CN106450301B - A kind of lithium ion battery boric acid ferrous iron lithium anode material and preparation method thereof - Google Patents
A kind of lithium ion battery boric acid ferrous iron lithium anode material and preparation method thereof Download PDFInfo
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- CN106450301B CN106450301B CN201610944636.0A CN201610944636A CN106450301B CN 106450301 B CN106450301 B CN 106450301B CN 201610944636 A CN201610944636 A CN 201610944636A CN 106450301 B CN106450301 B CN 106450301B
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- lithium
- boric acid
- acid ferrous
- anode material
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 239000004327 boric acid Substances 0.000 title claims abstract description 155
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 151
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 239000010405 anode material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 47
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052912 lithium silicate Inorganic materials 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 16
- 150000002148 esters Chemical class 0.000 claims description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 30
- 229910052710 silicon Inorganic materials 0.000 claims description 30
- 239000010703 silicon Substances 0.000 claims description 30
- 241001502050 Acis Species 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- 239000011261 inert gas Substances 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 21
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 14
- 239000007792 gaseous phase Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 5
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 238000005137 deposition process Methods 0.000 abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 17
- 239000000377 silicon dioxide Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 22
- 238000000576 coating method Methods 0.000 description 21
- 239000007791 liquid phase Substances 0.000 description 20
- -1 phosphate anion Chemical class 0.000 description 14
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 238000001354 calcination Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000011241 protective layer Substances 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001556 Li2Si2O5 Inorganic materials 0.000 description 2
- 229910007547 Li2Si5 Inorganic materials 0.000 description 2
- 229910010846 Li6Si2O7 Inorganic materials 0.000 description 2
- 229910010532 LiFeBO3 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910000904 FeC2O4 Inorganic materials 0.000 description 1
- 229910007562 Li2SiO3 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229940063013 borate ion Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- H01M4/5825—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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of lithium ion battery boric acid ferrous iron lithium anode materials and preparation method thereof, belong to technical field of lithium ion battery positive pole material preparation.The boric acid ferrous iron lithium anode material includes boric acid ferrous lithium and the lithium metasilicate for being coated on boric acid ferrous lithium surface, and the mass ratio of the lithium metasilicate and the boric acid ferrous lithium is 0.02:1~0.1:1.Vapour deposition process is used in the present invention, coats lithium metasilicate on boric acid ferrous lithium surface using the reaction of silica and lithia.The lithium metasilicate for being coated on boric acid ferrous lithium surface can prevent boric acid ferrous lithium directly and air contact, keep gained boric acid ferrous iron lithium anode material with good stability, be able to maintain good performance contacting for a long time with air.
Description
The application be on April 30th, 2015 applying date, application No. is 201510219844.X, entitled " a kind of
The divisional application of the patent application of lithium ion battery boric acid ferrous iron lithium anode material and preparation method thereof ".
Technical field
The present invention relates to technical field of lithium ion battery positive pole material preparation, in particular to a kind of lithium ion battery boric acid is sub-
Iron lithium anode material and preparation method thereof.
Background technique
Lithium ion battery has energy density height, long service life, good cycle and nothing as a kind of high-energy battery
The advantages that memory effect.LiFePO 4 (LiFePO4) it is one of currently used anode material for lithium-ion batteries, ferrous phosphate
The theoretical specific capacity of lithium is 170mAh/g, since there are the unavoidable factor that will lead to capacity reduction, LiFePO 4 is real
Border specific capacity has reached 140~160mAh/g, almost without the space of promotion.Therefore, it is necessary to develop new to have higher ratio
The anode material for lithium-ion batteries of capacity.
A kind of method effectively improving positive electrode specific capacity is mole of oxygen-containing acid group in reduction positive electrode molecular formula
Quality.The molal weight of phosphate anion in LiFePO 4 is 95, gentlier and is capable of forming oxygen-containing acid group than P elements
The element of ion only has boron element and nitrogen, but the oxygen-containing acid group that nitrogen is formed has oxidisability, is not suitable as lithium
Ion battery positive electrode.And the molal weight of borate ion is 58.8, phosphate anion is much smaller than, so boric acid ferrous lithium
(LiFeBO3) theoretical specific capacity be 220mAh/g.In addition, the conductivity of boric acid ferrous lithium is 3.9 × 10-7(phosphoric acid is sub- by S/cm
Iron lithium is 10-9S/cm), the volume change during removal lithium embedded is 2% (LiFePO 4 6%), therefore, boric acid ferrous lithium
Also there is better high rate performance and stable circulation performance.For example, disclosing boron in CN103553064A, CN104140111A
Ferrous silicate lithium positive electrode and preparation method thereof.But boric acid ferrous lithium is very sensitive to vapor and oxygen, puts in air
It sets 30 minutes its specific capacities and drops down to 70mAh/g.
In the implementation of the present invention, the inventors discovered that in the prior art the prior art has at least the following problems: existing boron
Ferrous silicate lithium positive electrode is unstable in air, and short-time contact air will lead to its performance and decline rapidly.
Summary of the invention
In order to solve the above technical problems, the present invention provide it is a kind of can in air the stable boric acid of retention properties it is sub-
Iron lithium anode material.
Specifically, including technical solution below:
First aspect present invention provides a kind of lithium ion battery boric acid ferrous iron lithium anode material, the boric acid ferrous lithium anode
Material includes boric acid ferrous lithium and the lithium metasilicate for being coated on boric acid ferrous lithium surface, and the lithium metasilicate and the boric acid are sub-
The mass ratio of iron lithium is 0.02:1~0.1:1.
Second aspect of the present invention provides a kind of lithium ion battery boric acid ferrous iron lithium anode material of first aspect present invention
Preparation method, the preparation method comprises the following steps:
Step 1, esters of silicon acis is dissolved in solvent, obtains the silicic acid ester solution of mass concentration 1~5%, the mass concentration
For SiO in esters of silicon acis molecular formula2Quality account for the mass percent of the silicic acid ester solution；It is added into the silicic acid ester solution
Boric acid ferrous lithium and lithia are stirred at room temperature after 1~12 hour heating in an inert gas atmosphere and remove before solvent obtains
Drive object；The mass ratio of the lithia and boric acid ferrous lithium is 0.001:1~0.006:1；The quality of the silicic acid ester solution
Ratio with the gross mass of the boric acid ferrous lithium and lithia is 1:1~1:3；
Step 2, the temperature lower calcination 1~4 by step 1 gained predecessor in an inert gas atmosphere at 500~700 DEG C is small
When, the lithium ion battery boric acid ferrous iron lithium anode material is obtained after cooling.
Preferably, esters of silicon acis described in step 1 is selected from ethyl orthosilicate, methyl orthosilicate, positive silicic acid propyl ester and positive silicon
At least one of acid butyl ester.
Preferably, solvent described in step 1 in alcohols solvent, ether solvent and alkane solvents at least one
Kind.
Preferably, solvent described in step 1 is in ethyl alcohol, propyl alcohol, tetrahydrofuran, ether, hexamethylene and n-hexane
At least one.
Preferably, inert gas described in step 1 and step 2 is selected from least one of nitrogen, argon gas.
Third aspect present invention provides the lithium ion battery boric acid ferrous lithium anode material of another first aspect present invention
The preparation method of material, the preparation method is that:
The mixture of boric acid ferrous lithium and lithia is added in gaseous phase deposition stove, is warming up in an inert gas atmosphere
500~700 DEG C, the mixed gas of esters of silicon acis steam and inert gas, the mixing are then passed through into the gaseous phase deposition stove
The time that is passed through of gas is 1~4 hour, and the mixed gas flow is 60~200mL/ minutes, then in inert gas atmosphere
Up to the boric acid ferrous iron lithium anode material after middle cooling；Lithia and boron in the mixture of the boric acid ferrous lithium and lithia
The mass ratio of ferrous silicate lithium is 0.001:1~0.006:1.
Preferably, the esters of silicon acis is in ethyl orthosilicate, methyl orthosilicate, positive silicic acid propyl ester and butyl silicate
At least one.
Preferably, the inert gas is selected from least one of nitrogen, argon gas.
Technical solution provided in an embodiment of the present invention the utility model has the advantages that
1, the embodiment of the present invention improves existing boric acid ferrous iron lithium anode material, is decomposed using esters of silicon acis and generates two
Silica and lithia reaction prevent boric acid ferrous lithium from directly connecing with air in boric acid ferrous lithium Surface Creation lithium metasilicate protective layer
Touching keeps gained boric acid ferrous iron lithium anode material with good stability, is able to maintain contacting for a long time with air good
Performance.
2, since boric acid ferrous iron lithium anode material obtained by the embodiment of the present invention in air stablize by property, in lithium ion
In battery anode slurry, anode pole piece preparation process, stringent anhydrous and oxygen-free environment is not needed, can adapt to large-scale industry
Metaplasia produces.
3, the embodiment of the present invention coats lithium metasilicate on boric acid ferrous lithium surface using liquid phase coating method or vapour deposition process,
Raw material is cheap and easy to get, simple process, is easy to control, and is advantageously implemented large-scale industrial production.
Specific embodiment
To keep technical solution of the present invention and advantage clearer, embodiment of the present invention is made below further detailed
Description.
First aspect present invention provides a kind of lithium ion battery boric acid ferrous iron lithium anode material, the boric acid ferrous lithium anode
Material includes boric acid ferrous lithium and the lithium metasilicate for being coated on boric acid ferrous lithium surface, and the lithium metasilicate and the boric acid are sub-
The mass ratio of iron lithium is 0.02:1~0.1:1.
Boric acid ferrous lithium theoretical specific capacity with higher, good high rate performance and cyclical stability, are very suitable to
As anode material for lithium-ion batteries.But boric acid ferrous lithium is very sensitive to oxygen and vapor, even if short-time contact
It will lead to its performance to decline rapidly, limit application of the boric acid ferrous lithium as anode material for lithium-ion batteries.The present invention is implemented
Example prevents boric acid ferrous lithium and oxygen, vapor from directly contacting, makes by coating lithium metasilicate protective layer on boric acid ferrous lithium surface
Gained boric acid ferrous iron lithium anode material is with good stability, is able to maintain good property contacting for a long time with air
Energy.And since covering amount is smaller, it will not influence other performances of gained boric acid ferrous iron lithium anode material.
In above-mentioned boric acid ferrous iron lithium anode material, the mass ratio of the lithium metasilicate and the boric acid ferrous lithium can be with
For 0.03:1,0.04:1,0.05:1,0.06:1,0.07:1,0.08:1,0.09:1 etc..
Second aspect of the present invention provides a kind of lithium ion battery boron using liquid phase coating method preparation first aspect present invention
The method of ferrous silicate lithium positive electrode, the preparation method comprises the following steps:
Step 1, esters of silicon acis is dissolved in solvent, obtains the silicic acid ester solution of mass concentration 1~5%, the mass concentration
For SiO in esters of silicon acis molecular formula2Quality account for the mass percent of the silicic acid ester solution；It is added into the silicic acid ester solution
Boric acid ferrous lithium and lithia are stirred at room temperature after 1~12 hour heating in an inert gas atmosphere and remove before solvent obtains
Drive object；The mass ratio of the lithia and boric acid ferrous lithium is 0.001:1~0.006:1；The quality of the silicic acid ester solution
Ratio with the gross mass of the boric acid ferrous lithium and lithia is 1:1~1:3；
Step 2, the temperature lower calcination 1~4 by step 1 gained predecessor in an inert gas atmosphere at 500~700 DEG C is small
When, the lithium ion battery boric acid ferrous iron lithium anode material is obtained after cooling.
The principle of above-mentioned liquid phase coating method are as follows: after boric acid ferrous lithium and lithia are added in silicic acid ester solution, boric acid is sub-
After water contact in iron lithium and air, surface can hydrolyze generation basic group；And meeting after the water contact in esters of silicon acis and air
Hydrolysis generates silicic acid；Silicate ion in the basic group adsorbent solution on boric acid ferrous lithium surface.Height is carried out after removing solvent
Temperature calcining.In high-temperature burning process, silicic acid is unstable to resolve into silica, and silica is sent out with lithia at high temperature
Raw reaction, generates lithium metasilicate, to form lithium metasilicate protective layer on boric acid ferrous lithium surface.Above-mentioned liquid phase coating method technique letter
List is easy to control, and lithium metasilicate is evenly distributed on boric acid ferrous lithium surface.
The reaction of silica and lithia can generate different products, such as Li due to the difference of the two ratio2SiO3、
Li6Si2O7、Li2Si2O5、Li2Si5O11Deng, therefore the composition for being coated on the lithium metasilicate on boric acid ferrous lithium surface may be a certain
The mixture of product either multi-products.
In above-mentioned liquid phase coating preparation method, the not stringent restriction of the specific type of the esters of silicon acis in step 1, this
The common esters of silicon acis in field, for example, can be ethyl orthosilicate, methyl orthosilicate, positive silicic acid propyl ester or positive silicic acid fourth
Ester etc., can be used alone esters of silicon acis, can also be used in mixed way with a variety of esters of silicon acis.
In above-mentioned liquid phase coating preparation method, the not stringent restriction of solvent in step 1, as long as silicic acid can be made
Ester sufficiently dissolves, such as can be alcohols solvent, ether solvent, alkane solvents etc..Alcohols solvent can be ethyl alcohol, third
Alcohol etc., ether solvent can be tetrahydrofuran, ether etc., and alkane solvents can be hexamethylene, n-hexane etc..It can be a kind of molten
Agent is used alone, and can also be used in mixed way with multi-solvents.Solvent used in step 1, which needs not move through, particularly removes water process,
Moisture in solvent is conducive to boric acid ferrous lithium adsorption silicate instead.
In above-mentioned liquid phase coating preparation method, the also not stringent limit of inert gas used in step 1 and step 2
It is fixed, inert gas, such as nitrogen, argon gas commonly used in the art etc..
In above-mentioned liquid phase coating preparation method, in step 1, the mass concentration of esters of silicon acis can for 2%, 2.5%,
3%, 3.5%, 4%, 4.5% etc..
In above-mentioned liquid phase coating preparation method, in step 1, the mass ratio of the lithia and boric acid ferrous lithium can
Think 0.002:1,0.003:1,0.004:1,0.005:1 etc..
In above-mentioned liquid phase coating preparation method, in step 1, the not stringent restriction of the temperature of heating removing solvent,
As long as solvent can be made thoroughly to remove.
In above-mentioned liquid phase coating preparation method, in step 1, the quality of the silicic acid ester solution and the boric acid are ferrous
The ratio of the gross mass of lithium and lithia can be 1:1.5,1:2,1:2.5 etc..
In above-mentioned liquid phase coating preparation method, in step 2, calcination temperature can be 550 DEG C, 600 DEG C, 650 DEG C etc..
In above-mentioned liquid phase coating preparation method, in step 2, be warming up to calcination temperature heating rate do not have it is special
It is required that such as can be 2~10 DEG C/min.
Third aspect present invention provides another using the lithium-ion electric of vapour deposition process preparation first aspect present invention
The method of pond boric acid ferrous iron lithium anode material, the preparation method is that:
The mixture of boric acid ferrous lithium and lithia is added in gaseous phase deposition stove, is warming up in an inert gas atmosphere
500~700 DEG C, the mixed gas of esters of silicon acis steam and inert gas, the mixing are then passed through into the gaseous phase deposition stove
The time that is passed through of gas is 1~4 hour, and the mixed gas flow is 60~200mL/ minutes, then in inert gas atmosphere
Up to the boric acid ferrous iron lithium anode material after middle cooling；Lithia and boron in the mixture of the boric acid ferrous lithium and lithia
The mass ratio of ferrous silicate lithium is 0.001:1~0.006:1.
The principle of above-mentioned vapour deposition process are as follows: after esters of silicon acis steam enters gaseous phase deposition stove, decompose at high temperature, point
Solving includes silica in product, and silica and lithia react generate lithium metasilicate at high temperature, thus in boric acid Asia
Iron lithium surface forms lithium metasilicate protective layer.Above-mentioned vapour deposition process technique is same simply, is easy to control.Moreover, because esters of silicon acis
Decomposition product in, further include carbon, therefore the boric acid ferrous iron lithium anode material surface being prepared with vapour deposition process also coats
There is carbon, the presence of carbon can be improved the electric conductivity of boric acid ferrous iron lithium anode material.
Similar with liquid phase coating method, lithium metasilicate protective layer obtained by vapour deposition process is also due to silica and lithia ratio
The difference of example generates different products, such as Li2SiO3、Li6Si2O7、Li2Si2O5、Li2Si5O11Deng, therefore it is coated on boric acid Asia
The composition of the lithium metasilicate on iron lithium surface may be the mixture of a certain product either multi-products.
In above-mentioned gas-phase deposition process for preparing, the specific type of esters of silicon acis used, can also without stringent restriction
To be the esters of silicon acis commonly used in the art such as ethyl orthosilicate, methyl orthosilicate, positive silicic acid propyl ester, butyl silicate.It can be one
Kind esters of silicon acis is used alone, and is also possible to a variety of esters of silicon acis and is used in mixed way.
In above-mentioned gas-phase deposition process for preparing, inert gas used also not stringent restriction is commonly used in the art
Inert gas, such as nitrogen, argon gas etc..
In above-mentioned gas-phase deposition process for preparing, reaction temperature can be 550 DEG C, 600 DEG C, 650 DEG C etc..
In above-mentioned gas-phase deposition process for preparing, the time that is passed through of the mixed gas of esters of silicon acis steam and inert gas can
Think 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours etc..
In above-mentioned gas-phase deposition process for preparing, the mixed gas flow of the esters of silicon acis and inert gas can be
80mL/ minutes, 100mL/ minutes, 120mL/ minutes, 140mL/ minutes, 160mL/ minutes, 180mL/ minutes etc..
In above-mentioned liquid phase coating method and vapour deposition process, since boric acid ferrous lithium is unstable, without commercialized production
Product, it is therefore desirable to which those skilled in the art voluntarily prepare.Preparation method does not specially require, and can use system commonly used in the art
Preparation Method, such as solid reaction process, sol-gel method, coprecipitation etc..It can make lithium source when preparing boric acid ferrous lithium
Amount is excessive, so that it may directly obtain the mixture of boric acid ferrous lithium and lithia, can thus make lithia and boric acid ferrous
Lithium mixing is more uniform, to keep finally formed lithium metasilicate protective layer more uniform.
Following example 1~6 the method according to the invention prepare boric acid ferrous iron lithium anode material, and wherein Examples 1 to 3 is adopted
With liquid phase coating method, embodiment 4~6 uses vapour deposition process.Gained boric acid ferrous iron lithium anode material is assembled to lithium-ion electric
Chi Zhong, and the performance of gained lithium ion battery is tested；Gained boric acid ferrous iron lithium anode material is placed in air again
It is assembled in lithium ion battery after a week, and the performance of gained lithium ion battery is tested.Wherein, the dress of lithium ion battery
Method of completing the square is as follows:
By gained boric acid ferrous iron lithium anode material and conductive agent acetylene black, binder PVDF (Kynoar) according to quality
Ratio than 80:10:10 is uniformly mixed, and said mixture is modulated into slurry with NMP (1-Methyl-2-Pyrrolidone), uniformly
Coated on aluminium foil, 100 DEG C are dried in vacuo 24 hours, obtained experimental cell pole piece.Then with lithium piece be to electrode, with
1mol/L LiPF6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1:1) solution be electrolyte, with
Celgard2400 film is diaphragm, is assembled into CR2025 type button cell in the glove box full of argon atmosphere.
Test condition: voltage is 2.5~4.2V, electric current 20mA/g.
In following example 1~6, the mixture of boric acid ferrous lithium and lithia used is prepared using following methods:
According to LiFeBO3Stoichiometric ratio by Li2CO3、FeC2O4·2H2O and B2O3It is uniformly mixed, wherein Li2CO3It crosses
Amount 1~5% calcines 4 hours under protection of argon gas with solid reaction process up to the mixing of boric acid ferrous lithium and lithia for 600 DEG C
Object, wherein the mass ratio of lithia and boric acid ferrous lithium is 0.001:1~0.006:1.
Embodiment 1
The present embodiment provides a kind of methods that liquid phase coating method prepares boric acid ferrous iron lithium anode material, and steps are as follows:
Step 1, ethyl orthosilicate is dissolved in ethyl alcohol, is configured to the solution of mass concentration 1% (with ethyl orthosilicate molecule
Middle SiO2Quality meter), into above-mentioned solution be added boric acid ferrous lithium and lithia mixture, be stirred at room temperature 1 hour
Afterwards, solvent evaporated obtains predecessor under nitrogen protection；Wherein, the mass ratio of lithia and boric acid ferrous lithium are as follows: 0.002:
1, the ratio of the gross mass of the mixture of the quality and boric acid ferrous lithium and lithia of solution is 1:1.
Step 2, step 1 gained predecessor is put into tube furnace, in 600 DEG C of temperature lower calcination 2 in nitrogen atmosphere
Hour, the lithium ion battery boric acid ferrous iron lithium anode material is obtained after cooling.
Lithium metasilicate and the boric acid that boric acid ferrous lithium surface is coated in boric acid ferrous iron lithium anode material obtained by the present embodiment are sub-
The ratio of iron lithium is 0.02:1.
It is with the be positive first discharge specific capacity of the battery of pole material of boric acid ferrous iron lithium anode material obtained by the present embodiment
208mAh/g, 100 times circulation after specific capacity still remain in 153mAh/g.
Above-mentioned material to be placed in air after a week, the first discharge specific capacity of gained battery is 201mAh/g, 100 times
Specific capacity stills remain in 134mAh/g after circulation.
Embodiment 2
The present embodiment provides a kind of methods that liquid phase coating method prepares boric acid ferrous iron lithium anode material, and steps are as follows:
Step 1, ethyl orthosilicate is dissolved in tetrahydrofuran, is configured to the solution of mass concentration 5% (with ethyl orthosilicate
SiO in molecule2Quality meter), into above-mentioned solution be added boric acid ferrous lithium and lithia mixture, be stirred at room temperature 4
After hour, solvent evaporated obtains predecessor under nitrogen protection；Wherein, the mass ratio of lithia and boric acid ferrous lithium are as follows:
0.006:1, the ratio of the gross mass of the mixture of the quality and boric acid ferrous lithium and lithia of solution are 1:3.
Step 2, step 1 gained predecessor is put into tube furnace, in 500 DEG C of temperature lower calcination 4 in nitrogen atmosphere
Hour, the lithium ion battery boric acid ferrous iron lithium anode material is obtained after cooling.
Lithium metasilicate and the boric acid that boric acid ferrous lithium surface is coated in boric acid ferrous iron lithium anode material obtained by the present embodiment are sub-
The ratio of iron lithium are as follows: 0.05:1.
It is with the be positive first discharge specific capacity of the battery of pole material of boric acid ferrous iron lithium anode material obtained by the present embodiment
195mAh/g, 100 times circulation after specific capacity still remain in 117mAh/g.
Above-mentioned material to be placed in air after a week, the first discharge specific capacity of gained battery is 186mAh/g, 100 times
Specific capacity stills remain in 102mAh/g after circulation.
Embodiment 3
The present embodiment provides a kind of methods that liquid phase coating method prepares boric acid ferrous iron lithium anode material, and steps are as follows:
Step 1, ethyl orthosilicate is dissolved in n-hexane, is configured to the solution of mass concentration 3% (with ethyl orthosilicate point
SiO in son2Quality meter), into above-mentioned solution be added boric acid ferrous lithium and lithia mixture, it is small to be stirred at room temperature 12
Shi Hou, solvent evaporated obtains predecessor under nitrogen protection；Wherein, the mass ratio of lithia and boric acid ferrous lithium are as follows:
0.005:1, the ratio of the gross mass of the mixture of the quality and boric acid ferrous lithium and lithia of solution are 1:1.
Step 2, step 1 gained predecessor is put into tube furnace, in 700 DEG C of temperature lower calcination 1 in nitrogen atmosphere
Hour, the lithium ion battery boric acid ferrous iron lithium anode material is obtained after cooling.
Lithium metasilicate and the boric acid that boric acid ferrous lithium surface is coated in boric acid ferrous iron lithium anode material obtained by the present embodiment are sub-
The ratio of iron lithium is 0.04:1.
It is with the be positive first discharge specific capacity of the battery of pole material of boric acid ferrous iron lithium anode material obtained by the present embodiment
211mAh/g, 100 times circulation after specific capacity still remain in 181mAh/g.
Above-mentioned material to be placed in air after a week, the first discharge specific capacity of gained battery is 207mAh/g, 100 times
Specific capacity stills remain in 163mAh/g after circulation.
In following example 4~6, the mixed gas of esters of silicon acis steam and inert gas used is obtained using following methods:
Esters of silicon acis volatilizees at room temperature generates esters of silicon acis steam, is brought esters of silicon acis steam in gaseous phase deposition stove into inert gas.
Embodiment 4
It is specific as follows the present embodiment provides a kind of method that vapour deposition process prepares boric acid ferrous iron lithium anode material:
The mixture of boric acid ferrous lithium and lithia is added in gaseous phase deposition stove, 500 DEG C are warming up in nitrogen atmosphere,
Then the mixed gas of ethyl orthosilicate steam and nitrogen is passed through into gaseous phase deposition stove with 100mL/ minutes flows, when being passed through
Between be 4 hours.Then it cools down in nitrogen atmosphere to get the boric acid ferrous iron lithium anode material；Wherein, the boric acid ferrous lithium
It is 0.004:1 with the mass ratio of lithia and boric acid ferrous lithium in the mixture of lithia.
Lithium metasilicate and the boric acid that boric acid ferrous lithium surface is coated in boric acid ferrous iron lithium anode material obtained by the present embodiment are sub-
The ratio of iron lithium are as follows: 0.05:1.
It is with the be positive first discharge specific capacity of the battery of pole material of boric acid ferrous iron lithium anode material obtained by the present embodiment
187mAh/g, 100 times circulation after specific capacity still remain in 102mAh/g.
Above-mentioned material to be placed in air after a week, the first discharge specific capacity of gained battery is 171mAh/g, 100 times
Specific capacity stills remain in 92mAh/g after circulation.
Embodiment 5
It is specific as follows the present embodiment provides a kind of method that vapour deposition process prepares boric acid ferrous iron lithium anode material:
The mixture of boric acid ferrous lithium and lithia is added in gaseous phase deposition stove, 650 DEG C are warming up in nitrogen atmosphere,
Then the mixed gas of ethyl orthosilicate steam and nitrogen is passed through into gaseous phase deposition stove with 200mL/ minutes flows, when being passed through
Between be 2 hours.Then it cools down in nitrogen atmosphere to get the boric acid ferrous iron lithium anode material；Wherein, the boric acid ferrous lithium
It is 0.006:1 with the mass ratio of lithia and boric acid ferrous lithium in the mixture of lithia.
Lithium metasilicate and the boric acid that boric acid ferrous lithium surface is coated in boric acid ferrous iron lithium anode material obtained by the present embodiment are sub-
The ratio of iron lithium are as follows: 0.08:1.
It is with the be positive first discharge specific capacity of the battery of pole material of boric acid ferrous iron lithium anode material obtained by the present embodiment
196mAh/g, 100 times circulation after specific capacity still remain in 158mAh/g.
Above-mentioned material to be placed in air after a week, the first discharge specific capacity of gained battery is 201mAh/g, 100 times
Specific capacity stills remain in 154mAh/g after circulation.
Embodiment 6
It is specific as follows the present embodiment provides a kind of method that vapour deposition process prepares boric acid ferrous iron lithium anode material:
The mixture of boric acid ferrous lithium and lithia is added in gaseous phase deposition stove, 700 DEG C are warming up in nitrogen atmosphere,
Then the mixed gas of ethyl orthosilicate steam and nitrogen is passed through into gaseous phase deposition stove with 60mL/ minutes flows, when being passed through
Between be 2 hours.Then it cools down in nitrogen atmosphere to get the boric acid ferrous iron lithium anode material；Wherein, the boric acid ferrous lithium
It is 0.004:1 with the mass ratio of lithia and boric acid ferrous lithium in the mixture of lithia.
Lithium metasilicate and the boric acid that boric acid ferrous lithium surface is coated in boric acid ferrous iron lithium anode material obtained by the present embodiment are sub-
The ratio of iron lithium are as follows: 0.03:1.
It is with the be positive first discharge specific capacity of the battery of pole material of boric acid ferrous iron lithium anode material obtained by the present embodiment
204mAh/g, 100 times circulation after specific capacity still remain in 176mAh/g.
Above-mentioned material to be placed in air after a week, the first discharge specific capacity of gained battery is 193mAh/g, 100 times
Specific capacity stills remain in 147mAh/g after circulation.
Boric acid ferrous iron lithium anode material performance data obtained by 1 Examples 1 to 6 of table summarizes
It is seen from the above data that the boric acid ferrous iron lithium anode material of preparation of the embodiment of the present invention is with higher for the first time
Specific discharge capacity close to the theoretical specific capacity of boric acid ferrous iron lithium anode material, while having good cyclical stability.In air
It is middle to place after a week, first discharge specific capacity and cyclical stability no apparent difference compared with initially, it can be seen that, this
The method in boric acid ferrous lithium surface cladding lithium metasilicate protective layer that inventive embodiments use can significantly improve boric acid ferrous lithium
The stability of positive electrode, gained boric acid ferrous iron lithium anode material are placed one week in air, and also there is no apparent for performance
Variation.And the lithium metasilicate of cladding does not have an impact other performances of boric acid ferrous iron lithium anode material.No matter and liquid phase coating
In method or vapour deposition process, technique is simple and easy, is easy to control, and is conducive to large-scale industrial production.
The above is merely for convenience of it will be understood by those skilled in the art that technical solution of the present invention, not to limit
The present invention.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in this
Within the protection scope of invention.
Claims (4)
1. a kind of preparation method of lithium ion battery boric acid ferrous iron lithium anode material, which is characterized in that the boric acid ferrous lithium is just
Pole material includes boric acid ferrous lithium and the lithium metasilicate for being coated on boric acid ferrous lithium surface, the lithium metasilicate and the boric acid
The mass ratio of ferrous lithium is 0.02:1~0.1:1；
The preparation method is that:
The mixture of boric acid ferrous lithium and lithia is added in gaseous phase deposition stove, it is warming up to 500 in an inert gas atmosphere~
700 DEG C, the mixed gas of esters of silicon acis steam and inert gas is then passed through into the gaseous phase deposition stove, the mixed gas
Being passed through the time is 1~4 hour, and the mixed gas flow is 60~200mL/ minutes, is then cooled down in an inert gas atmosphere
Afterwards up to the boric acid ferrous iron lithium anode material；Lithia and boric acid are ferrous in the mixture of the boric acid ferrous lithium and lithia
The mass ratio of lithium is 0.001:1~0.006:1.
2. preparation method according to claim 1, which is characterized in that the esters of silicon acis is selected from ethyl orthosilicate, positive silicic acid
At least one of methyl esters, positive silicic acid propyl ester and butyl silicate.
3. preparation method according to claim 1, which is characterized in that the inert gas in nitrogen, argon gas extremely
Few one kind.
4. a kind of lithium ion battery boric acid ferrous lithium being prepared using the described in any item preparation methods of claims 1 to 3
Positive electrode.
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