CN110492060A - A kind of differentiating stage lithium manganese phosphate/carbon composite anode material preparation method of receiving - Google Patents
A kind of differentiating stage lithium manganese phosphate/carbon composite anode material preparation method of receiving Download PDFInfo
- Publication number
- CN110492060A CN110492060A CN201810460766.6A CN201810460766A CN110492060A CN 110492060 A CN110492060 A CN 110492060A CN 201810460766 A CN201810460766 A CN 201810460766A CN 110492060 A CN110492060 A CN 110492060A
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- Prior art keywords
- lithium
- solution
- source
- manganese
- preparation
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- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 title claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000010405 anode material Substances 0.000 title claims description 21
- 239000000463 material Substances 0.000 claims abstract description 78
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 72
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000002245 particle Substances 0.000 claims abstract description 31
- 239000011572 manganese Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 18
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 18
- 239000011164 primary particle Substances 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 229920002521 macromolecule Polymers 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 87
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 9
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical group Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 9
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 9
- 239000011565 manganese chloride Substances 0.000 claims description 9
- 235000002867 manganese chloride Nutrition 0.000 claims description 9
- 229940099607 manganese chloride Drugs 0.000 claims description 9
- 229940099596 manganese sulfate Drugs 0.000 claims description 9
- 239000011702 manganese sulphate Substances 0.000 claims description 9
- 235000007079 manganese sulphate Nutrition 0.000 claims description 9
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- 150000002696 manganese Chemical class 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims 1
- 150000002085 enols Chemical class 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 238000004321 preservation Methods 0.000 description 13
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 230000004087 circulation Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000006210 lotion Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000001875 compounds Chemical group 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- BXRRQHBNBXJZBQ-UHFFFAOYSA-L dichloromanganese;hydrate Chemical compound O.Cl[Mn]Cl BXRRQHBNBXJZBQ-UHFFFAOYSA-L 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000011282 treatment 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
- H01M4/36—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to battery technology fields, specifically disclose it is a kind of with receive differential level structure manganese phosphate lithium/carbon composite material preparation method, material solution comprising manganese source, lithium source, phosphorus source, hexamethylenetetramine, ethylene glycol is heat-treated at 70 DEG C~80 DEG C in advance, then solvent heat obtains at 160 DEG C~200 DEG C again.It will be made and mix with macromolecule carbon source, dry and obtained in protective atmosphere in 500 DEG C~650 DEG C calcinings with receiving the lithium manganese phosphate material of differential level structure.Material prepared primary particle of the present invention is nanoscale, has preferred growth and is evenly distributed, is conducive to lithium ion and spreads in the material.Second particle size is other in the micron-scale, is conducive to stable structure, the material of preparation charge/discharge capacity with higher, excellent cyclical stability, good rate capability.
Description
Technical field
The invention belongs to technical field of lithium ion battery positive pole material preparation, relate to a kind of hierarchical structure lithium ion battery
Composite positive pole LiMnPO4The synthetic method of/C.
Background technique
Develop high security, high-energy density, the new type power type lithium ion battery of long-life and has become research hotspot.
LiMnPO4With olivine structural, theoretical capacity and LiFePO4 are quite 170mAh/g, but its voltage platform is that 4.1V is (right
In Li/Li+), it is higher by 0.7V than LiFePO4 (3.4V), to improve energy density, therefore LiMnPO4Positive electrode causes
The research interest of numerous researchers.
However pure phase LiMnPO4Electric conductivity ratio LiFePO4It is worse, while lithium ion diffusion is also limited one-dimensional channel, makes
The migration rate for obtaining lithium ion at room temperature is smaller.Invention patent publication number is CN105070912A, entitled " a kind of spherical shape lithium from
The Chinese patent of the preparation method of sub- battery cathode material lithium manganese phosphate " is described and is first generated using coprecipitation auxiliary calcining
Li3PO4.Then polyalcohol assisting alcohol-hydrothermal method synthesizes to obtain LiMnPO4.The program is complicated for operation, and obtained lithium manganese phosphate spherical
For grain particle size between 0.3~2 μm, particle is larger, is difficult to obtain the primary particle of nano-grade size.Researcher mainly passes through
Synthesis nano LiMnPO4Material come shorten lithium ion diffusion path, enhance lithium ion deintercalation invertibity.Dokko etc.
[Kaoru Dokko, Takeshi Hachida, Masayoshi Watanabe.J Electrochem Soc, 2,011 158
(12): A1275-A1281] with Li3PO4With MnSO4·nH2O has synthesized nanometer at 190 DEG C by hydro-thermal method for raw material
LiMnPO4, then cladding processing is carried out by carbon source of glucose.The specific discharge capacity of 0.01C is 135mAhg-1, but compared with high magnification
Specific discharge capacity is only 83mAhg under 1C-1, 5 performances of circulation have been only referred in text, have been showed bad.Due to LiMnPO4Structure
Anisotropy when middle Li ion transmits, Li+ is minimum along [010] direction migration activation energy, is obtained by the control crystal face direction of growth
The regular material of suitable high preferred orientation, crystallization is to guaranteeing that lithium ion and electron propagation ducts are particularly significant.With particular crystal
The nanometer LiMnPO of orientation4The focus adjusted as pattern.
The LiMnPO that the reports such as Ping Nie pass through solvent structure single crystal nanoplate composition4Flower-shaped hierarchical structure,
But electro-chemical activity is lower, and capacity is below 60mAh/g under the low range of C/40 and C/20.[Ping Nie, Laifa
Shen, Fang Zhang, Lin Chen, Haifu Deng, Xiaogang Zhang.CrystEngComm, 2012,14,4284-
4288]
Therefore, it is to obtain high magnification LiMnPO that preparation, which has the micro-nano compound structure of particular crystal plane oriented growth,4Material
A major challenge.
Summary of the invention
For existing micro-nano structure LiMnPO4Preparation process is complicated in material preparation process, and the grain diameter of synthesis is larger,
The deficiencies of chemical property is bad, an object of the present disclosure be, provides a kind of with receiving the lithium manganese phosphate material of differential level structure
The preparation method of material, it is intended to be obtained by control particle growth by the micro-nano of the primary nanocrystalline secondary porous particle assembled
Structure LiMnPO4Material.
Second purpose of the invention is, provide it is a kind of receive differentiating stage lithium manganese phosphate/carbon composite anode material preparation method,
It is intended to obtain by control particle growth by the carbon-coated primary nanocrystalline secondary porous particle assembled of amorphous, improves material
The electro-chemical activity and circulation stability of material.
It is a kind of with receive differential level structure lithium manganese phosphate material preparation method, will include manganese source, lithium source, phosphorus source, six
The material solution heat treatment (first segment heating) at 70 DEG C~80 DEG C in advance of methine tetramine (HMT), ethylene glycol, then exists again
Solvent heat (second segment heating) obtains at 160 DEG C~200 DEG C.
The method of the present invention, innovatively using hexamethylenetetramine, ethylene glycol dicyandiamide solution under, cooperate the gradient warm area
Two sections of gradient warm areas processing method, can be made with receiving the lithium manganese phosphate material of differential level structure.The study found that passing through
The processing of two sections of gradient warm areas under dicyandiamide solution, lithium manganese phosphate material obtained are the nanoscale with high preferred orientation primary
The Multi-hole secondary particle that grain is self-assembled into；The primary particle has (010) advantage high preferred orientation, the second particle
For micron order or submicron particles.By the method for the invention, the lithium manganese phosphate material haveing excellent performance can be made.
The study found that there is unexpected advantage using HMT.In the present invention, hexamethylenetetramine cooperates of the invention
Ethylene glycol solution system and the processing of two sections of gradient warm areas of the innovation, can control crystal nucleation and facilitate nucleus preferentially
Oriented growth, in addition, the emulsification of HMT hydrolysate can reach reaction equably effect, and then coordinate system obtain structure it is excellent,
Crystal grain is smaller, and particle size distribution is narrow, has different-shape, the LiFePO 4 material haveing excellent performance.
In the present invention, HMT is under two sections of gradient warm area treatment processes, and slowly hydrolysis generates NH3It, can be with formaldehyde
Make to react uniform progress while adjusting pH, controls the growth of crystal grain；Secondly, the formaldehyde suitably generated has emulsifying effectiveness, match
Two sections of solvent heats are closed, is conducive to particle and refines.In addition, the present invention selects solvent thermal reaction under ethylene glycol solution system,
With larger viscosity, ion is spread in ethylene glycol solution intermediate ion relatively to be delayed, and crystal too fast will not be grown.In addition, ethylene glycol also has
There are reproducibility and surface-active action, can both prevent Mn2+It is oxidized and also can control crystal growth, keep the tiny knot of particle
Structure is more advantageous to form porous differentiating stage lithium manganese phosphate material of receiving.
In the present invention, not only handled with the ethylene glycol and two sections of gradient temperatures using hexamethylenetetramine
Cooperation can be made described and receive differential level structure, can also can be regulated and controled described by regulating and controlling hexamethylenetetramine dosage
Receive differential level structure lithium manganese phosphate pattern.It that is to say, the present invention innovatively has found, can pass through regulation hexamethylenetetramine
Dosage regulates and controls the pattern of primary particle, and controls the pattern of the second particle obtained by the primary particle self assembly of special appearance
(pattern of lithium manganese phosphate).
Preferably, the mole of hexamethylenetetramine is 0.5-2.5 times of lithium manganese phosphate.It is also contemplated that described six times
The molar ratio of tetramine and manganese source (in terms of Mn) are 0.5-2.5: 1.
In the present invention, by the HMT additional amount, it can control the pH of solvent thermal reaction liquid 6~10；Preferably 7~9
In the range of, help to be made the lithium manganese phosphate material excellent with superperformance.
In the present invention, the manganese source is that can provide Mn2+Material, preferably Mn2+Water soluble salt.
Preferably, the manganese source is at least one of manganese chloride, manganese acetate and manganese nitrate, manganese sulfate.
In the present invention, the lithium source is the material that can provide Li+, and preferred lithium source is lithium nitrate, lithium chloride and acetic acid
At least one of lithium.
In the present invention, the lithium source is that can provide PO4 3-Material, preferably lithium dihydrogen phosphate, phosphoric acid at least one
Kind.
Preferably, reactant concentration is in 0.1-3mol/l in the material solution.It that is to say, in the original
Expect in solution, the concentration comprising the reactant including manganese source, lithium source, phosphorus source, hexamethylenetetramine is preferably 0.1-3mol/l.It grinds
Study carefully discovery, under the preferred concentration, the structure of obtained lithium manganese phosphate material, pattern are more preferable, and the performance of product further mentions
It rises.
Preferably, Li: Mn: P molar ratio is 2.5~3.5: 1: 1~1.1.Under this preferably range, it is more conducive to obtain
Obtain lithium manganese phosphate material.
The present invention is innovatively heat-treated under the solution system of the ethylene glycol and solvent heat.
Preferably, also allowing in the material solution containing water.For example, if the phosphorus source is PO4 3-Salt, and
Allow to dissolve the phosphorus source using water, then the aqueous solution and lithium source of the phosphorus source, the ethylene glycol of manganese source and hexamethylenetetramine is molten
It is mixed in liquid, obtains the material solution.
The present invention innovatively uses heat treatment and solvent heat under two sections of warm areas at the temperature, passes through the not equality of temperature
The heat treatment in area and solvent heat can well control the hydrolysis degree of HMT, the pH of control system and the content of formaldehyde, in turn
Regulate and control the primary particle that nanoscale is made and is evenly distributed, and obtains to have by the primary particle self assembly and have excellent performance
Lithium manganese phosphate second particle.
In the present invention, the heat heat treatment and solvent heat are preferably carried out under closed container.
Preferably, the time of heat treatment is 1~2h.
Preferably, the time of solvent heat is 10~15h.
After the completion of solvent heat treatment, it is separated by solid-liquid separation, is adopted after being washed with deionized isolated solid 2 times after cooling,
At least one solvent for using n-butanol, dehydrated alcohol, acetone again carries out 2~3 washings, is dried to obtain the lithium manganese phosphate
Material.
Existing conventional method can be used in the mode that the present invention is separated by solid-liquid separation, and is for example, centrifuged.
A kind of preferred preparation method of the present invention, comprising the following steps:
Manganese source, lithium source and hexamethylenetetramine are dissolved in ethylene glycol by step (1) respectively, and stirring is obtained to abundant dissolution
Concentration be the solution A of 0.1mol/L~1mol/L manganese salt, concentration is the solution B of 0.1mol/L~3mol/L lithium salts, concentration is
The solution C of 0.2mol/L~2mol/L hexamethylenetetramine, stirs 30min-60min respectively；
Step (2) weighs phosphorus source and is dissolved in ethylene glycol or water, forms the solution that concentration is 0.2mol/L~1mol/L, will
In its solution A for instilling the step (1) in stirring, the B solution instillation in step 1) is wherein then obtained into mixed solution D,
Stir 20min-60min；
Step (3) instills the C solution in step (1) in the solution D in step (2), forms solution E, in solution mole
Than Li: Mn: P: HMT=2.5~3.5: 1: 1~1.1: 1~2.5,30min-60min is sufficiently stirred；
Solution E is transferred to autoclave by step (4), is successively being carried out the heat treatment and solvent heat, is being passed through after
It is separated by solid-liquid separation, washs, is dried to obtain.
Preferred preparation method by dissolving respectively to each raw material, and obtains the solution under the concentration range respectively, then
Pass through the ingredient relationship, it is ensured that raw material sufficiently dissolves mixing, conducive to nucleation be made the pattern uniformly, have excellent performance
The lithium manganese phosphate material of nanostructure.Research also found that solution concentration is too low to be difficult to form degree of supersaturation, and crystal nucleation is tired
Difficulty, it is too low to will lead to yield, and solution concentration is excessively high to be will lead to degree of supersaturation and formed too fast, and crystal growth is not easy to control, and particle holds
It easily grows up, material morphology is difficult to control, and particle is inhomogenous.
Preparation method of the present invention is obtained to receive differential level structure LiMnPO with different-shape4Material, primary particle are
Nanoscale with high preferred orientation growth, having a size of 10~60nm, second particle is that 0.2~20 μm of micron order is spherical.
It is smaller by solvent structure partial size, it is evenly distributed, the manganese-lithium phosphate anode material of stable circulation.The method simple process,
Condition is easily controllable.
The present invention provides differentiating stage lithium manganese phosphate/carbon composite anode material preparation method is received described in one kind, use
The preparation method is made described having and receives lithium manganese phosphate/carbon material of differential level structure；
By it is described have receive differential level structure lithium manganese phosphate material mixed with carbon source, dry and in protective atmosphere in
500 DEG C~650 DEG C calcinings obtain.
The present invention is made described having using the method for the innovation and receives the lithium manganese phosphate material of differential level structure, then
It using the packet carbon method, is first uniformly mixed with carbon source, through calcination processing to get the table arrived in the primary particle after
The composite positive pole of carbon material is coated in face or porous gap.
Preferably, the carbon source is at least one of cellulose, starch, polyethylene glycol, polyvinyl alcohol high polymer.
Preferably, carbon source dosage is 10wt%~30wt% of lithium manganese phosphate.
In calcination process, the protective atmosphere is argon gas, nitrogen, argon gas-hydrogen gas mixture, nitrogen-hydrogen mixing
One kind of gas.
Preferably, calcination time is 2-6h.
It is currently preferred it is a kind of receive differentiating stage lithium manganese phosphate/carbon composite anode material preparation method, specific steps are as follows:
Manganese salt, lithium salts, microcosmic salt and hexamethylenetetramine are dissolved in ethylene glycol respectively, stirring is obtained to abundant dissolution
Acquisition concentration is the solution A of 0.1mol/L~1mol/L manganese salt, concentration is the solution B of 0.1mol/L~3mol/L lithium salts, concentration
For the solution C of 0.2mol/L~2mol/L hexamethylenetetramine, 30min-60min is stirred respectively；It weighs phosphorus source and is dissolved in ethylene glycol
Or in deionized water, the solution that concentration is 0.2mol/L~1mol/L is formed, is instilled in manganese salt solution, will then be contained
The instillation of lithium solution wherein obtains mixed solution, molar ratio Li: Mn: P=2.5~3.5: 1: 1~1.1 in solution, and stirring 20~
60min；
HMT solution will be contained to be added dropwise in Li, Mn and P mixed solution, keep molar ratio Li: Mn: P: HMT=2.5~3.5: 1
: 1~1.1: 1.0~2.5,30~60min of stirring forms lotion；It is transferred to high pressure sealing reaction kettle, is kept the temperature at 70 DEG C -80 DEG C
1h~2h then proceedes to that reactant slurry is washed with deionized 2 times after cooling in 160 DEG C~200 DEG C heat preservation 10-15h
Afterwards, then at least one solvent of n-butanol, dehydrated alcohol, acetone 2~3 washings are carried out；It is dried at a temperature of 65-100 DEG C；
In 500 DEG C~650 DEG C high-temperature calcination 2-6h in protective atmosphere after the material of drying and 10-30wt% carbon source are mixed and dried,
It obtains crystallizing complete LiMnPO4/ C composite positive pole.
The present invention provides differentiating stage lithium manganese phosphate/carbon composite anode material is received made from the preparation method, include
With receive differential level structure lithium manganese phosphate material and be coated on the carbon material on its surface；
The carbon material be macromolecule carbon source pyrolysis after amorphous carbon, wherein carbon material content be it is described it is compound just
2%~5%wt of pole material.
Beneficial effect
It is comprehensive raising LiMnPO that designing, which has the micro-nano compound structure of dynamic stabilization feature,4The pass of chemical property
Key.For the LiMnPO with good high rate performance4For material, the lithium ion that can adapt under high current is quickly embedding de-,
And need to provide stable structure and morphology.Micro-nano compound structure is existed using the overall dimension that nanocell structures are constituted as core
The structural system of micron order or submicron order can not only provide higher bulk density and short lithium ion diffusion path, and
And can guarantee the overall stability of structure, the kinetic advantage of lithium ion and electronics conduction in nano structured unit has both been played,
Again embody micro-nano structure in the lithium storage process stable structure, interface stability the advantages of.
The micro-nano hierarchical structure LiMnPO that the present invention obtains4/ C composite, with nanostructure it is quick transmission (electronics and
Ion) active particle be core, combine good stability.Porous second particle by be orientated with particular crystal plane one
It is secondary it is nanocrystalline assemble, nanocrystal surface is then pyrolyzed carbon film conductive coating.The primary particle of nanoscale shorten lithium from
The distance of son diffusion and electronics transfer has structural stability by the second particle that self assembly obtains, while being conducive to electrolyte
With abundant effective contact of active material, promotes the progress of electrochemical reaction, improve LiMnPO under high magnification4Positive electrode
Reversible capacity simultaneously improves its cycle performance.The invention proposes it is a kind of synthesize hierarchical structure manganese-lithium phosphate anode material method,
Appearance structure of the method by the controllable prepared material of the amount for changing hexamethylenetetramine, simple process, the material of preparation
Material has purity is high, complete crystallization, good physical properties, the good feature of circulation performance.
Detailed description of the invention
Fig. 1 is lithium manganese phosphate/carbon composite anode material shape appearance figure of hierarchical structure prepared by embodiment 1；
Fig. 2 is lithium manganese phosphate/carbon composite anode material shape appearance figure of hierarchical structure prepared by embodiment 2；
Fig. 3 is X-ray diffraction (XRD) map of embodiment 1,2 lithium manganese phosphate nano anode materials；
Fig. 4 is bent for charge and discharge under lithium manganese phosphate/carbon composite anode material different multiplying of 1 hierarchical structure of embodiment
Line；
Fig. 5 is bent for charge and discharge under lithium manganese phosphate/carbon composite anode material different multiplying of 2 hierarchical structure of embodiment
Line；
Fig. 6 is lithium manganese phosphate/carbon composite anode material shape appearance figure of 3 hierarchical structure of embodiment.
Fig. 7 is charging and discharging curve under lithium manganese phosphate/carbon composite anode material 1C multiplying power of 3 hierarchical structure of embodiment；
Fig. 8 is lithium manganese phosphate/carbon composite anode material shape appearance figure of 4 hierarchical structure of embodiment.
Fig. 9 is charging and discharging curve under lithium manganese phosphate/carbon composite anode material 1C multiplying power of 4 hierarchical structure of embodiment；
Figure 10 is lithium manganese phosphate/carbon composite anode material shape appearance figure prepared by comparative example 1；
Figure 11 is lithium manganese phosphate/carbon composite anode material shape appearance figure prepared by comparative example 2；
Specific embodiment
Embodiment 1
Fixed metering weighs 0.054mol lithium nitrate, 0.019mol sulfuric acid than Li: Mn: P: HMT=2.7: 0.95: 1: 1.2
Manganese, 0.02mol phosphoric acid (85%) and 0.024mol hexa distinguish lithium nitrate, manganese sulfate and hexa
It is dissolved in 20ml ethylene glycol, obtains lithium nitrate solution, manganese sulfate solution, phosphoric acid solution and hexa solution respectively, 35 DEG C add
Thermal agitation 20min；Phosphoric acid solution is instilled in the manganese sulfate solution in stirring, is then instilled lithium nitrate solution wherein, finally
Hexa solution solution is instilled, stirring sufficiently finally obtains mixed emulsion；Emulsion slurry shifts the high pressure for setting 180ml
Autoclave is placed in 80 DEG C of heat preservations 1h, 180 DEG C of heat preservation 10h in baking oven, takes out autoclave after cooling by reaction kettle, from
Heart slurry washes twice reactant with deionized water and dehydrated alcohol respectively, and the material after washing is placed at 65 DEG C of baking oven
Drying；Material after drying is taken into 1g, weighs the cellulose of 0.2g, after being mixed and dried under suitable alcohols, under an argon atmosphere 600
DEG C calcining 4h, be made composite positive pole.The attached drawing of material made from the embodiment is shown in that Fig. 1, the upper left attached drawing of Fig. 1 are SEM figure,
Upper right attached drawing is transmission electron microscope (TEM) granule-morphology figure next time；Lower part attached drawing is the big multiplying power transmission electron microscope picture of primary particle.
XRD diagram is shown in a of Fig. 3, from diffracting spectrum it can be seen that substantially conforming to lithium manganese phosphate standard card.Charge and discharge are bent under different multiplying
Line is shown in Fig. 4.
Fig. 1 can be seen that product is the nano-particle of the bell shape of symmetry, and the sheet thickness for forming second particle is to receive
Meter level is other, and open three-dimensional porous structure is presented in micron-scale in length.The surface that TEM picture can see nanometer sheet has very
Mostly tiny aperture, it can be seen that form the microscopic particles of product and assemble for the nanometer sheet assembling of porous surface diameter, simultaneously
Have 2-4nm amorphous carbon layer continuously distributed on the surface of nanometer sheet, constitute good conductive network, can give full play to ion with
Electron-transport effect.Detecting carbon containing 3.56wt% in the composite positive pole, discharge capacity is 141.5mAh/g for the first time under 0.1C,
Specific discharge capacity is maintained at 119.9mAh/g under 1C.
Embodiment 2
Will measure than Li: Mn: P: HMT=3: 1: 1: 1.7, weigh 0.06mol lithium chloride, 0.02mol manganese chloride,
0.02mol phosphoric acid (85%) and 0.034mol hexa, by lithium chloride, four chloride hydrate manganese and hexa point
It is not dissolved in 20ml ethylene glycol, obtains lithium nitrate solution, manganese chloride solution, phosphoric acid solution and hexa solution respectively；40℃
Heating stirring 30min；Phosphoric acid solution is instilled in the manganese chloride solution in stirring, is then instilled lithium chloride solution wherein, most
After instill hexa solution, stirring 50min obtains mixed emulsion；Lotion shifts the autoclave for setting 180ml, will be high
Pressure reaction kettle is placed in 75 DEG C of heat preservations 2h, 160 DEG C of heat preservation 12h in baking oven, and autoclave is taken out after cooling, is centrifuged slurry, spends
Ionized water and dehydrated alcohol wash twice reactant respectively, and the material after washing is placed at 65 DEG C of baking oven and is dried；It will drying
Material afterwards takes 1g, weighs the polyvinyl alcohol of 0.3g, after being mixed and dried under suitable alcohols, 550 DEG C of calcining 4h under an argon atmosphere,
Composite positive pole is made.The attached drawing of material made from the embodiment is shown in Fig. 2, and the upper left attached drawing of Fig. 2 is 5000 times of SEM figures, right
Upper attached drawing is TEM figure；Lower part attached drawing is high magnification TEM figure.XRD diagram is shown in the b of Fig. 3.Charging and discharging curve is shown in figure under different multiplying
5。
The spindle shaped particles that Fig. 2 can be seen that as tiny product, size form particle clusters in 0.3 micron level
It is then a uniform nanoparticle.TEM is observed that the 2-4nm amorphous carbon of growth then exists in the grain surface of 20-50nm
There is continuous conductive carbon film, carbon conductive nano network is formd, in favor of the biography of the transmitting of charge and lithium ion in electrode process
It is defeated.XRD, which detects the material, has single olivine structural (see implementation example figure 3), carbon containing 2.09wt% in the composite positive pole,
Specific discharge capacity is maintained at 109.5mAh/g at 0.2C discharge capacity 140.5mAh/g, 2C.
Embodiment 3
Metering is weighed into 0.06mol lithium nitrate, 0.019mol manganese nitrate than Li: Mn: P: HMT=3: 0.95: 1: 1
(50%), 0.02mol lithium dihydrogen phosphate and 0.02mol hexa, by lithium nitrate, manganese nitrate and hexa point
Be not dissolved in 20ml ethylene glycol, lithium dihydrogen phosphate is dissolved in 30ml deionized water, respectively lithium nitrate solution, manganese nitrate solution,
Lithium dihydrogen phosphate solution and hexa solution.Lithium dihydrogen phosphate solution will be added to instill in the manganese nitrate solution in stirring,
Then lithium chloride solution is instilled wherein, finally instills hexa solution, stirring 30min obtains mixed emulsion；Lotion
The autoclave of 180ml is set in transfer, autoclave is placed in 70 DEG C of heat preservations 1h, 200 DEG C of heat preservation 10h in baking oven, after cooling
Autoclave is taken out, slurry is centrifuged, washes twice reactant respectively with deionized water and acetone, the material after washing is placed
It is dried at 70 DEG C of baking oven；Material after drying is taken into 1g, weighs the polyethylene glycol of 0.25g, after being mixed and dried under suitable alcohols,
Composite positive pole is made in 500 DEG C of calcining 8h under an argon atmosphere.The attached drawing of material made from the embodiment is shown in Fig. 6, Fig. 6's
Upper left attached drawing is 5000 times of SEM figures, and upper right attached drawing is 1000 times of SEM figures；Lower part attached drawing is that TEM schemes under high magnification.Fig. 6 can be with
Find out the secondary spherical particle being assembled into for a rod-shpaed particle, nanometer stub crystal grain in the direction b size minimum, be conducive to lithium from
The diffusion of son, composite material show flat voltage platform, as shown in fig. 7, specific discharge capacity is 121.5mAh/g under 1C.
TEM is observed that amorphous carbon, and then in a grain surface, there are continuous conductive carbon films, form carbon conductive nano network,
Carbon containing 3.1wt% in the composite positive pole.
Embodiment 4
It will measure and weigh 0.062mol lithium acetates than Li: Mn: P: HMT=3.1: 1: 1.1: 1.2,0.02mol manganese sulfate,
0.022mol lithium dihydrogen phosphate and 0.024mol hexa are distinguished lithium acetate, manganese sulfate and hexa molten
In 20ml ethylene glycol, lithium dihydrogen phosphate is dissolved in 20ml deionized water, obtains lithium acetate solution, manganese sulfate solution, phosphoric acid respectively
Dihydro lithium solution and hexa solution.Lithium dihydrogen phosphate solution will be added to instill in the manganese sulfate solution in stirring, then
Lithium acetate solution is instilled wherein, hexa solution is finally instilled, stirring 30min obtains mixed emulsion；Lotion transfer
Autoclave is placed in 70 DEG C of heat preservations 2h, 200 DEG C of heat preservation 11h in baking oven, taken out after cooling by the autoclave for setting 180ml
Autoclave is centrifuged slurry, washes twice reactant respectively with deionized water and dehydrated alcohol, and the material after washing is placed
It is dried at 65 DEG C of baking oven；Material after drying is taken into 1g, the starch of 0.21g is weighed, after being mixed and dried under suitable alcohols, in argon
Composite positive pole is made in the lower 650 DEG C of calcinings 2h of gas atmosphere.The attached drawing of material made from the embodiment is shown in Fig. 8, and a left side of Fig. 8 is attached
Figure is the SEM figure that diameter is 20 microns of second particles, and right attached drawing is that the SEM of sheet primary particle schemes.Fig. 8 can be seen that as by crystalline substance
The Three-dimensional Open structure spherical particle that assembles of nanometer sheet of planar orientation growth, conducive to sufficiently having for electrolyte and active material
Effect contact.Carbon containing 4.1wt% in the composite positive pole, it is shown that good cycle performance, as shown in figure 9, being passed through under 1C multiplying power
After crossing 100 weeks circulations, capacity retention ratio > 98%.
Comparative example 1
This comparative example is inquired into, specific as follows using the urea HMT described as mineralizer replacement:
It will measure than Li: Mn: P: urea=3: 1: 1: 1.5, weigh 0.06mol lithium chloride, 0.02mol manganese chloride, 0.02mol
Lithium chloride, four chloride hydrate manganese and urea are dissolved in 20ml ethylene glycol by phosphoric acid (85%) and 0.03mol urea respectively, and 30 DEG C add
Thermal agitation 30min；Phosphoric acid solution is instilled in the manganese chloride solution in stirring, is then instilled lithium chloride solution wherein, finally
Urea liquid is instilled, stirring 50min obtains mixed solution；Lotion shifts the autoclave for setting 180ml, and autoclave is set
80 DEG C of heat preservations 2h, 180 DEG C of heat preservation 12h in baking oven take out autoclave after cooling, slurry is centrifuged, with deionized water and nothing
Water-ethanol washes twice reactant respectively, and the material after washing is placed at 65 DEG C of baking oven and is dried；Material after drying is taken into 1g,
The polyvinyl alcohol of 0.3g is weighed, after being mixed and dried under suitable alcohols, 550 DEG C of calcining 4h, are made anode composite under an argon atmosphere
Material.The attached drawing of material made from the comparative example is shown in Figure 10, urea as mineralizer in the case where the pattern that is formed it is uncontrollable,
Grain is larger and disorderly and unsystematic.The material prepared charge-discharge test under 0.1C multiplying power only has 95mAh/g.
Comparative example 2
This comparative example is inquired into, and carries out two sections of warm area heat treatments using the solution system without ethylene glycol, concrete operations are as follows:
Will measure than Li: Mn: P: HMT=3: 1: 1: 1.5, weigh 0.06mol lithium chloride, 0.02mol manganese chloride,
0.02mol phosphoric acid (85%) and 0.03mol hexa are distinguished lithium chloride, four chloride hydrate manganese and hexa-methylene molten
In 20ml deionized water, stirring and dissolving；Phosphoric acid solution is instilled in the manganese chloride solution in stirring, then by lithium chloride solution
It instills wherein, finally instills hexa solution, stirring 30min obtains mixed solution；Solution shifts the high pressure for setting 180ml
Autoclave is placed in 80 DEG C of heat preservations 2h, 180 DEG C of heat preservation 10h in baking oven, takes out autoclave after cooling by reaction kettle, from
Heart slurry washes twice reactant with deionized water and dehydrated alcohol respectively, and the material after washing is placed at 65 DEG C of baking oven
Drying；Material after drying is taken into 1g, weighs the glucose of 0.3g, after being mixed and dried under suitable alcohols, under an argon atmosphere 600
DEG C calcining 4h, be made composite positive pole.The attached drawing of material made from the comparative example is shown in Figure 11, deionized water as solvent, from
Son diffusion faster, crystal grow up become apparent from synthesis material particle size be several microns more than, it is very fine and close, porous classification cannot be formed
Nano-micro structure.The material prepared charge-discharge test under 0.1C multiplying power only has 104.3mAh/g.
It is found by above embodiments and comparative example, using HMT as mineralizer, solution atmosphere of the cooperation containing ethylene glycol
Under, two sections of warm areas heat treatment is carried out, the lithium manganese phosphate material with excellent electric property is made in the performance of controllable prepared material
Material.
Claims (10)
1. it is a kind of with receive differential level structure lithium manganese phosphate material preparation method, which is characterized in that will include manganese source, lithium
Source, phosphorus source, hexamethylenetetramine, ethylene glycol material solution be heat-treated at 70 DEG C~80 DEG C in advance, then again 160 DEG C~
Solvent heat obtains at 200 DEG C.
2. preparation method as described in claim 1, which is characterized in that the mole of hexamethylenetetramine is 0.5-2.5 times of phosphorus
Sour manganese lithium.
3. preparation method as described in claim 1, which is characterized in that manganese source is manganese chloride, manganese acetate and manganese nitrate, manganese sulfate
At least one of；
Lithium source is at least one of lithium nitrate, lithium chloride and lithium acetate；
Phosphorus source is at least one of lithium dihydrogen phosphate, phosphoric acid.
4. preparation method as described in claim 1, which is characterized in that in the material solution, reactant concentration be
0.1-3mol/1。
5. preparation method as described in claim 1, which is characterized in that Li: Mn: P molar ratio be 2.5~3.5: 1: 1~
1.1。
6. preparation method as described in claim 1, which is characterized in that the time of heat treatment is 1~2h；The time of solvent heat is
10~15h.
7. preparation method as described in any one of claims 1 to 6, which comprises the following steps:
Manganese source, lithium source and hexamethylenetetramine are dissolved in ethylene glycol by step (1) respectively, and stirring obtains dense to abundant dissolution
Degree be 0.1mol/L~1mol/L manganese salt solution A, concentration be the solution B of 0.1mol/L~3mol/L lithium salts, concentration is
The solution C of 0.2mol/L~2mol/L hexamethylenetetramine, stirs 30min-60min respectively；
Step (2) weighs phosphorus source and is dissolved in ethylene glycol or water, forms the solution that concentration is 0.2mol/L~1mol/L, is dripped
In the solution A for entering the step (1) in stirring, the B solution instillation in step 1) is wherein then obtained into mixed solution D, is stirred
20min-60min；
Step (3) instills the C solution in step (1) in the solution D in step (2), forms solution E, molar ratio Li in solution:
Mn: P: HMT=2.5~3.5: 1: 1~1.1: 1~2.5,30min-60min is sufficiently stirred；
Solution E is transferred to autoclave by step (4), the heat treatment and solvent heat is successively being carried out, through solid-liquid after
It separates, wash, be dried to obtain.
8. a kind of differentiating stage lithium manganese phosphate/carbon composite anode material preparation method of receiving, which is characterized in that use claim 1
~7 described in any item preparation methods are made described having and receive the lithium manganese phosphate material of differential level structure；
By it is described have receive the lithium manganese phosphate material of differential level structure and mix, dry and in protective atmosphere in 500 with carbon source
DEG C~650 DEG C of calcinings obtain.
9. preparation method as claimed in claim 8, which is characterized in that the carbon source is cellulose, starch, polyethylene glycol, poly- second
At least one of enol high polymer；Carbon source dosage is 10wt%~30wt% of lithium manganese phosphate.
10. receive differentiating stage lithium manganese phosphate/carbon composite anode material made from preparation method described in a kind of claim 8 or 9,
Be characterized in that, comprising have receive differential level structure lithium manganese phosphate material and be coated on the carbon material on its surface；
With receive differential level structure lithium manganese phosphate material be the nanoscale primary particle with high preferred orientation be self-assembled into it is more
Hole second particle；The second particle is micron order or submicron particles；
The primary particle has (010) high preferred orientation growth characteristics；
The size of primary particle is 10~60nm；Second particle is having a size of 0.2~20 μm；
The carbon material is that macromolecule carbon source is pyrolyzed the amorphous carbon to be formed, wherein carbon material content is the anode composite
2%~5%wt of material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112018364A (en) * | 2020-09-05 | 2020-12-01 | 河南科技学院 | Equimolar hydrothermal method for preparing LiMnPO4Method for preparing composite material and application of composite material in lithium battery |
| CN112938918A (en) * | 2019-12-10 | 2021-06-11 | 湖南杉杉能源科技股份有限公司 | Preparation method of cobalt phosphate powder material |
| WO2024174374A1 (en) * | 2023-02-21 | 2024-08-29 | 湖北亿纬动力有限公司 | Electrode material and preparation method therefor, and battery |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101673819A (en) * | 2009-09-25 | 2010-03-17 | 清华大学 | Method for preparing manganese lithium phosphate/carbon composite material by manganese phosphate |
| CN101785995A (en) * | 2010-02-05 | 2010-07-28 | 华中科技大学 | Solvothermal preparation method for visible-light photocatalyst Bi2WO6 nano structure |
| CN102745663A (en) * | 2012-07-09 | 2012-10-24 | 四川九驰能源科技股份有限公司 | Method for preparing lithium iron phosphate material |
| CN104241645A (en) * | 2014-04-29 | 2014-12-24 | 常州普格纳能源材料有限公司 | Synthesis method of lithium-manganese-phosphate anode material |
| CN104716318A (en) * | 2015-04-03 | 2015-06-17 | 长沙理工大学 | Preparation method of spherical nickel-cobalt-manganese precursor |
| CN105417574A (en) * | 2014-09-05 | 2016-03-23 | 天津工业大学 | Preparation method of three-dimensional layered porous zinc oxide microspheres assembled from nano-sheets |
| CN107185543A (en) * | 2017-06-05 | 2017-09-22 | 衢州学院 | A kind of catalyst and its preparation and application for synthesizing methanol by hydrogenating carbon dioxide |
| CN107785570A (en) * | 2016-08-24 | 2018-03-09 | 德阳威旭锂电科技有限责任公司 | A kind of preparation method for improving olivine structural electrode material hydro-thermal method yield |
-
2018
- 2018-05-14 CN CN201810460766.6A patent/CN110492060B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101673819A (en) * | 2009-09-25 | 2010-03-17 | 清华大学 | Method for preparing manganese lithium phosphate/carbon composite material by manganese phosphate |
| CN101785995A (en) * | 2010-02-05 | 2010-07-28 | 华中科技大学 | Solvothermal preparation method for visible-light photocatalyst Bi2WO6 nano structure |
| CN102745663A (en) * | 2012-07-09 | 2012-10-24 | 四川九驰能源科技股份有限公司 | Method for preparing lithium iron phosphate material |
| CN104241645A (en) * | 2014-04-29 | 2014-12-24 | 常州普格纳能源材料有限公司 | Synthesis method of lithium-manganese-phosphate anode material |
| CN105417574A (en) * | 2014-09-05 | 2016-03-23 | 天津工业大学 | Preparation method of three-dimensional layered porous zinc oxide microspheres assembled from nano-sheets |
| CN104716318A (en) * | 2015-04-03 | 2015-06-17 | 长沙理工大学 | Preparation method of spherical nickel-cobalt-manganese precursor |
| CN107785570A (en) * | 2016-08-24 | 2018-03-09 | 德阳威旭锂电科技有限责任公司 | A kind of preparation method for improving olivine structural electrode material hydro-thermal method yield |
| CN107185543A (en) * | 2017-06-05 | 2017-09-22 | 衢州学院 | A kind of catalyst and its preparation and application for synthesizing methanol by hydrogenating carbon dioxide |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112938918A (en) * | 2019-12-10 | 2021-06-11 | 湖南杉杉能源科技股份有限公司 | Preparation method of cobalt phosphate powder material |
| CN112018364A (en) * | 2020-09-05 | 2020-12-01 | 河南科技学院 | Equimolar hydrothermal method for preparing LiMnPO4Method for preparing composite material and application of composite material in lithium battery |
| WO2024174374A1 (en) * | 2023-02-21 | 2024-08-29 | 湖北亿纬动力有限公司 | Electrode material and preparation method therefor, and battery |
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