach the technical purpose of the present invention, the technical solution adopted by the present invention is as shown in figure 1, can specifically include such as
Lower step：
Embodiment one
With LiOHH2O、FeSO4·7H2O、MnCO3、H3PO4It is Li according to mol ratio for base stock：Fe：Mn：P=
3.0：0.5：0.5：1 is added separately to volume ratio as 1：Reaction is moved into after being stirred 30 minutes in 1 water and glycerine mixed solution
180 DEG C are heated in kettle, is reacted 5 hours, above-mentioned reactant concentration is calculated as 0.5mol/L with lithium concentration, and passes through H2SO4Adjust
It is 8 to save reactant pH value.
After the completion for the treatment of above-mentioned reaction, in being by the pH value that the sediment of generation is cleaned to solution with deionized water and ethanol
Property, obtained sediment obtains pale powder after being dried 5 hours under 100 DEG C of vacuum conditions, by above-mentioned pale powder with
Glucose is according to mass ratio 100:10 are added in deionized water, and mixing is spray-dried after 2 hours, then by spray drying
Powder is in H2Room temperature is naturally cooled to after being heat-treated 10 hours under the conditions of 600 DEG C under the protection of/Ar mixed gas, finely ground, mistake
Sieve, that is, obtain ball-type LiFe0.5Mn0.5PO4/ C composite positive poles.SEM electron-microscope scannings result is as shown in Figure 2 and Figure 3.
Embodiment two
With LiOHH2O、FeSO4·7H2O、MnCO3、H3PO4It is Li according to mol ratio for base stock：Fe：Mn：P=
3.0：0.5：0.5：1 is added separately to volume ratio as 1：Reaction is moved into after being stirred 30 minutes in 1 water and glycerine mixed solution
180 DEG C are heated in kettle, is reacted 5 hours, above-mentioned reactant concentration is calculated as 0.5mol/L with lithium concentration, and passes through H2SO4Adjust
It is 10 to save reactant pH value.
After the completion for the treatment of above-mentioned reaction, in being by the pH value that the sediment of generation is cleaned to solution with deionized water and ethanol
Property, obtained sediment obtains pale powder after being dried 5 hours under 100 DEG C of vacuum conditions, by above-mentioned pale powder with
Glucose is according to mass ratio 100:10 are added in deionized water, and mixing is spray-dried after 2 hours, then by spray drying
Powder is in H2Room temperature is naturally cooled to after being heat-treated 10 hours under the conditions of 700 DEG C under the protection of/Ar mixed gas, finely ground, mistake
Sieve, that is, obtain ball-type LiFe0.5Mn0.5PO4/ C composite positive poles.
Embodiment three
With LiOHH2O、FeSO4·7H2O、MnCO3、H3PO4It is Li according to mol ratio for base stock：Fe：Mn：P=
3.0：0.25：0.75：1 is added separately to volume ratio as 1：Moved into after being stirred 30 minutes in 1 water and glycerine mixed solution anti-
Answer and 180 DEG C are heated in kettle, react 5 hours, above-mentioned reactant concentration is calculated as 0.5mol/L with lithium concentration, and passes through H2SO4
It is 8 to adjust reactant pH value.
After the completion for the treatment of above-mentioned reaction, in being by the pH value that the sediment of generation is cleaned to solution with deionized water and ethanol
Property, obtained sediment obtains pale powder after being dried 5 hours under 100 DEG C of vacuum conditions, by above-mentioned pale powder with
Glucose is according to mass ratio 100:10 are added in deionized water, and mixing is spray-dried after 2 hours, then by spray drying
Powder is in H2Room temperature is naturally cooled to after being heat-treated 8 hours under the conditions of 700 DEG C under the protection of/Ar mixed gas, finely ground, mistake
Sieve, that is, obtain ball-type composite positive pole.Through XRD elementary analyses, as a result as shown in Figure 4, it was demonstrated that obtained composite is
LiFe0.25Mn0.75PO4/ C composite positive poles.
Example IV
With LiOHH2O、FeSO4·7H2O、MnCO3、H3PO4It is Li according to mol ratio for base stock：Fe：Mn：P=
3.0：0.25：0.75：1 is added separately to volume ratio as 1：Moved into after being stirred 30 minutes in 1 water and glycerine mixed solution anti-
Answer and 180 DEG C are heated in kettle, react 5 hours, above-mentioned reactant concentration is calculated as 0.5mol/L with lithium concentration, and passes through H2SO4
It is 10 to adjust reactant pH value.
After the completion for the treatment of above-mentioned reaction, in being by the pH value that the sediment of generation is cleaned to solution with deionized water and ethanol
Property, obtained sediment obtains pale powder after being dried 5 hours under 100 DEG C of vacuum conditions, by above-mentioned pale powder with
Glucose is according to mass ratio 100:10 are added in deionized water, and mixing is spray-dried after 2 hours, then by spray drying
Powder is in H2Room temperature is naturally cooled to after being heat-treated 12 hours under the conditions of 750 DEG C under the protection of/Ar mixed gas, finely ground, mistake
Sieve, that is, obtain ball-type LiFe0.25Mn0.75PO4/ C composite positive poles.
Embodiment five
With LiOHH2O、FeSO4·7H2O、MnCO3、H3PO4It is Li according to mol ratio for base stock：Fe：Mn：P=
3.0：0.25：0.75：1 is added separately to volume ratio as 1：Moved into after being stirred 30 minutes in 2 water and glycerine mixed solution anti-
Answer and 200 DEG C are heated in kettle, react 10 hours, above-mentioned reactant concentration is calculated as 0.5mol/L with lithium concentration, and passes through
H2SO4It is 10 to adjust reactant pH value.
After the completion for the treatment of above-mentioned reaction, in being by the pH value that the sediment of generation is cleaned to solution with deionized water and ethanol
Property, obtained sediment obtains pale powder after being dried 5 hours under 100 DEG C of vacuum conditions, by above-mentioned pale powder with
Glucose is according to mass ratio 100:10 are added in deionized water, and mixing is spray-dried after 2 hours, then by spray drying
Powder is in H2Room temperature is naturally cooled to after being heat-treated 10 hours under the conditions of 760 DEG C under the protection of/Ar mixed gas, finely ground, mistake
Sieve, that is, obtain ball-type LiFe0.25Mn0.75PO4/ C composite positive poles.
Detect example
Composite positive pole prepared by above-described embodiment carries out performance detection, as a result as shown in table 1.
Table 1
Claims (3)
1. a kind of anode material for lithium-ion batteries, it is characterised in that be spherical structure, outer surface is carbon coating layer, and inside includes
LiFexMnyPO4Nano-particle, the particle diameter of the anode material for lithium-ion batteries is 11.8-14.2 μm, carbon content 1.9-
3.2%, tap density 1.32-1.54g/cm3, wherein 0 ＜ x≤0.5,0.5≤y ＜ 1, x+y=1；The LiFexMnyPO4
The particle diameter 200-300nm of nano-particle；
The preparation method of the anode material for lithium-ion batteries, comprises the following steps：
(1) hydro-thermal solvent thermal reaction is carried out as raw material using Li source compound, Fe source compound, manganese source compound, P source compound,
After the sediment washing of generation, drying, it is well mixed with the carbonaceous organic material aqueous solution, is spray-dried and powder is made；
(2) under gas shield, the powder is calcined, after the carbonaceous organic material carbonization, naturally cools to room temperature, then
By grinding, sieving, the anode material for lithium-ion batteries is made；
In step (1), Li source compound, Fe source compound, manganese source compound, P source compound are according to Li：Fe：Mn：P mol ratios
For 3.0：x：y：1.0 mixing, wherein 0 ＜ x≤0.5,0.5≤y ＜ 1, x+y=1；
Volume ratio of the hydro-thermal solvent thermal reaction using the mixture of glycerine and water as reaction medium, wherein glycerine and water
For 1：1；PH value in reaction is adjusted between 8.0~10.0 by inorganic acid after raw material mixing, is finally placed in reactor sealing
Reacted 5~24 hours at 140~240 DEG C；
In step (1), the mass ratio of sediment and carbonaceous organic material is 100：1-20；
In step (2), the condition of calcining is to be heat-treated 1~24 hour at 400~800 DEG C.
2. anode material for lithium-ion batteries as claimed in claim 1, it is characterised in that the carbonaceous organic material be glucose,
One or more in sucrose, ascorbic acid, polyvinyl alcohol or starch.
3. anode material for lithium-ion batteries as claimed in claim 1, it is characterised in that in step (2), the gas is N2、
Ar、Ar/H2Mixed gas or N2/H2Mixed gas.
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| CN108461786A (en) * | 2016-12-10 | 2018-08-28 | 中国科学院大连化学物理研究所 | A kind of preparation method and fuel cell of fuel cell membrane electrode |
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| CN111816851B (en) * | 2020-06-22 | 2022-07-01 | 南昌大学 | Hierarchical porous LiMnxFe1-xPO4Template-free hydrothermal preparation method of/C composite microsphere cathode material |
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