CN105789625A - A kind of preparation method of lithium ion battery cathode material LiCoBO3 - Google Patents
A kind of preparation method of lithium ion battery cathode material LiCoBO3 Download PDFInfo
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- CN105789625A CN105789625A CN201610260023.5A CN201610260023A CN105789625A CN 105789625 A CN105789625 A CN 105789625A CN 201610260023 A CN201610260023 A CN 201610260023A CN 105789625 A CN105789625 A CN 105789625A
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- 229910013020 LiCoBO3 Inorganic materials 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010406 cathode material Substances 0.000 title claims description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000004327 boric acid Substances 0.000 claims abstract description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 10
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract 10
- 239000007774 positive electrode material Substances 0.000 claims abstract 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 239000006230 acetylene black Substances 0.000 claims description 7
- 239000003273 ketjen black Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims 3
- 238000001816 cooling Methods 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 abstract 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 abstract 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 13
- 229960000935 dehydrated alcohol Drugs 0.000 description 12
- 239000010405 anode material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000010532 solid phase synthesis reaction Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- -1 borate compound Chemical class 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910010532 LiFeBO3 Inorganic materials 0.000 description 3
- 229910011154 LiMBO3 Inorganic materials 0.000 description 3
- 229910014928 LiMnBO3 Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000447 polyanionic polymer Polymers 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910013184 LiBO Inorganic materials 0.000 description 2
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000374 eutectic mixture Substances 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910019167 CoC2 Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910013178 LiBO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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- 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)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种锂离子电池正极材料LiCoBO3的制备方法，包括如下步骤：将氢氧化锂、碳酸锂、氧化钴或碳酸钴分散在无水乙醇中混合后球磨，干燥后在惰性气氛下450～600℃烧结1～4小时，再随炉冷却得前驱体(I)；然后将前驱体(I)和硼酸分散在无水乙醇中混合后球磨，干燥后在惰性气氛下180～350℃烧结1～4小时烧结，得前驱体(II)；将前驱体(II)在惰性气氛下450～700℃烧结2～10小时，冷却得到产品。还可在制备过程中进行碳掺杂和Li2O‑2B2O3掺杂。本发明降低了反应温度，明显缩短了反应时间，从而显著降低了生产成本，节约了能源，同时本发明所得产品的放电比容量、循环稳定性均明显提高。
The invention discloses a preparation method of LiCoBO3 , a positive electrode material for lithium ion batteries, comprising the following steps: dispersing lithium hydroxide, lithium carbonate, cobalt oxide or cobalt carbonate in absolute ethanol, mixing, ball milling, and drying in an inert atmosphere Sinter at 450-600°C for 1-4 hours, and then cool with the furnace to obtain the precursor (I); then disperse the precursor (I) and boric acid in absolute ethanol, mix them, ball mill, and dry them at 180-350°C under an inert atmosphere Sintering for 1-4 hours to obtain the precursor (II); sintering the precursor (II) at 450-700° C. for 2-10 hours in an inert atmosphere, and cooling to obtain the product. Carbon doping and Li 2 O‑2B 2 O 3 doping can also be performed during the preparation process. The invention reduces the reaction temperature and obviously shortens the reaction time, thereby significantly reducing the production cost and saving energy, and at the same time, the discharge specific capacity and cycle stability of the product obtained by the invention are obviously improved.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, prepare LiCoBO particularly to one3The side of positive electrode
Method.
Background technology
Lithium ion battery has the advantages such as running voltage height, specific energy height, memory-less effect, self discharge is little, have extended cycle life,
Can be used for the storage of mobile phone, notebook computer, electric motor car, solar energy and wind energy and the construction etc. of intelligent grid.From electricity
From the point of view of the development of pole material, the development of positive electrode lags behind negative material, and positive electrode is for improving lithium ion battery
The chemical properties such as running voltage, specific energy, cycle life are most important.Thus anode material for lithium-ion batteries is lithium ion
The key of battery development.Polyanion shaped material have Stability Analysis of Structures, safety high, can be by changing polyanion or transition
The advantage that metal changes running voltage, it has also become a new generation's anode material for lithium-ion batteries.
With SO4 2-、PO4 3-Or SiO4 4-Compare Deng polyanion, BO3 3-Advantage be little (the 58.8g mol of molal weight-1).Therefore,
LiMBO3(M=Mn, Fe, Co) is likely to be of higher specific capacity, such as LiFeBO3、LiMnBO3、LiCoBO3Theory
Specific capacity is respectively 220,222,215mAh g-1, compare LiFePO4About exceed 50mAh g-1.This shows LiMBO3Likely send out
Generated is the lithium ion battery novel anode material of height ratio capacity.Add the advantage in terms of its heat stability and security performance,
Lithium-ion-power cell has huge application prospect.In the ferrum of report, manganese, three kinds of borate positive electrodes of cobalt at present,
First-principles calculations shows, ferrum, manganese, the discharge voltage of three kinds of borate positive electrodes of cobalt are followed successively by 3.03,3.67 and 4.09V.
With LiFeBO3、LiMnBO3Compare, LiCoBO3There is higher theoretical energy density.Additionally, China is that a boron resource is big
State, proved reserves account for the 16% of world's boron rock reserves.Therefore, in view of discharge voltage, the composite factor of theoretical energy density,
LiCoBO3The research and development of positive electrode have positive effect to the utilization of China's boron resource with the development of the national economy.
Although LiFeBO3、LiMnBO3、LiCoBO3It is synthesized Deng borate compound, but about this kind of material
Research as anode material for lithium-ion batteries is also in the starting stage.Especially LiCoBO3Positive electrode, puts first
Electricity specific capacity is far still below the theoretical specific capacity of its 222mAh/g, and its cycle performance is the most undesirable.So, synthesis is same
Time possess that reversible specific capacity is high, LiCoBO that have extended cycle life (such as cycle-index is more than 50 times), high rate performance are excellent3Extremely
Modern there is not been reported, how to synthesize the LiCoBO of electrochemical performance3Material is still that electrochemist's facing
A difficult problem.
At present, LiCoBO3The preparation method of positive electrode is mainly solid phase method.Because easily generating simple substance cobalt during He Cheng,
So in preparation process, first using CoC2O4And H3BO3Or B2O3Prepare intermediate Co2B2O5, then the Co that will obtain2B2O5
With Li2CO3End product (non-patent literature 1, non-patent literature 2) is obtained by sintering after mixing.Further, it is also possible to will
LiBO2With Co3O4By after the mixed in molar ratio of 3:1 at a temperature of 800-850 DEG C, react in air atmosphere, then use water
Or ethanol washes away the LiBO of excess2.LiBO can also be passed through2React under an inert atmosphere with CoO 20h or LiOH,
Co(OH)2、H3BO3Reaction 10h prepares LiCoBO under an inert atmosphere3(non-patent literature 3).
Although at present to LiCoBO3The research of preparation method is more, but the performance of products obtained therefrom still and in theory exists the biggest
Difference, in consideration of it, the present invention provides one to prepare LiCoBO3New method.The method is first with LiOH-Li2CO3Low
Eutectic mixture (eutectic point 434 DEG C) is lithium source and doubles as fused-salt medium, is mixed between mushy stage by lithium source and cobalt source
Close and promote each component mix homogeneously, then by the H of low melting point3BO3(fusing point 169 DEG C) infiltrated with molten metal is uniformly mixed
LiCoBO3Presoma, thus it is effectively reduced preparation LiCoBO3Reaction temperature and shorten the response time, improve material
Crystal structure and performance.
Non-patent literature 1:The electrochemical activity for nano-LiCoBO3as a cathode material for
Li-ion batteries [J], Solid State Ionics, 2001,139:37 46.
Non-patent literature 2:Demonstration of Co3+/Co2+Electrochemical Activity in LiCoBO3Cathode at
4.0V [J], ECS Electrochemistry Letters, 2013,2 (8): A75-A77.
Non-patent literature 3:Magnetic Structures of LiMBO3(M=Mn, Fe, Co) Lithiated Transition Metal
Borates [J], Inorganic Chemistry, 2013,52:11966-11974.
Summary of the invention
It is an object of the invention to provide a kind of anode material for lithium-ion batteries LiCoBO3Preparation method.The present invention is all right
Product is carried out carbon doping and ion conductor Li2O-2B2O3Doping.
It is an object of the invention to realize by the following technical solutions:
(1) presoma (I) is prepared
First by Lithium hydrate, lithium carbonate, CoO or CoCO3It is dispersed in dehydrated alcohol ball milling 0.5～4 hours after mixing,
450～600 DEG C sinter 1～4 hour the most under an inert atmosphere, then furnace cooling obtains presoma (I)；
(2) presoma (II) is prepared
Presoma (I) and boric acid are dispersed in dehydrated alcohol ball milling 2～5 hours after mixing, the most under an inert atmosphere in
180～350 DEG C sinter 1～4 hour, obtain presoma (II)；
(3) sintering reaction
The presoma (II) that step (2) is obtained under an inert atmosphere 450～700 DEG C sinter 2～10 hours, then furnace cooling,
I.e. obtain anode material for lithium-ion batteries LiCoBO3。
Further, Lithium hydrate is 0.84: 0.16 with the ratio of the amount of the material of lithium carbonate, lithium, the ratio of amount of material of cobalt element
It is 1～1.632: 1；Lithium, the ratio of amount of material of boron element are (1+2x): (1+4x), x represents at LiCoBO3/Li2O-2B2O3
Composite intermediate ion conductor Li2O-2B2O3With LiCoBO3The ratio of amount of material, span is 0～0.316；
Further, step (2) also includes the interpolation of material with carbon element, material with carbon element and boric acid common distribution, thus finally obtains carbon
The LiCoBO of doping3Positive electrode, the LiCoBO of described carbon doping3In positive electrode, the amount of residual carbon accounts for the total matter of positive electrode
The 1%～10% of amount.
Further, described material with carbon element is acetylene black or/and Ketjen black.
The beneficial effects of the present invention is:
(1) present invention utilizes LiOH-Li2CO3Eutectic mixture (eutectic point 434 DEG C) is lithium source and doubles as fused-salt medium,
Between mushy stage, carry out mixing by lithium source and cobalt source and promote each component mix homogeneously, then by the H of low melting point3BO3(molten
Point 169 DEG C) LiCoBO that is uniformly mixed of infiltrated with molten metal3Presoma, thus it is effectively reduced preparation LiCoBO3Anti-
Answer temperature, the most substantially shorten the response time, thus significantly reduce production cost, saved the energy.
(2) compared with prior art, the invention have the advantages that products obtained therefrom purity is high, there is no an impurity phase, rather than patent
Document 2,3 uses the LiCoBO that solid phase method obtains3Product all contains a small amount of CoO or simple substance Co impurity；Products obtained therefrom
Performance be significantly improved, specific discharge capacity, cyclical stability all significantly improve, and non-patent literature 1 uses solid phase method to obtain
The LiCoBO arrived3Product, even if discharge-rate as little as C/100, the most only 0.015 lithium is at LiCoBO3In reversible deintercalation (phase
When being 3.2mAh/g in first discharge specific capacity), and LiCoBO prepared by the present invention3First discharge specific capacity reach
25.7mAh/g.Non-patent literature 2 uses the LiCoBO that solid phase method obtains3Product, after 5 circulations, specific capacity drops to
20mAh/g, capability retention is 67%, and LiCoBO prepared by the present invention3After 30 times circulate, specific capacity is maintained at
20.4mAh/g, capability retention is 79%.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the embodiment of the present invention 1 sample.
Fig. 2 is the scanning electron microscope (SEM) photograph of the embodiment of the present invention 1 sample.
Fig. 3 is the X-ray diffractogram of embodiment 2 sample.
Fig. 4 is the first charge-discharge curve of embodiment 2, wherein: constant current-constant voltage (cut-off current 2mA/g), discharge and recharge times
Rate is C/20, and charging/discharging voltage is 2-4.5V,.
Fig. 5 is the cycle performance figure of embodiment 2, wherein: constant current-constant voltage (cut-off current 2mA/g), charge-discharge magnification is
C/20, charging/discharging voltage is 2-4.5V.
Fig. 6 is the X-ray diffractogram of embodiment 3.
Detailed description of the invention
In order to be more fully understood that the present invention, below in conjunction with embodiment and accompanying drawing, the invention will be further described, but the present invention wants
The scope asking protection is not limited to the scope that embodiment represents.
Embodiment 1
By 1.019g Li2CO3, 1.734g LiOH and 7.493g CoO be dispersed in dehydrated alcohol ball milling 1 hour after mixing,
Sinter 1 hour in 500 DEG C the most under an inert atmosphere, then furnace cooling obtains presoma (I)；By cobalt, the material of boron element
The ratio of amount is to weigh H at 1: 13BO3, and presoma (I) and boric acid are dispersed in ball milling 3 hours in dehydrated alcohol, exist after drying
In 200 DEG C of sintering 3 hours under inert atmosphere, sinter 8 hours in 600 DEG C, then furnace cooling.
The XRD figure of products therefrom is as shown in Figure 1.As shown in Figure 1, monoclinic LiCoBO has been synthesized at 600 DEG C3
, there are not other impurity peaks in positive electrode, product purity is high in spectrogram.As shown in Figure 2, sample particle is evenly distributed, chi
Very little about 1 μm.
Embodiment 2
By 1.019g Li2CO3, 1.734g LiOH and 7.493g CoO be dispersed in dehydrated alcohol ball milling 4 hours after mixing,
Sinter 4 hours in 450 DEG C the most under an inert atmosphere, then furnace cooling obtains presoma (I)；By cobalt, the material of boron element
The ratio of amount is to weigh H at 1: 13BO3, account for the 10% of positive electrode gross mass by the amount of residual carbon and weigh Ketjen black, by presoma
(I), boric acid and Ketjen black be dispersed in ball milling 2 hours in dehydrated alcohol, the most under an inert atmosphere in 180 DEG C sinter 4 hours,
Sinter 8 hours in 500 DEG C, then furnace cooling.
The XRD figure of products therefrom is as shown in Figure 3.From the figure 3, it may be seen that synthesized monoclinic system LiCoBO at 500 DEG C3/
, there are not other impurity peaks in Ketjen black composite positive pole, product purity is high in spectrogram.The result of Fig. 4, Fig. 5 shows, with
Solid phase method is compared, and this positive electrode has higher specific discharge capacity.In non-patent literature 1, even if discharge-rate is low
To C/100, the most only 0.015 lithium is at LiCoBO3In reversible deintercalation (being equivalent to first discharge specific capacity is 3.2mAh/g),
LiCoBO prepared by the present invention3First discharge specific capacity reach 25.7mAh/g.Sample also shows excellent cyclical stability,
After 30 times circulate, specific capacity is maintained at 20.4mAh/g, and capability retention is 79%.
Embodiment 3
By 1.663g Li2CO3, 2.830g LiOH and 11.894g CoCO3After being dispersed in dehydrated alcohol mixing, ball milling 0.5 is little
Time, sinter 2 hours in 600 DEG C the most under an inert atmosphere, then furnace cooling obtains presoma (I)；By LiCoBO3、
Li2O-2B2O3The ratio of amount of material be to weigh H at 1: 0.3163BO3, and presoma (I) and boric acid are dispersed in dehydrated alcohol
Middle ball milling 5 hours, 350 DEG C sinter 2 hours, sinter 2 hours in 700 DEG C, then furnace cooling the most under an inert atmosphere,
Obtain LiCoBO3/Li2O-2B2O3Composite.
The XRD figure of products therefrom is as shown in Figure 6.It will be appreciated from fig. 6 that synthesized monoclinic LiCoBO at 700 DEG C3
, there are not other impurity peaks in positive electrode, product purity is high in spectrogram.
Embodiment 4
By 1.325g Li2CO3, 2.255g LiOH and 7.493g CoO be dispersed in dehydrated alcohol ball milling 2 hours after mixing,
Sinter 1 hour in 500 DEG C the most under an inert atmosphere, then furnace cooling obtains presoma (I)；By LiCoBO3、Li2O-2B2O3
The ratio of amount of material be to weigh H at 1: 0.153BO3, account for the 1% of positive electrode gross mass by the amount of residual carbon and weigh acetylene black,
And presoma (I) and boric acid, acetylene black are dispersed in ball milling 1 hour in dehydrated alcohol, the most under an inert atmosphere 250 DEG C of burnings
Tie 1 hour, sinter 10 hours in 450 DEG C, then furnace cooling, obtain LiCoBO3/ (acetylene black+Li2O-2B2O3) composite wood
Material.
Embodiment 5
By 1.019g Li2CO3, 1.734g LiOH and 7.493g CoO be dispersed in dehydrated alcohol ball milling 3 hours after mixing,
Sinter 1 hour in 500 DEG C the most under an inert atmosphere, then furnace cooling obtains presoma (I)；By cobalt, the material of boron element
The ratio of amount is to weigh H at 1: 13BO3, account for the 5% of positive electrode gross mass by the amount of residual carbon and weigh acetylene black, by presoma
(I), boric acid and acetylene black be dispersed in ball milling 3 hours in dehydrated alcohol, the most under an inert atmosphere in 200 DEG C sinter 1 hour,
Sinter 5 hours in 500 DEG C, then furnace cooling.
Being only more than presently preferred embodiments of the present invention, according to the above-mentioned design of the present invention, those skilled in the art are all right
To this, various modification can be adapted and conversion, such as, in the proportioning be given in the present invention and process condition range, to proportioning and technique
Condition is combined, converts, and these similar conversion and amendment belong to the essence of the present invention.
Claims (4)
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| CN102348640A (en) * | 2009-03-09 | 2012-02-08 | 独立行政法人产业技术综合研究所 | Process for producing lithium borate compound |
| WO2012060084A1 (en) * | 2010-11-05 | 2012-05-10 | 株式会社豊田自動織機 | Lithium borate compound and method for producing same |
| US20140361216A1 (en) * | 2013-06-05 | 2014-12-11 | Korea Institute Of Science And Technology | Cathode active material for lithium ion secondary battery including lithium manganese borate compound and manganese oxide, and method for producing the same |
| CN104617297A (en) * | 2015-02-09 | 2015-05-13 | 湖南科技大学 | A kind of molten salt method prepares lithium-ion battery cathode material LiMnBO3 method |
| CN104821390A (en) * | 2015-04-24 | 2015-08-05 | 中南大学 | Lithium manganese borate/graphene as cathode materials for lithium-ion batteries and preparation method of lithium manganese borate / graphene |
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| CN102348640A (en) * | 2009-03-09 | 2012-02-08 | 独立行政法人产业技术综合研究所 | Process for producing lithium borate compound |
| WO2012060084A1 (en) * | 2010-11-05 | 2012-05-10 | 株式会社豊田自動織機 | Lithium borate compound and method for producing same |
| US20140361216A1 (en) * | 2013-06-05 | 2014-12-11 | Korea Institute Of Science And Technology | Cathode active material for lithium ion secondary battery including lithium manganese borate compound and manganese oxide, and method for producing the same |
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