CN104882602B - A kind of synthesis in solid state Al3+,Cu2+Adulterate cubic structure fluorination bismuth anode material for lithium-ion batteries and preparation method thereof - Google Patents
A kind of synthesis in solid state Al3+,Cu2+Adulterate cubic structure fluorination bismuth anode material for lithium-ion batteries and preparation method thereof Download PDFInfo
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- CN104882602B CN104882602B CN201510197217.0A CN201510197217A CN104882602B CN 104882602 B CN104882602 B CN 104882602B CN 201510197217 A CN201510197217 A CN 201510197217A CN 104882602 B CN104882602 B CN 104882602B
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 26
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- 238000003682 fluorination reaction Methods 0.000 title claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000007787 solid Substances 0.000 title claims abstract description 9
- 239000010405 anode material Substances 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 146
- 239000011737 fluorine Substances 0.000 claims abstract description 14
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 12
- 150000001450 anions Chemical class 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims description 48
- 150000001621 bismuth Chemical class 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 13
- 229920001400 block copolymer Polymers 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 4
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 4
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- ZWBAMYVPMDSJGQ-UHFFFAOYSA-N perfluoroheptanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZWBAMYVPMDSJGQ-UHFFFAOYSA-N 0.000 claims description 4
- CCUWGJDGLACFQT-UHFFFAOYSA-N 2,2,3,3,4,4-hexafluoropentanedioic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(O)=O CCUWGJDGLACFQT-UHFFFAOYSA-N 0.000 claims description 3
- GTDKXDWWMOMSFL-UHFFFAOYSA-M tetramethylazanium;fluoride Chemical compound [F-].C[N+](C)(C)C GTDKXDWWMOMSFL-UHFFFAOYSA-M 0.000 claims description 3
- 241000233803 Nypa Species 0.000 claims description 2
- 235000005305 Nypa fruticans Nutrition 0.000 claims description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- NQFNBCXYXGZSPI-UHFFFAOYSA-L copper;diacetate;dihydrate Chemical compound O.O.[Cu+2].CC([O-])=O.CC([O-])=O NQFNBCXYXGZSPI-UHFFFAOYSA-L 0.000 claims description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 150000004677 hydrates Chemical class 0.000 claims 1
- IXYXXQNFKSEXJM-UHFFFAOYSA-N n,n-dimethylmethanamine;hydron;fluoride Chemical compound F.CN(C)C IXYXXQNFKSEXJM-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002671 adjuvant Substances 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 3
- 238000003746 solid phase reaction Methods 0.000 abstract description 3
- 230000003335 steric effect Effects 0.000 abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- KFSZGBHNIHLIAA-UHFFFAOYSA-M benzyl(trimethyl)azanium;fluoride Chemical compound [F-].C[N+](C)(C)CC1=CC=CC=C1 KFSZGBHNIHLIAA-UHFFFAOYSA-M 0.000 description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 description 6
- BDJYZEWQEALFKK-UHFFFAOYSA-N bismuth;hydrate Chemical compound O.[Bi] BDJYZEWQEALFKK-UHFFFAOYSA-N 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910007086 Li1+xV3O8 Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- JYPVGDJNZGAXBB-UHFFFAOYSA-N bismuth lithium Chemical compound [Li].[Bi] JYPVGDJNZGAXBB-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- GCSVCUMDOQKEMT-UHFFFAOYSA-N butan-1-amine;hydrofluoride Chemical compound [H+].[F-].CCCCN GCSVCUMDOQKEMT-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 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
- H01M4/58—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
- H01M4/582—Halogenides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A kind of synthesis in solid state Al3+, Cu2+Adulterate cubic structure fluorination bismuth anode material for lithium-ion batteries and preparation method thereof, this method uses the quaternary ammonium salt using fluorine as anion to be raw material, space steric effect by macoradical and the direct synthesis of cubic structure fluorination bismuth of the effect solid phase by specific adjuvant, while passing through Cu2+Doping improves the electric discharge average potential of material, passes through Al3+Doping improves capacity circulating stability, and the fluorination bismuth material is used with more than 200mAh.g as anode material for lithium-ion batteries‑1Specific capacity.This method equipment requirement is low, and product purity is high, is avoided that in solid phase reaction generation is fluorinated the side reaction products such as a variety of double salt of bismuth and with excellent chemical property.
Description
Technical field
The present invention relates to a kind of electric positive electrode manufacture method technical field of high power capacity fluorination bismuth complex lithium.
Background technology
Lithium rechargeable battery has volume, weight energy higher than high, voltage, low self-discharge rate, memory-less effect, circulation
Long lifespan, power density height etc. definitely advantage, had more than at present in global portable power source market 30,000,000,000 dollar/year shares and with
Speed more than 10% gradually increases.Particularly in recent years, petering out with fossil energy, solar energy, wind energy, biomass
The new energy such as energy are increasingly becoming the alternative of traditional energy, and wherein wind energy, solar energy has intermittence, to meet lasting electricity
Power supply needs to use substantial amounts of energy-storage battery simultaneously；The urban air-quality problem that vehicle exhaust is brought is increasingly serious, electronic
Very urgent stage has been arrived in vigorously advocating and developing for car (EV) or hybrid electric vehicle (HEV)；These demands are provided
Lithium ion battery explosive growth point, while also the performance to lithium ion battery proposes higher requirement.
The raising of the capacity of anode material for lithium-ion batteries is the primary goal of scientific and technical personnel's research, high power capacity positive electrode
Research and development can to alleviate current Li-ion batteries piles volume big, heavy weight, price high-leveled and difficult to meet high power consumption and high-power equipment
The situation needed.But since lithium ion battery commercialization in 1991, the actual specific capacity of positive electrode is hovered all the time
Between 100-180mAh/g, the low bottleneck for having become lifting lithium ion battery specific energy of positive electrode specific capacity.It is commercial at present
The most commonly used practical positive electrode of lithium ion battery be LiCoO2, the theoretical specific capacity of cobalt acid lithium is 274mAh/g, and
Actual specific capacity is between 130-140mAh/g, and cobalt is strategic materials, expensive and have larger toxicity.Therefore in recent years
Come, the researcher of countries in the world is directed to the research and development of Olivine-type Cathode Material in Li-ion Batteries always, to current, screening
Up to tens of kinds of the lithium ion cell positive gone out, but really have potential commercial applications prospect or be already present in the market just
Pole material is really very few.Such as lithium manganate having spinel structure LiMn2O4, its cost is relatively low, is easier to prepare, security performance
It is relatively good, but capacity is relatively low, theoretical capacity is 148mAh/g, and actual capacity is in 100-120mAh/g, and the material capacity
Circulate holding capacity it is not good, under high temperature capacity attenuation quickly, Mn3+John-Teller effects and dissolving in the electrolyte it is long
Researcher has been annoying since phase.The LiNiO of layer structure2And LiMnO2Although there is larger theoretical specific capacity, it is respectively
275mAh/g and 285mAh/g, but they prepare extremely difficult, heat endurance is poor, and cyclicity is very poor, and capacity attenuation is quickly.And
Progressively commercialized LiFePO4 LiFePO at present4Cost is low, heat endurance is good, environment-friendly, but its theoretical capacity
About there was only 170mAh/g, and actual capacity is in 140mAh/g or so [Chun SY, Bloking J T, Chiang Y M, Nature
Materials, 2002,1：123-128.].The positive electrode more than 200mAh/g specific capacities for having market prospects at present only has vanadium
Sour lithium Li1+xV3O8, Li1+xV3O8Material can have possesses even close to 300mAh/g capacity, but its discharge average voltage it is relatively low and
And in production process barium oxide often toxicity is larger.High lithium is than on positive electrode in recent years, particularly manganese base manganese-nickel binary and
The high lithium of manganese base manganese-nickel-cobalt ternary solid solution system is steady with the Capacity Ratio more than 200mAh/g, higher heat than positive electrode
The cost of qualitative and relative moderate and paid close attention to by people, but the performance under the material high magnification is very undesirable, limitation
Its application [Young-Sik Hong, Yong Joon Park, et al., Solid State in electrokinetic cell
Ionics, 2005,176：1035-1042].
In recent years, fluoride positive electrode is because its capacity is high, the prices of raw materials are low and enter the visual field of researcher.Fluorine
The operation principle of compound material and conventional lithium ion battery positive electrode is different, traditional lithium ion cell positive and negative pole
All exist lithium ion can be embedded in or deintercalation space, and lithium ion in electrolyte it is embedded back and forth between a positive electrode and a negative electrode and
Deintercalation and " rocking chair " battery proposed as Armand etc. that discharges.And fluoride is then a kind of transition material, that is, whole
In individual discharge process, although Me has nothing in common with each other, MeFnCan occur similar following change [Badway F, Cosandey F,
Pereira N, et al., Electrodes for Li Batteries, J.Electrochem.Soc., 2003,150 (10)：
A1318-A1327.]：
nLi++MeFn+ne-→nLiF+Me0
It can discharge more than 200mAh.g in this process-1Specific capacity, thus obtain investigation of materials personnel height
Attention.Wherein fluorination bismuth is due to there is about 7170WhL-1Volume and capacity ratio and have big advantage.Conventional fluorination
The synthetic method of bismuth is to be carried out instead with metal simple-substance with hydrogen fluoride gas and metal oxide/hydroxide or fluorine gas at high temperature
Should, process conditions are harsh, and equipment requirement is very high, high energy consumption, therefore price is very expensive.And liquid phase reactor prepares fluorination bismuth then
It can not often be used because by-products content is too high as positive electrode while also lacking economy because producing many costs height of waste liquid
Property.Bismuth, which is fluorinated, as lithium ion secondary battery anode material also has a negative characteristic to be that its electronic conductivity is extremely low, because
This can cause very high polarizing voltage in charge and discharge process.
In addition fluorination bismuth crystal formation and pattern in lattice electrons transport property influence it is very big, therefore be directly connected to lithium from
The chemical property of sub- battery such as charge/discharge rates, capacity and circulation volume holding capacity；Ion doping is a kind of effective tune
The microstructure of lattice is saved, changes the means of lattice electron and ionic transport properties, however, ion doping even polyion is assisted
Extremely complex to the mechanism of action of parent with doping, effect is often difficult to expect.
Therefore a kind of simple technique, product quality stabilization, the synthesis in solid state fluorine with excellent electrochemical performance crystal formation are developed
It is to be fluorinated the key that bismuth material is applied as secondary cell to change bismuth preparation method.
The content of the invention
The present invention proposes a kind of synthesis in solid state Al for existing background technology3+, Cu2+Adulterate cubic structure fluorination bismuth lithium
Ion battery positive electrode and preparation method thereof, this method uses the quaternary ammonium salt using fluorine as anion to be raw material, passes through macoradical
Space steric effect and bismuth is fluorinated by the direct synthesis of cubic structure of the effect solid phase of specific adjuvant, while passing through Cu2+Doping
The electric discharge average potential of material is improved, passes through Al3+Doping improves capacity circulating stability, and the fluorination bismuth material is used as lithium-ion electric
Pond positive electrode, which is used, to be had more than 200mAh.g-1Specific capacity.This method equipment requirement is low, and product purity is high, is avoided that
Generation is fluorinated the side reaction products such as a variety of double salt of bismuth and with excellent chemical property in solid phase reaction.
This synthesis in solid state Al3+, Cu2+Adulterate cubic structure fluorination bismuth anode material for lithium-ion batteries and preparation method thereof,
It is characterized in that：By bismuth salt, the amount 0.5-2% of bismuth salt material aluminium salt, the amount 0.5-2% of bismuth salt material mantoquita, bismuth salt quality
Ball mill is put into after 0.5-2% auxiliary agent Z1 mixing, the mass ratio of ball milling and material is 20: 1, with 200-400 revs/min
Speed ball milling 10-20 hours, is referred to as material I by this material；By the quaternary ammonium salt using fluorine as anion, using fluorine as the quaternary ammonium of anion
Ball is put into after the 0.5-2% of salt quality auxiliary agent Z2, the 2-4% of the quaternary ammonium salt quality by anion of fluorine absolute ethyl alcohol mixing
Grinding machine, ball milling is 20: 1 with the mass ratio of material, with 200-400 revs/min of speed ball milling 10-20 hours, by this material
Referred to as material II；Material I, material II, material I and material II gross masses 2-4% crystal controlling agent Z3 are put into ball mill, ball
The mass ratio of mill and material is 20: 1, while it is 95: 5 that volume ratio is filled with ball grinder, an atmospheric pressure nitrogen and ammonia
Mixed gas, with 300-400 revs/min of speed ball milling 5-10 hours；Material after ball milling is taken out, after three times are washed,
This Al is made after being dried 10-20 hours in 100 DEG C of -120 DEG C of drying boxes3+, Cu2+Adulterate cubic structure fluorination bismuth.
Bismuth salt in preparation method as described above is one kind in five nitric hydrate bismuths, bismuth chloride；Aluminium salt is nine hydrations
One kind in aluminum nitrate, aluminium chloride, Patent alum；Mantoquita is Salzburg vitriol, Gerhardite, a hydration second
One kind in sour copper；Auxiliary agent Z1 is one kind in perfluoro-heptanoic acid, 2,2- difluoros cyclopropyl carboxylic acid, perfluoroglutaric acid；Auxiliary agent Z2 is to tell
One kind in temperature -60, op-10, Arlacel-80；Quaternary ammonium salt using fluorine as anion is tetra-n-butyl ammonium fluoride, tetramethyl fluorination
One kind in ammonium, benzyl trimethyl ammonium fluoride.The amount of the material of bismuth salt and the amount of the material of quaternary ammonium salt in material II in material I
Than for 1: 3；Crystal controlling agent Z3 is one kind in following block copolymer：
(1) acrylic acid and the number-average molecular weight of NIPA block copolymer PAA-b-PNIPAM, PAA parts
For 8000-12000, the number-average molecular weight of PNIPAM parts is 22000-26000, and molecular weight distributing index is 1.20-1.45；
(2) methacrylic acid and the number of methacrylic acid peopentyl ester block copolymer PMAA-b-PNPMA, PMAA parts are equal
Molecular weight is 8000-12000, and the number-average molecular weight of PNPMA parts is 20000-24000, and molecular weight distributing index is 1.1-
1.3；
(3) acrylic acid and the number-average molecular weight of n-butyl acrylate block copolymer PnBuA-b-PAA, PnBuA parts are
The number-average molecular weight of 7000-8000, PAA part is 5000-6000, and molecular weight distributing index is 1.4-1.6；
Three kinds of block copolymers as described above can directly be bought, such as Polymer Source companies of Canada.
Fig. 1 is charging capacity, discharge capacity and the efficiency for charge-discharge figure of preceding 10 circulations of the material, voltage range
1.8V-4.0V, charging and discharging currents 0.1C.Fig. 2 is the XRD of the material, and display structure is cubic structure.
Compared with prior art, the advantage of the invention is that：It is raw material to use the quaternary ammonium salt using fluorine as anion, by big
The space steric effect of group is simultaneously fluorinated bismuth by the direct synthesis of cubic structure of effect solid phase of specific adjuvant, while passing through Cu2+
Doping improves the electric discharge average potential of material, passes through Al3+Doping improve capacity circulating stability, the fluorination bismuth material as lithium from
Sub- cell positive material, which is used, to be had more than 200mAh.g-1Specific capacity.This method equipment requirement is low, and product purity is high, can keep away
Exempt from the generation in solid phase reaction and be fluorinated the side reaction products such as a variety of double salt of bismuth and with excellent chemical property.
Brief description of the drawings
Charging capacity, discharge capacity and the efficiency for charge-discharge figure of preceding 10 circulations of Fig. 1 materials, voltage range 1.8V-
4.0V, charging and discharging currents 0.1C.
The XRD of Fig. 2 materials, display structure is cubic structure.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1：By five nitric hydrate bismuths, the ANN aluminium nitrate nonahydrate of the amount 0.5% of five nitric hydrate bismuth materials, five hydrations
Ball is put into after the Salzburg vitriol of the amount 0.5% of bismuth nitrate material, the perfluoro-heptanoic acid mixing of five nitric hydrate bismuth quality 0.5%
Grinding machine, ball milling is 20: 1 with the mass ratio of material, and with 200 revs/min of speed ball milling 10 hours, this material is referred to as into material
I；By tetra-n-butyl ammonium fluoride, the Tween-60 of tetra-n-butyl ammonium fluoride quality 0.5%, tetra-n-butyl ammonium fluoride quality 2% nothing
Ball mill is put into after water-ethanol mixing, the sub mass ratio with material of ball milling is 20: 1, small with 200 revs/min of speed ball milling 10
When, this material is referred to as material II；By material I and material II according to quaternary ammonium in the amount of the material of bismuth salt in material I and material II
Ratio and material I and the crystal controlling agent acrylic acid of material II gross mass 2% and N- isopropyl of the ratio of the amount of salt material for 1: 3
Acrylamide block copolymer p AA-b-PNIPAM is put into ball mill, and the mass ratio of ball milling and material is 20: 1, while in ball
Nitrogen and the mixed gas of ammonia of the volume ratio for 95: 5 atmospheric pressure are filled with grinding jar, with 300 revs/min of speed ball milling
5 hours；Material after ball milling is taken out, after three times are washed, this Al is made after being dried 10 hours in 100 DEG C of drying boxes3+, Cu2+
Adulterate cubic structure fluorination bismuth.
Embodiment 2：By bismuth chloride, the aluminium chloride of the amount 1.0% of bismuth chloride material, the amount 1.0% of bismuth chloride material three
Ball mill, the matter of ball milling and material are put into after nitric hydrate copper, 2, the 2- difluoros cyclopropyl carboxylic acid mixing of bismuth chloride quality 1.0%
This material, with 300 revs/min of speed ball milling 15 hours, is referred to as material I by amount than being 20: 1；By Methanaminium, N,N,N-trimethyl-, fluoride, tetramethyl
Ball mill, ball are put into after 1.0% op-10 of base ammonium fluoride quality, the 3% absolute ethyl alcohol mixing of Methanaminium, N,N,N-trimethyl-, fluoride quality
The mass ratio of mill and material is 20: 1, and with 300 revs/min of speed ball milling 15 hours, this material is referred to as into material II；By thing
Expect the ratio that I and material II is 1: 3 according to the ratio of the amount of quaternary ammonium material in the amount and material II of the material of bismuth salt in material I
With material I and the crystal controlling agent methacrylic acid of material II gross masses 3% and methacrylic acid peopentyl ester block copolymer
PMAA-b-PNPMA is put into ball mill, and the mass ratio of ball milling and material is 20: 1, while being filled with volume ratio in ball grinder and being
The nitrogen and the mixed gas of ammonia of 95: 5 atmospheric pressure, with 350 revs/min of speed ball milling 7 hours；Take out thing after ball milling
Material, after three times are washed, this Al is made after being dried 15 hours in 110 DEG C of drying boxes3+, Cu2+The cubic structure that adulterates is fluorinated
Bismuth.
Embodiment 3：By bismuth chloride, the Patent alum of the amount 2% of bismuth chloride material, bismuth chloride material amount
Ball mill, ball milling and material are put into after 1.8% copper acetate dihydrate, the perfluoroglutaric acid mixing of bismuth chloride quality 2%
Mass ratio is 20: 1, and with 390 revs/min of speed ball milling 20 hours, this material is referred to as into material I；Benzyl trimethyl is fluorinated
Ammonium, 2% Arlacel-80 of benzyl trimethyl ammonium fluoride quality, the 4% absolute ethyl alcohol mixing of benzyl trimethyl ammonium fluoride quality
After be put into ball mill, the mass ratio of ball milling and material is 20: 1, with 400 revs/min of speed ball milling 19 hours, by this material
Referred to as material II；By material I and material II according to the amount of quaternary ammonium material in the amount of the material of bismuth salt in material I and material II
It is more common than the ratio for 1: 3 and material I and the crystal controlling agent acrylic acid of material II gross masses 3.8% and n-butyl acrylate block
Polymers PnBuA-b-PAA is put into ball mill, and the mass ratio of ball milling and material is 20: 1, while being filled with volume ratio in ball grinder
For the nitrogen and the mixed gas of ammonia of 95: 5 atmospheric pressure, with 390 revs/min of speed ball milling 9 hours；Take out after ball milling
Material, after three times are washed, this Al is made after being dried 20 hours in 120 DEG C of drying boxes3+, Cu2+The cubic structure that adulterates is fluorinated
Bismuth.
Embodiment 4：By bismuth chloride, the aluminium chloride of the amount 1% of bismuth chloride material, the amount 1.2% of bismuth chloride material three water
Ball mill, the quality of ball milling and material are put into after closing copper nitrate, 2, the 2- difluoros cyclopropyl carboxylic acid mixing of bismuth chloride quality 1.5%
Than for 20: 1, with 350 revs/min of speed ball milling 17 hours, this material is referred to as material I；By tetra-n-butyl ammonium fluoride, four just
It is put into after 1.5% Arlacel-80 of butyl ammonium fluoride quality, the 3.2% absolute ethyl alcohol mixing of tetra-n-butyl ammonium fluoride quality
Ball mill, ball milling is 20: 1 with the mass ratio of material, and with 360 revs/min of speed ball milling 15 hours, this material is referred to as into thing
Expect II；According to the ratio of the amount of quaternary ammonium material in the amount of the material of bismuth salt in material I and material II it is 1 by material I and material II:
3 ratio and material I and the crystal controlling agent acrylic acid of material II gross masses 3.2% and n-butyl acrylate block copolymer
PnBuA-b-PAA is put into ball mill, and the sub mass ratio with material of ball milling is 20: 1, while it is 95 that volume ratio is filled with ball grinder
: the nitrogen of 5 one atmospheric pressure and the mixed gas of ammonia, with 320 revs/min of speed ball milling 6 hours；Take out thing after ball milling
Material, after three times are washed, this Al is made after being dried 16 hours in 110 DEG C of drying boxes3+, Cu2+The cubic structure that adulterates is fluorinated
Bismuth.
Embodiment 5：By five nitric hydrate bismuths, Patent alum, five water of the amount 0.8% of five nitric hydrate bismuth materials
Ball is put into after closing the Salzburg vitriol of the amount 1.5% of bismuth nitrate material, the perfluoro-heptanoic acid mixing of five nitric hydrate bismuth quality 2%
Grinding machine, ball milling is 20: 1 with the mass ratio of material, and with 350 revs/min of speed ball milling 12 hours, this material is referred to as into material
I；By benzyl trimethyl ammonium fluoride, 1.3% Tween-60 of benzyl trimethyl ammonium fluoride quality, benzyl trimethyl ammonium fluoride matter
Ball mill is put into after the 3.6% absolute ethyl alcohol mixing of amount, the mass ratio of ball milling and material is 20: 1, with 380 revs/min
Speed ball milling 17 hours, is referred to as material II by this material；By material I and material II according to the amount of the material of bismuth salt in material I with
The ratio that the ratio of the amount of quaternary ammonium material is 1: 3 in material II and material I and the crystal controlling agent first of material II gross masses 3.5%
Base acrylic acid is put into ball mill, the quality of ball milling and material with methacrylic acid peopentyl ester block copolymer PMAA-b-PNPMA
Than for 20: 1, while nitrogen and the mixed gas of ammonia of the volume ratio for 95: 5 atmospheric pressure are filled with ball grinder, with 330
Rev/min speed ball milling 8 hours；Material after ball milling is taken out, after three times are washed, 18 are dried in 110 DEG C of drying boxes small
When after be made this Al3+, Cu2+Adulterate cubic structure fluorination bismuth.
Claims (2)
1. a kind of synthesis in solid state Al3+、Cu2+The cubic structure that adulterates is fluorinated the preparation method of bismuth anode material for lithium-ion batteries, and it is special
Levy the aluminium salt for being the amount 0.5-2% by bismuth salt, bismuth salt material, the amount 0.5-2% of bismuth salt material mantoquita, bismuth salt quality 0.5-
Ball mill is put into after 2% auxiliary agent Z1 mixing, the mass ratio of ball milling and material is 20: 1, with 200-400 revs/min of speed
Ball milling 10-20 hours, is referred to as material I by this material；By the quaternary ammonium salt using fluorine as anion, the quaternary ammonium salt matter by anion of fluorine
Ball milling is put into after the 0.5-2% of amount auxiliary agent Z2, the 2-4% of the quaternary ammonium salt quality by anion of fluorine absolute ethyl alcohol mixing
Machine, ball milling is 20: 1 with the mass ratio of material, and with 200-400 revs/min of speed ball milling 10-20 hours, this material is claimed
For material II；Material I, material II, material I and material II gross masses 2-4% crystal controlling agent Z3 are put into ball mill, ball milling
The mass ratio of son and material is 20: 1, while being filled with the nitrogen and ammonia that volume ratio is 95: 5 atmospheric pressure in ball grinder
Mixed gas, with 300-400 revs/min of speed ball milling 5-10 hours；Material after ball milling is taken out, after three times are washed,
This Al is made after being dried 10-20 hours in 100 DEG C of -120 DEG C of drying boxes3+、Cu2+Adulterate cubic structure fluorination bismuth；
Bismuth salt in preparation method as described above is one kind in five nitric hydrate bismuths, bismuth chloride；Aluminium salt is nine nitric hydrates
One kind in aluminium, aluminium chloride, Patent alum；Mantoquita is Salzburg vitriol, Gerhardite, copper acetate dihydrate
In one kind；Auxiliary agent Z1 is one kind in perfluoro-heptanoic acid, 2,2- difluoros cyclopropyl carboxylic acid, perfluoroglutaric acid；Auxiliary agent Z2 be tween-
60th, one kind in op-10, Arlacel-80；Quaternary ammonium salt using fluorine as anion is tetra-n-butyl ammonium fluoride, Methanaminium, N,N,N-trimethyl-, fluoride, benzyl
One kind in base trimethyl ammonium fluoride；The ratio of the amount of the material of bismuth salt and the amount of the material of quaternary ammonium salt in material II is 1 in material I
∶3；Crystal controlling agent Z3 is one kind in following block copolymer：
(1) acrylic acid and the number-average molecular weight of NIPA block copolymer PAA-b-PNIPAM, PAA parts are
The number-average molecular weight of 8000-12000, PNIPAM part is 22000-26000, and molecular weight distributing index is 1.20-1.45；
(2) methacrylic acid and the equal molecule of number of methacrylic acid peopentyl ester block copolymer PMAA-b-PNPMA, PMAA parts
Measure as 8000-12000, the number-average molecular weight of PNPMA parts is 20000-24000, and molecular weight distributing index is 1.1-1.3；
(3) number-average molecular weight of acrylic acid and n-butyl acrylate block copolymer PnBuA-b-PAA, PnBuA parts is 7000-
The number-average molecular weight of 8000, PAA parts is 5000-6000, and molecular weight distributing index is 1.4-1.6.
2. synthesis in solid state Al according to claim 13+、Cu2+Adulterate cubic structure fluorination bismuth anode material for lithium-ion batteries
Preparation method, it is characterised in that the fluorination bismuth prepared have more than 200mAhg-1Specific capacity.
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