CN105552340A - Cathode material for lithium-ion battery and preparation method of cathode material - Google Patents
Cathode material for lithium-ion battery and preparation method of cathode material Download PDFInfo
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- CN105552340A CN105552340A CN201610074046.7A CN201610074046A CN105552340A CN 105552340 A CN105552340 A CN 105552340A CN 201610074046 A CN201610074046 A CN 201610074046A CN 105552340 A CN105552340 A CN 105552340A
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- lithium
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- source compound
- cathode material
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Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010406 cathode material Substances 0.000 title abstract 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- 239000011572 manganese Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000010405 anode material Substances 0.000 claims description 18
- 239000013049 sediment Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- 239000003595 mist Substances 0.000 claims description 9
- 239000011368 organic material Substances 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
- 239000008103 glucose Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 6
- 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
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 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
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 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
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 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
- 239000002131 composite material Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 13
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 238000001694 spray drying Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 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
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 7
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 229910011844 LiFe0.25Mn0.75PO4 Inorganic materials 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 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
- 229910011990 LiFe0.5Mn0.5PO4 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007613 environmental effect Effects 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
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus 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
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 229910009891 LiAc Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 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
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 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
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 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
- 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
- 238000007789 sealing Methods 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
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 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 cathode material for a lithium-ion battery and a preparation method of the cathode material. The cathode material LiFe<x>Mn<y>PO<4>/C for the lithium-ion battery has a spherical structure; a carbon coating is arranged on the outer surface; LiFe<x>Mn<y>PO<4> nanoparticles are contained in the cathode material; the particle sizes of the cathode material for the lithium-ion battery are 5-15 microns; the carbon content is 0.5%-10%; the tap density is 1.3-1.6g/cm<3>; x is smaller than or equal to 0.5 and greater than 0; y is smaller than 1 and greater than or equal to 0.5; and x+y is equal to 1. The nanoscale LiFe<x>Mn<y>PO<4> material is firstly prepared by a hydrothermal-solvothermal method; carbon-containing organic matters and the nanoscale LiFe<x>Mn<y>PO<4> material are mixed; spray drying is carried out; and a carbon-containing compound on the material surface after high-temperature calcination is transformed into a high-conductivity carbon material. The composite cathode material prepared by the method has excellent electrochemical properties, and has good application value for a power lithium-ion battery.
Description
Technical field
The present invention relates to technical field of lithium-ion battery, be specifically related to a kind of anode material for lithium-ion batteries and preparation method thereof.
Background technology
Along with lack of energy and to environmental protection requirement; lithium ion battery is clean as one, green battery is widely used; and anode material for lithium-ion batteries is limiting lithium ion cell extensive use in power; in current business-like positive electrode, LiFePO4 has the advantages such as fail safe is good, environmental friendliness, rate charge-discharge characteristic and good cycling stability, abundant raw materials cheapness; but its discharge voltage plateau lower (3.4V), thus have impact on the performance of its energy density.And lithium manganese phosphate has same olivine structural, theoretical gram volume is close to 170mAh/g, and its discharge voltage plateau higher (4.1V), theoretical energy density reaches 697Whkg
-1, than the energy density (578Whkg of LiFePO4
-1) exceed 20%, but in charge and discharge process, there is Mn due to it
3+jahn-Teller effect cause the distortion of lattice, Mn
3+dissolving and the unfavorable factor such as lower lithium ion diffusion rate and electronic conductivity, thus cause electrical property effectively not play, so can in conjunction with the advantage of the two, the ratio of Reasonable Regulation And Control Mn and Fe, replaces Fe by the Mn of a part and prepares the lithium ferric manganese phosphate positive electrode with high-energy-density and high conductance.
Synthetic method at present about lithium ferric manganese phosphate has many preparation methods, as far back as 2005, publication No. is the preparation method that patent document discloses a kind of high-density spherical ferric lithium phosphate and iron manganese phosphate for lithium of CN1632970A, its method is first by ferrous sulfate, phosphorus source, complexing agent or add manganese sulfate more wherein, mixture aqueous solution is made in proportion after mixing, use ammonia spirit Reactive Synthesis ferrous ammonium phosphate or manganese phosphate ferrous ammonium presoma again, after washing is dry and lithium carbonate with mol ratio 1:1 Homogeneous phase mixing, under nitrogen atmosphere protection, within 8 ~ 48 hours, LiFePO4 or iron manganese phosphate for lithium is obtained through 600 ~ 900 DEG C of high-temperature heat treatment.But have use ammoniacal liquor in said method, cause preparation condition sometimes uncontrolled, operating environment is poor, not easily suitability for industrialized production.
Publication No. be CN103280579A patent document discloses a kind of high performance lithium ion battery anode material lithium ferric manganese phosphate and preparation method thereof.Utilize solid phase method to prepare lithium ferric manganese phosphate/carbon matrix precursor by after independent source of iron, manganese source, lithium source, phosphorus source and the mixing of carbon source ball milling, then prepare the lithium ferric manganese phosphate/carbon composite of Fe/Mn=4:6 through double sintering.But other mixes to use iron in the lithium ferric manganese phosphate prepared of the method just to reach molecular level by ball grinding method with manganese, is difficult to the Homogeneous phase mixing reaching iron and manganese atom rank, causes the consistency of material poor.
Publication No. is patent document discloses of CN104701536A is the technique that a kind of spray drying process prepares high-performance LiFePO4/C anode material of lithium battery.Its technical scheme is: by adding polyvinyl alcohol (PVA) additive as auxiliary template in precursor solution, adopts organic substance assistant spray seasoning successfully to prepare the high performance spherical LiFePO4/C anode material of lithium battery with secondary structure.Optimize addition and the presoma sintering temperature of PVA, improved process simultaneously, adapt to the needs of industrialization large-scale production.This characteristic feature of an invention is: the specimen material prepared using PVA as organic additive not only has beautiful pattern but also has very excellent chemical property.
Summary of the invention
Not enough for prior art, the invention provides a kind of anode material for lithium-ion batteries LiFe
xmn
ypO
4/ C and preparation method thereof, utilizes preparation method of the present invention to not only increase the chemical property of material, also improves the tap density of material simultaneously, have good using value for power lithium-ion battery.
A kind of anode material for lithium-ion batteries, be spherical structure, outer surface is carbon coating layer, and inside comprises LiFe
xmn
ypO
4nano particle, the particle diameter of described anode material for lithium-ion batteries is 5-15 μm, and carbon content is 0.5%-10%, and tap density is 1.3-1.6g/cm
3, wherein 0 < x≤0.5,0.5≤y < 1, x+y=1.
As preferably, the particle diameter of described anode material for lithium-ion batteries is 11.8-14.2 μm, and carbon content is 1.9-3.2%, and tap density is 1.32-1.54g/cm
3.
LiFe provided by the invention
xmn
ypO
4/ C composite positive pole material with carbon-coated surface is even, has higher specific capacity, can reach more than 150mAh/g; Coulombic efficiency is greater than 95% first; Circulate 100 conservation rates more than 94% under 0.5C.
As preferably, described LiFe
xmn
ypO
4the 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) carry out hydro-thermal solvent thermal reaction with Li source compound, Fe source compound, manganese source compound, P source compound for raw material, by generate sediment washing, after drying, even with carbonaceous organic material aqueous solution, spraying dry obtains powder;
(2) under Buchholz protection, described powder is calcined, after described carbonaceous organic material carbonization, naturally cool to room temperature, then through grinding, sieving, obtained described anode material for lithium-ion batteries.
First preparation method of the present invention has prepared nanoscale LiFe by hydro-thermal solvent-thermal method
xmn
ypO
4material, then by carbonaceous organic material and nanoscale LiFe
xmn
ypO
4after material carries out mixed at high speed, carry out spraying dry, spraying dry can not only by nanoscale LiFe
xmn
ypO
4material is gathered into micron-sized ball-type second particle, meanwhile effectively carbon containing chemicals can be evenly spread to nanoscale LiFe
xmn
ypO
4the surface of material, after high-temperature calcination, the carbon compound of material surface is transformed into High-conductivity carbon material.
As preferably, in step (1), Li source compound, Fe source compound, manganese source compound, P source compound are 3.0:x:y:1.0 mixing according to Li:Fe:Mn:P mol ratio, wherein 0 < x≤0.5,0.5≤y < 1, x+y=1.More preferred, x is 0.5 or 0.25.
Described Li source compound is Li
2cO
3, LiNO
3, one or several in LiOH or LiAc.
Described Fe source compound is FeC
2o
4, Fe (Ac)
2, FeSO
4, FeCl
2or Fe (NO
3)
2in one or several.
Described manganese source compound is MnSO
4, MnCl
2, MnCO
3in one or several.
Described P source compound is H
3pO
4, NH
4h
2pO
4, (NH
4)
2hPO
4in one or several.
As preferably, described hydro-thermal solvent thermal reaction is using the mixture of organic solvent and water as reaction medium, and wherein the volume ratio of organic solvent and water is 1:1-10.In this reaction medium, effectively can not only shorten the migration distance of lithium ion, and in the method, the mixing of Fe and Mn reaches the mixing of atomic level, make that end product is dispersed and consistency is good.Described organic solvent is one or several in methyl alcohol, ethanol, glycerol, polyethylene glycol.More preferred, the volume ratio of glycerol and water is 1:1.
Regulate pH value in reaction between 6.0 ~ 12.0 by inorganic acid after raw material mixing, finally reactor sealing is reacted 5 ~ 24 hours at 140 ~ 240 DEG C.As preferably, pH value is 8.0 ~ 10.0, and more preferably, pH value is 8.0.Described inorganic acid is HCl, H
2sO
4, H
3pO
4, HAc, H
2c
2o
4in one or several.
In step (1), the sediment be obtained by reacting need be neutral by washed with de-ionized water to the pH value of solution, then the sediment after cleaning is obtained pale solid powder for 2 ~ 12 hours in 60 ~ 120 DEG C of vacuumizes is nanoscale LiFe
xmn
ypO
4material.
As preferably, described carbonaceous organic material is one or more in glucose, sucrose, ascorbic acid, polyvinyl alcohol or starch.
As preferably, in step (1), the mass ratio of sediment and carbonaceous organic material is 100:1-20.More preferred, the mass ratio of sediment and glucose is 100:10.
As preferably, in step (2), described gas is N
2, Ar, Ar/H
2mist or N
2/ H
2mist.
As preferably, in step (2), the condition of calcining is heat treatment 1 ~ 24 hour at 400 ~ 800 DEG C.
The beneficial effect that the present invention possesses: (1) the present invention adopts hydro-thermal solvent-thermal method to prepare nanometer LiFe
xmn
ypO
4, wherein the mixing of Fe and Mn reaches the mixing of atomic level, makes that end product is dispersed and consistency is good; (2) improve composite material tap density by spraying dry, make carbon compound be dispersed in second particle surface simultaneously, be conducive to subsequent calcination and form complete carbon coating layer, improve electric conductivity; (3) preparation method's technical process of the present invention is simple, cheap, is beneficial to enforcement, is very suitable for commercialization and applies.
Accompanying drawing explanation
Fig. 1 is lithium ion anode material preparation principle schematic diagram of the present invention.
Fig. 2 is ball-type LiFe of the present invention
0.5mn
0.5pO
4the SEM figure of/C composite positive pole.
Fig. 3 is the LiFe of Fig. 2
0.5mn
0.5pO
4the enlarged drawing of/C composite positive pole SEM figure.
Fig. 4 is the XRD elementary analysis figure that embodiment 3 obtains composite material.
Embodiment
Below in conjunction with embodiment, the invention will be further described; what be necessary to herein means out is that following examples can only be used for further illustrating for of the present invention; can not be interpreted as and limit protection scope of the present invention, nonessential improvement on this basis and adjustment still belong to protection scope of the present invention.
In order to reach technical purpose of the present invention, the technical solution used in the present invention as shown in Figure 1, specifically can comprise the steps:
Embodiment one
With LiOHH
2o, FeSO
47H
2o, MnCO
3, H
3pO
4for base stock, be that Li:Fe:Mn:P=3.0:0.5:0.5:1 joins respectively in the water and glycerol mixed solution that volume ratio is 1:1 to stir to move in reactor after 30 minutes and is heated to 180 DEG C according to mol ratio, react 5 hours, above-mentioned reactant concentration counts 0.5mol/L with lithium concentration, and passes through H
2sO
4reactant pH value is regulated to be 8.
After above-mentioned reaction completes, be neutral by the sediment deionized water of generation and ethanol purge to the pH value of solution, the sediment obtained obtains pale powder after dry 5 hours under 100 DEG C of vacuum conditions, above-mentioned pale powder and glucose are added in deionized water according to mass ratio 100:10, mix and carry out spraying dry after 2 hours, then by spray-dired powder at H
2under the protection of/Ar mist, under 600 DEG C of conditions, heat treatment naturally cooled to room temperature after 10 hours, and porphyrize sieves, and namely obtained ball-type LiFe
0.5mn
0.5pO
4/ C composite positive pole.SEM electron-microscope scanning result as shown in Figure 2 and Figure 3.
Embodiment two
With LiOHH
2o, FeSO
47H
2o, MnCO
3, H
3pO
4for base stock, be that Li:Fe:Mn:P=3.0:0.5:0.5:1 joins respectively in the water and glycerol mixed solution that volume ratio is 1:1 to stir to move in reactor after 30 minutes and is heated to 180 DEG C according to mol ratio, react 5 hours, above-mentioned reactant concentration counts 0.5mol/L with lithium concentration, and passes through H
2sO
4reactant pH value is regulated to be 10.
After above-mentioned reaction completes, be neutral by the sediment deionized water of generation and ethanol purge to the pH value of solution, the sediment obtained obtains pale powder after dry 5 hours under 100 DEG C of vacuum conditions, above-mentioned pale powder and glucose are added in deionized water according to mass ratio 100:10, mix and carry out spraying dry after 2 hours, then by spray-dired powder at H
2under the protection of/Ar mist, under 700 DEG C of conditions, heat treatment naturally cooled to room temperature after 10 hours, and porphyrize sieves, and namely obtained ball-type LiFe
0.5mn
0.5pO
4/ C composite positive pole.
Embodiment three
With LiOHH
2o, FeSO
47H
2o, MnCO
3, H
3pO
4for base stock, be that Li:Fe:Mn:P=3.0:0.25:0.75:1 joins respectively in the water and glycerol mixed solution that volume ratio is 1:1 to stir to move in reactor after 30 minutes and is heated to 180 DEG C according to mol ratio, react 5 hours, above-mentioned reactant concentration counts 0.5mol/L with lithium concentration, and passes through H
2sO
4reactant pH value is regulated to be 8.
After above-mentioned reaction completes, be neutral by the sediment deionized water of generation and ethanol purge to the pH value of solution, the sediment obtained obtains pale powder after dry 5 hours under 100 DEG C of vacuum conditions, above-mentioned pale powder and glucose are added in deionized water according to mass ratio 100:10, mix and carry out spraying dry after 2 hours, then by spray-dired powder at H
2under the protection of/Ar mist, under 700 DEG C of conditions, heat treatment naturally cooled to room temperature after 8 hours, and porphyrize sieves, and namely obtained ball-type composite positive pole.Through XRD elementary analysis, result as shown in Figure 4, proves that the composite material obtained is LiFe
0.25mn
0.75pO
4/ C composite positive pole.
Embodiment four
With LiOHH
2o, FeSO
47H
2o, MnCO
3, H
3pO
4for base stock, be that Li:Fe:Mn:P=3.0:0.25:0.75:1 joins respectively in the water and glycerol mixed solution that volume ratio is 1:1 to stir to move in reactor after 30 minutes and is heated to 180 DEG C according to mol ratio, react 5 hours, above-mentioned reactant concentration counts 0.5mol/L with lithium concentration, and passes through H
2sO
4reactant pH value is regulated to be 10.
After above-mentioned reaction completes, be neutral by the sediment deionized water of generation and ethanol purge to the pH value of solution, the sediment obtained obtains pale powder after dry 5 hours under 100 DEG C of vacuum conditions, above-mentioned pale powder and glucose are added in deionized water according to mass ratio 100:10, mix and carry out spraying dry after 2 hours, then by spray-dired powder at H
2under the protection of/Ar mist, under 750 DEG C of conditions, heat treatment naturally cooled to room temperature after 12 hours, and porphyrize sieves, and namely obtained ball-type LiFe
0.25mn
0.75pO
4/ C composite positive pole.
Embodiment five
With LiOHH
2o, FeSO
47H
2o, MnCO
3, H
3pO
4for base stock, be that Li:Fe:Mn:P=3.0:0.25:0.75:1 joins respectively in the water and glycerol mixed solution that volume ratio is 1:2 to stir to move in reactor after 30 minutes and is heated to 200 DEG C according to mol ratio, react 10 hours, above-mentioned reactant concentration counts 0.5mol/L with lithium concentration, and passes through H
2sO
4reactant pH value is regulated to be 10.
After above-mentioned reaction completes, be neutral by the sediment deionized water of generation and ethanol purge to the pH value of solution, the sediment obtained obtains pale powder after dry 5 hours under 100 DEG C of vacuum conditions, above-mentioned pale powder and glucose are added in deionized water according to mass ratio 100:10, mix and carry out spraying dry after 2 hours, then by spray-dired powder at H
2under the protection of/Ar mist, under 760 DEG C of conditions, heat treatment naturally cooled to room temperature after 10 hours, and porphyrize sieves, and namely obtained ball-type LiFe
0.25mn
0.75pO
4/ C composite positive pole.
Test example
The composite positive pole prepared by above-described embodiment carries out Performance Detection, and result is as shown in table 1.
Table 1
Claims (10)
1. an anode material for lithium-ion batteries, is characterized in that, be spherical structure, outer surface is carbon coating layer, and inside comprises LiFe
xmn
ypO
4nano particle, the particle diameter of described anode material for lithium-ion batteries is 5-15 μm, and carbon content is 0.5%-10%, and tap density is 1.3-1.6g/cm
3, wherein 0 < x≤0.5,0.5≤y < 1, x+y=1.
2. anode material for lithium-ion batteries as claimed in claim 1, is characterized in that, described LiFe
xmn
ypO
4the particle diameter 200-300nm of nano particle.
3. a preparation method for anode material for lithium-ion batteries, comprises the following steps:
(1) carry out hydro-thermal solvent thermal reaction with Li source compound, Fe source compound, manganese source compound, P source compound for raw material, by generate sediment washing, after drying, even with carbonaceous organic material aqueous solution, spraying dry obtains powder;
(2) under Buchholz protection, described powder is calcined, after described carbonaceous organic material carbonization, naturally cool to room temperature, then through grinding, sieving, obtained described anode material for lithium-ion batteries.
4. preparation method as claimed in claim 3, it is characterized in that, in step (1), Li source compound, Fe source compound, manganese source compound, P source compound are 3.0:x:y:1.0 mixing according to Li:Fe:Mn:P mol ratio, wherein 0 < x≤0.5,0.5≤y < 1, x+y=1.
5. preparation method as claimed in claim 3, is characterized in that, described hydro-thermal solvent thermal reaction is using the mixture of organic solvent and water as reaction medium, and wherein the volume ratio of organic solvent and water is 1:1-10.
6. preparation method as claimed in claim 5, is characterized in that, described organic solvent is one or several in methyl alcohol, ethanol, glycerol, polyethylene glycol.
7. preparation method as claimed in claim 3, it is characterized in that, in step (1), the mass ratio of sediment and carbonaceous organic material is 100:1-20.
8. preparation method as claimed in claim 3, it is characterized in that, described carbonaceous organic material is one or more in glucose, sucrose, ascorbic acid, polyvinyl alcohol or starch.
9. preparation method as claimed in claim 3, it is characterized in that, in step (2), described gas is N
2, Ar, Ar/H
2mist or N
2/ H
2mist.
10. preparation method as claimed in claim 3, is characterized in that, in step (2), the condition of calcining is heat treatment 1 ~ 24 hour at 400 ~ 800 DEG C.
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| CN107768613A (en) * | 2017-09-01 | 2018-03-06 | 上海交通大学 | A kind of preparation method of the iron manganese phosphate for lithium of carbon coated |
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