CN104425799A - Lithium ferric borate block type electrode and preparation method thereof - Google Patents
Lithium ferric borate block type electrode and preparation method thereof Download PDFInfo
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- CN104425799A CN104425799A CN201310406639.5A CN201310406639A CN104425799A CN 104425799 A CN104425799 A CN 104425799A CN 201310406639 A CN201310406639 A CN 201310406639A CN 104425799 A CN104425799 A CN 104425799A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 26
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title abstract 4
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 48
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 19
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 229910052796 boron Inorganic materials 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 5
- ZOIKAOIYOCLPME-UHFFFAOYSA-N lithium iron(2+) borate Chemical compound B([O-])([O-])[O-].[Fe+2].[Li+] ZOIKAOIYOCLPME-UHFFFAOYSA-N 0.000 claims description 36
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 238000003825 pressing Methods 0.000 claims description 17
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 239000007900 aqueous suspension Substances 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 10
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 7
- 229930006000 Sucrose Natural products 0.000 claims description 7
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- 239000011975 tartaric acid Substances 0.000 claims description 7
- 235000002906 tartaric acid Nutrition 0.000 claims description 7
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 5
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000243 solution Substances 0.000 abstract description 15
- 239000000725 suspension Substances 0.000 abstract description 9
- 239000002243 precursor Substances 0.000 abstract 6
- 229910010532 LiFeBO3 Inorganic materials 0.000 abstract 4
- 239000005416 organic matter Substances 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 10
- 229910013870 LiPF 6 Inorganic materials 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000007888 film coating Substances 0.000 description 4
- 238000009501 film coating Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 239000002491 polymer binding agent Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 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
- H01M4/13—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium ferric borate block type electrode and a preparation method thereof. The preparation method of the lithium ion battery cathode comprises the following steps: (1), sequentially adding a lithium source water solution or suspension, a ferric iron source water solution or suspension and a boron source water solution or suspension in a carbon source water solution to obtain a mixed solution; (2) drying the mixed solution obtained in the step (1) to obtain a lithium ferric borate precursor; (3) mixing the lithium ferric borate precursor obtained in the step (2) with an organic matter to obtain a LiFeBO3/C precursor; (4) forming the LiFeBO3/C precursor obtained in the step (3) into a blocky shape to obtain a LiFeBO3/C blocky type electrode precursor; and (5) calcining the LiFeBO3/C block type electrode precursor obtained in the step (4) under the protection of an inert atmosphere. The lithium ion battery assembled by adopting the lithium ion battery cathode prepared according to the preparation method provided by the invention has excellent electrochemical performance.
Description
Technical field
The present invention relates to a kind of iron borate lithium block type electrode and preparation method thereof.
Background technology
Lithium ion battery is as the green high-capacity battery of a new generation, there is the advantages such as operating voltage is high, specific energy is high, self discharge is little, memory-less effect, with its long circulation life and high security and stability, small size lithium ion battery occupies consequence in small size digital equipment is powered, especially for portable electronic instruments such as notebook computer, mobile phone and personal digital products.Meanwhile, large scale lithium ion battery is as the energy storing device having most prospect for the energy storage device and electric automobile and mixed power electric car of storing emerging energy (as wind energy, solar energy, tidal power generation electric energy etc.), industry can be alleviated depend on unduly fossil fuel, and then reducing city greenhouse gas emission, people are especially to which imparts high expectation.But along with scientific and technological development, no matter be small size lithium ion battery or large scale lithium ion battery, all in the urgent need to promoting its energy density further.
Lithium ion battery is mainly made up of positive pole, negative pole, electrolyte and barrier film four parts.Usually adopt electrode film coating technique to improve battery volume and capacity ratio in prior art, thus the energy density of battery is improved.For traditional electrode film coating techniques, positive active material is generally coated on the aluminium foil as collector, traditional LiFeBO
3the preparation flow of positive plate comprises: mixing LiFeBO
3positive electrode, conductive agent, adhesive slurrying material → coating → roll-in → cutting → drying, thus obtain LiFeBO
3positive plate.This complex technical process, need adhesive and kinds of processes equipment, electrode manufacturing cost is high, refers to document Nature2001 (414): described in 359-367.
Its disadvantage of traditional electrode film coating techniques is in electrode production process, overall film thickness less (being less than 100nm).Further, in electrode film, 50% volume fraction of having an appointment again is occupied by non-electroactive material, comprises Metal Substrate collector, low-density conductive additive (for improving electronics, the conductive performance of ion between positive electrode internal interface) etc.For practical commercial battery, the interpolation of insulating polymer binding agent, as polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVDF), is absolutely necessary again.And in order to these insulating polymer binding agents can being dissolved, expensive, poisonous, VOC also to be used, be n-N-methyl-2-2-pyrrolidone N-(NMP) under normal circumstances.
Tie Shi China Dominant Mineral Resources, the iron resource reserves verified occupy the 5th, the world, account for global gross reserves 9.0%, and in the earth's crust, iron content is also very high, and its abundance is 4.75%, occupy the 4th in all elements.Polyanionic compound iron system positive electrode Theoretical Mass specific capacity is general higher, but is used in electrode film coating technique and is still difficult to make lithium ion battery volume and capacity ratio obtain larger improvement.
Ye Shiyige boron resource big country of China, proved reserves account for 16% of world's boron rock reserves, occupy the 4th, the world.Iron borate lithium (LiFeBO
3) as a kind of novel polyanion positive electrode had compared with height ratio capacity, with regard to structure, adopt (the BO that molal weight is less
3)
3-polyanion, can reach the high theoretical specific capacity of 220mAh/g.Meanwhile, this structure of iron borate lithium makes it have better conductivity (conductivity is 3.9 × 10
-7s/cm), there is minimum volume change (about 2%), good invertibity and the chemistry of excellence and electrochemical stability etc. before and after discharge and recharge.Therefore, iron borate lithium (LiFeBO
3) be a kind of anode material for lithium-ion batteries having application prospect, further investigation is carried out to it not only there is important strategic importance, also there is great economic and social benefit.
Summary of the invention
The object of the invention is the defect overcoming prior art, provide that a kind of specific capacity is large, the high performance lithium ion battery anode of good cycling stability and preparation method thereof.
To achieve these goals, the invention provides a kind of preparation method of lithium ion cell positive, the method comprises the following steps:
(1) the lithium source aqueous solution or suspension, the ferric iron source aqueous solution or suspension and the boron source aqueous solution or suspension are added in the carbon source aqueous solution successively, obtain mixed solution;
(2) by dry for the mixed solution obtained in step (1), iron borate lithium presoma is obtained;
(3) the iron borate lithium presoma obtained in step (2) is mixed with organic substance, obtain LiFeBO
3/ C presoma;
(4) LiFeBO will obtained in step (3)
3/ C presoma is shaped to bulk, obtains LiFeBO
3/ C block type electrode presoma;
(5) LiFeBO will obtained in step (4)
3/ C block type electrode presoma is calcined under inert atmosphere protection, obtains lithium ion cell positive.
Present invention also offers a kind of lithium ion cell positive, describedly just very to prepare according to preparation method provided by the invention.
The present invention has following beneficial effect:
1, the present invention is by LiFeBO
3/ C block type electrode presoma is calcined, and is directly prepared into block type electrode and is assembled into battery, does not need to add adhesive and aluminium foil coating, add the content of positive electrode, up to 95% time preferred, improve energy and the power density of electrode material, one-stoply obtain iron borate lithium block type electrode.
2, block type electrode thickness of the present invention can reach about 2mm, and the business button cell on market comprises electrode also only this thickness, even also slightly thin.Usually, battery electrode is thicker, and its battery performance is poorer, and it is that the electrode performance of 10 microns is suitable that this patent obtains so thick block type electrode and thickness, and illustrating that the performance of this material is quite superior, is the optimum performance of report at present.
The single-phase purity of the lithium iron borate anode material of lithium ion battery 3, adopting preparation method provided by the invention to prepare is high, grain diameter between 50-500nm, the good dispersion of particle, good cycling stability, specific capacity is large, can meet the needs of lithium ion battery practical application.
4, the present invention uses ferric iron source to be more conducive to the synthesis of iron borate lithium, significantly can reduce the cost of raw material.
5, method of the present invention does not specially require raw-material purity, expands raw-material source.
6, calcining preferable temperature of the present invention is 600-750 DEG C, and the technological temperature of synthetic material is lower, and the high-temperature process time is shorter, thus substantially reduces manufacturing cycle, effectively reduces production technology cost.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the XRD collection of illustrative plates of lithium ion cell positive prepared in the embodiment of the present invention 1;
Fig. 2 is the second to five charging and discharging curve figure of lithium ion battery prepared in the embodiment of the present invention 6;
Fig. 3 is scanning electron microscopy (SEM) photo of lithium ion cell positive prepared in the embodiment of the present invention 1;
Fig. 4 is the cycle performance curve of lithium ion battery under different multiplying prepared in the embodiment of the present invention 6.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of lithium ion cell positive, the method comprises the following steps:
(1) the lithium source aqueous solution or suspension, the ferric iron source aqueous solution or suspension and the boron source aqueous solution or suspension are added in the carbon source aqueous solution successively, obtain mixed solution;
(2) by dry for the mixed solution obtained in step (1), iron borate lithium presoma is obtained;
(3) the iron borate lithium presoma obtained in step (2) is mixed with organic substance, obtain LiFeBO
3/ C presoma;
(4) LiFeBO will obtained in step (3)
3/ C presoma is shaped to bulk, obtains LiFeBO
3/ C block type electrode presoma;
(5) LiFeBO will obtained in step (4)
3/ C block type electrode presoma is calcined under inert atmosphere protection, obtains lithium ion cell positive.
In preparation method provided by the invention, described boron source, lithium source and ferric iron source are the raw material preparing iron borate lithium.The selectable range of the consumption of described boron source, lithium source, ferric iron source is wider, under preferable case, in constituent content, the mol ratio of described boron source, lithium source and ferric iron source is (1.05-1.15): (1-1.1): 1, more preferably (1.1-1.15): (1-1.05): 1.The effect of described carbon source in preparation process is reduction ferric iron source, coated described iron borate lithium increase its conductivity, the selectable range of carbon source consumption is wider, under preferable case, with the content meter of compound, the mol ratio of described ferric iron source and described carbon source is 1:(0.5-2), more preferably 1:(1-2).The effect of described organic substance in preparation process forms cavernous structure and coated described iron borate lithium and increase its conductivity, the selectable range of organic substance consumption is wider, under preferable case, in compound, described ferric iron source and described organic mol ratio are 1:(0.2-0.5), more preferably 1:(0.4-0.5).
The kind selectable range of described boron source, lithium source, ferric iron source and carbon source is wider, as long as ensure that it can form the aqueous solution or suspension, under preferable case, described boron source be selected from boric acid, ammonium borate and diboron trioxide one or more; Under preferable case, described lithium source be selected from lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate and lithium nitrate one or more; Under preferable case, described ferric iron source be selected from di-iron trioxide, ferric nitrate, ferric oxalate and ironic citrate one or more; Described carbon source is preferably organic substance, is more preferably one or more in glucose, citric acid, sucrose, Glycolic acid, tartaric acid and ascorbic acid.
For raw material that can not be water-soluble, conventional method can be used to make it form suspension, such as, can first raw material be joined in deionized water, carry out ultrasonic disperse process, then carry out the suspension that magnetic agitation prepares raw material.
The scope that described organic substance is selected is also wider, under preferable case, described organic substance be selected from glucose, sucrose and ascorbic acid one or more.
In addition, do not specially require in the present invention to raw-material purity, technical pure, chemical pure, analytically pure raw material, this expands raw-material source, and uses ferric iron source significantly can reduce the cost of raw material.
In preparation method provided by the invention, described step (1) is one of key point of the present invention, the described lithium source aqueous solution or suspension, the ferric iron source aqueous solution or suspension and the boron source aqueous solution or suspension are added in the described carbon source aqueous solution successively in order, the order of reacting between different material can well be controlled, and then the progress of impact reaction, thus contribute to the iron borate lithium obtaining single pure phase, the single-phase purity of material can be improved, obtain the structure of material, pattern more even, greatly improve its chemical property simultaneously.Under preferable case, add described in described step (1) and under agitation carry out, described mixing speed is 900-1200r/min, and the stirring duration is 2-8h, stir the abundant reaction be conducive between raw material, after preferably stirring further, obtain the mixed solution of clear.
In preparation method provided by the invention, the usual manner that the described drying of described step (2) can adopt those skilled in the art to expect, the temperature of described drying is preferably 60-80 DEG C, and drying time is preferably 12-20h.Described drying can also be preferably carries out twice drying in atmosphere, the temperature that more preferably first time is dry is 60-80 DEG C, time is 12-20h, the temperature of second time drying is 120-220 DEG C, time is 4-8h, solution combustion can be impelled thus to explode, thus obtain grain diameter less and uniform iron borate lithium presoma.
In preparation method provided by the invention, mixing described in described step (3) can adopt this area usual manner, preferred employing ball-milling treatment, the speed of ball milling is 200-300r/min, the time of ball milling is 1.5-2.5h, preferably further carries out in planetary ball mill, with 220r/min speed ball milling 2h, ratio of grinding media to material is preferably 10:1, and ball milling is conducive to the iron borate lithium presoma obtained in step (2) to mix with organic substance.
In preparation method provided by the invention, shapingly described in described step (4) adopt this area usual manner, preferred cold pressing treatment, the pressure of colding pressing is 1-100MPa, and the time of colding pressing is 120-600 second.Preferred compacting of uniaxially colding pressing at room temperature further.
In preparation method provided by the invention, the condition of the described calcining of described step (5) can adopt this area usual manner, and the temperature of described calcining is preferably 600-750 DEG C, is more preferably 600-650 DEG C, and the time of calcining is preferably 6-24h, is more preferably 6-8h.
Under preferable case, in described step (5), before described calcining, also comprise described LiFeBO
3/ C block type electrode presoma carries out preliminary treatment under inert atmosphere protection, and this preliminary treatment can make the undecomposed feed material degradation that may exist in presoma, thus further by eliminatings such as unnecessary water or carbon dioxide.This pretreated temperature is preferably 300-400 DEG C, and the time is preferably 2-24h.
Above-mentioned inert atmosphere is the gas do not reacted with described iron borate lithium presoma or product, and preferred described inert atmosphere is selected from least one in nitrogen and periodic table of elements zero group gas.Further preferred described inert atmosphere is Dynamic Atmosphere, and the gaseous impurity etc. that material breakdown can be produced thus is got rid of in time, thus minimizing impacts the synthesis of material, and preferred gas flow velocity is 2-50mL/min.
Present invention also offers a kind of lithium ion cell positive, describedly just very to prepare according to preparation method provided by the invention, the particle diameter of iron borate lithium is 50-500nm, is preferably 50-400nm.
Below will be described the present invention by embodiment.
Lithium hydroxide, lithium oxalate and ironic citrate are all purchased from Shantou Xilong Chemical Factory Co., Ltd;
Glucose, sucrose, citric acid, boric acid, diboron trioxide, lithium acetate and di-iron trioxide are all purchased from Beijing North fine chemicals Co., Ltd;
Tartaric acid, Glycolic acid, ascorbic acid, ammonium borate, lithium carbonate and ferric oxalate are all purchased from Chemical Reagent Co., Ltd., Sinopharm Group;
Lithium nitrate and ferric nitrate are purchased from 1Guanghua Chemical Plant Co., Ltd., Guangdong.
Embodiment 1-5 is for illustration of the preparation and characterization of lithium ion cell positive of the present invention.
Embodiment 1
0.0144mol lithium carbonate, 0.0288mol boric acid, 0.0288mol ferric nitrate are dissolved in 20mL water separately, 0.014mol citric acid and 0.009mol glucose are dissolved in 20mL water jointly, under the speed of 1200r/min stirs, successively lithium carbonate suspension, iron nitrate solution and BAS are joined in citric acid, glucose solution, Keep agitation mixed solution 6h, obtains the mixed solution of clear.By this mixed solution dry 16h at 80 DEG C, then heat resolve 4h at 220 DEG C, after grinding evenly, obtain iron borate lithium presoma.Iron borate lithium presoma and 0.0072mol glucose are carried out common ball-milling treatment, obtains LiFeBO
3/ C presoma.By LiFeBO
3the cold moudling in the mould of Φ 10mm of/C presoma, pressure of colding pressing is 80MPa, and the time of colding pressing is 120 seconds, obtains LiFeBO
3/ C block type electrode presoma.By this LiFeBO
3/ C block type electrode presoma moves in high temperature furnace, in 600 DEG C of calcining 8h under argon shield, with stove cool to room temperature, obtains lithium ion battery iron borate lithium matrix shape electrode product, can directly as lithium ion cell positive.
Embodiment 2
0.0288mol lithium hydroxide, 0.0325mol boric acid, 0.0144mol di-iron trioxide are joined in 40mL water separately, 0.014mol citric acid and 0.015mol sucrose are dissolved in 20mL water jointly, under the speed of 1000r/min stirs, successively lithium hydroxide solution, di-iron trioxide suspension and BAS are joined in citric acid, sucrose solution, Keep agitation mixed solution 8h, obtains the mixed solution of clear.By this mixed solution dry 20h at 60 DEG C, then heat resolve 6h at 220 DEG C, after grinding evenly, obtain iron borate lithium presoma.Iron borate lithium presoma and 0.0072mol ascorbic acid are carried out common ball-milling treatment, obtains LiFeBO
3/ C presoma.By LiFeBO
3the cold moudling in the mould of Φ 10mm of/C presoma, pressure of colding pressing is 60MPa, and the time of colding pressing is 240 seconds, obtains LiFeBO
3/ C block type electrode presoma.By this LiFeBO
3/ C block type electrode presoma moves in high temperature furnace, in 650 DEG C of calcining 8h under argon shield, with stove cool to room temperature, obtains lithium ion battery iron borate lithium matrix shape electrode product, can directly as lithium ion cell positive.
Embodiment 3
0.0288mol lithium acetate, 0.0082mol ammonium borate and 0.0144mol ferric oxalate are dissolved in 40mL water separately, 0.014mol citric acid and 0.008mol tartaric acid are dissolved in 20mL water, under the speed of 1100r/min stirs, successively lithium acetate aqueous solution, ferric oxalate suspension and ammonium borate aqueous solution are joined in citric acid, tartaric acid solution, Keep agitation mixed solution 6h, obtains the mixed solution of clear.By this mixed solution dry 16h at 80 DEG C, then heat resolve 4h at 200 DEG C, after grinding evenly, obtain iron borate lithium presoma.Iron borate lithium presoma and 0.00288mol glucose are carried out common ball-milling treatment, obtains LiFeBO
3/ C presoma.By LiFeBO
3the cold moudling in the mould of Φ 10mm of/C presoma, pressure of colding pressing is 1MPa, and the time of colding pressing is 600 seconds, obtains LiFeBO
3/ C block type electrode presoma.By this LiFeBO
3/ C block type electrode presoma moves in high temperature furnace, in 600 DEG C of calcining 8h under argon shield, with stove cool to room temperature, obtains lithium ion battery iron borate lithium matrix shape electrode product, can directly as lithium ion cell positive.
Embodiment 4
0.0288mol lithium nitrate, 0.0144mol diboron trioxide and 0.0288mol ferric nitrate are dissolved in 30mL water separately, 0.05mol Glycolic acid is dissolved in 40mL water, under the speed of 900r/min stirs, successively lithium nitrate solution, iron nitrate solution and diboron trioxide solution are joined in Glycolic acid solution, Keep agitation mixed solution 2h, obtains the mixed solution of clear.By this mixed solution dry 12h at 60 DEG C, then heat resolve 4h at 120 DEG C, after grinding evenly, obtain iron borate lithium presoma.Iron borate lithium presoma and 0.00868mol ascorbic acid are carried out common ball-milling treatment, obtains LiFeBO
3/ C presoma.By LiFeBO
3the cold moudling in the mould of Φ 10mm of/C presoma, pressure of colding pressing is 30MPa, and the time of colding pressing is 600 seconds, obtains LiFeBO
3/ C block type electrode presoma.By this LiFeBO
3/ C block type electrode presoma moves in high temperature furnace, in 700 DEG C of calcining 12h under argon shield, with stove cool to room temperature, obtains lithium ion battery iron borate lithium matrix shape electrode product, can directly as lithium ion cell positive.
Embodiment 5
0.0144mol lithium oxalate, 0.0288mol boric acid and 0.0288mol ironic citrate are joined in 40mL water separately, 0.014mol citric acid and 0.005mol tartaric acid are dissolved in 30mL water jointly, under the speed of 1100r/min stirs, successively the lithium oxalate aqueous solution, ironic citrate suspension and boric acid aqueous solution are joined in citric acid, tartaric acid solution, Keep agitation mixed solution 8h, obtains the mixed solution of clear.By this mixed solution dry 20h at 80 DEG C, then heat resolve 6h at 120 DEG C, after grinding evenly, obtain iron borate lithium presoma.Iron borate lithium presoma and 0.00868mol ascorbic acid are carried out common ball-milling treatment, obtains LiFeBO
3/ C presoma.By LiFeBO
3the cold moudling in the mould of Φ 10mm of/C presoma, pressure of colding pressing is 100MPa, and the time of colding pressing is 600 seconds, obtains LiFeBO
3/ C block type electrode presoma.By this LiFeBO
3/ C block type electrode presoma moves in high temperature furnace, in 700 DEG C of calcining 12h under argon shield, with stove cool to room temperature, obtains lithium ion battery iron borate lithium matrix shape electrode product, can directly as lithium ion cell positive.
Characterization of The Products
Measure composition and the content thereof of carbon in products therefrom with carbon and sulfur analytical instrument, result shows, embodiment 1-5 products therefrom comprises iron borate lithium and carbon.Wherein, the content of iron borate lithium is as shown in table 1 below.
Table 1
| Embodiment | Iron borate lithium accounts for the percentage of total product weight |
| Embodiment 1 | 98% |
| Embodiment 2 | 97% |
| Embodiment 3 | 96% |
| Embodiment 4 | 95% |
| Embodiment 5 | 95% |
Adopt the crystal structure of X ray powder diffracting technology determination product mesoboric acid iron lithium, X-ray diffractometer model is: D/MAX-TTRIII (CBO), and test condition is: angular range is 15-80 °, sweep speed 8 °/min, adopts Cu rake.Use the pattern of scanning electron microscopy sign iron borate lithium particle, size and dispersiveness, scanning electron microscopy (SEM) model is: FESEM Sirion200, FEI.Co..Result is as shown in table 2 below.
Table 2
| Embodiment | Composition | Degree of crystallinity | Particle diameter/nm | Dispersed |
| Embodiment 1 | Pure phase, does not have other dephasign | High | 50 | Good |
| Embodiment 2 | Pure phase, does not have other dephasign | High | 160 | Good |
| Embodiment 3 | Pure phase, does not have other dephasign | High | 450 | Good |
| Embodiment 4 | Pure phase, does not have other dephasign | High | 500 | Good |
| Embodiment 5 | Pure phase, does not have other dephasign | High | 400 | Good |
For the XRD collection of illustrative plates that embodiment 1, Fig. 1 is lithium ion cell positive prepared in the embodiment of the present invention 1; Fig. 3 is scanning electron microscopy (SEM) photo of lithium ion cell positive prepared in the embodiment of the present invention 1.
Embodiment 6-10 is for illustration of the performance of the assembling of lithium ion cell positive of the present invention and the lithium ion battery of assembling.
Embodiment 6
A. the preparation of electrolyte:
Meet ethylene carbonate (EC) with volume ratio: the mixed solvent of dimethyl carbonate (DMC)=1:1 for solvent, with LiPF
6for solute, obtained LiPF
6concentration is the electrolyte of 1 mol/L.
B. the assembling of battery:
In the glove box being full of argon gas, the product obtained by embodiment 1 is as battery anode slice, with diameter be 15 millimeters, the metal lithium sheet of purity 99.9% is as to electrode, the polypropylene diaphragm paper being 19 millimeters with diameter forms battery battery core, add 0.15 milliliter of electrolyte, make experiment fastening lithium ionic cell.
Embodiment 7
A. the preparation of electrolyte:
Meet ethylene carbonate (EC) with volume ratio: the mixed solvent of dimethyl carbonate (DMC)=1:1 for solvent, with LiPF
6for solute, obtained LiPF
6concentration is the electrolyte of 1 mol/L.
B. the assembling of battery:
In the glove box being full of argon gas, the product obtained by embodiment 2 is as battery anode slice, with diameter be 13 millimeters, the metal lithium sheet of purity 99% is as to electrode, the polypropylene diaphragm paper being 19 millimeters with diameter forms battery battery core, add 0.14 milliliter of electrolyte, make experiment fastening lithium ionic cell.
Embodiment 8
A. the preparation of electrolyte:
Meet ethylene carbonate (EC) with volume ratio: the mixed solvent of dimethyl carbonate (DMC)=1.5:1 for solvent, with LiPF
6for solute, obtained LiPF
6concentration is the electrolyte of 1 mol/L.
B. the assembling of battery:
In the glove box being full of argon gas, the product obtained by embodiment 3 is as battery anode slice, with diameter be 16 millimeters, the metal lithium sheet of purity 98% is as to electrode, the polypropylene diaphragm paper being 19 millimeters with diameter forms battery battery core, add 0.16 milliliter of electrolyte, make experiment fastening lithium ionic cell.
Embodiment 9
A. the preparation of electrolyte:
Meet ethylene carbonate (EC) with volume ratio: the mixed solvent of dimethyl carbonate (DMC)=1:0.9 for solvent, with LiPF
6for solute, obtained LiPF
6concentration is the electrolyte of 1 mol/L.
B. the assembling of battery:
In the glove box being full of argon gas, the product obtained by embodiment 1 is as battery anode slice, with diameter be 10 millimeters, the metal lithium sheet of purity 97% is as to electrode, the polypropylene diaphragm paper being 19 millimeters with diameter forms battery battery core, add 0.13 milliliter of electrolyte, make experiment fastening lithium ionic cell.
Embodiment 10
A. the preparation of electrolyte:
Meet ethylene carbonate (EC) with volume ratio: the mixed solvent of dimethyl carbonate (DMC)=0.9:1 for solvent, with LiPF
6for solute, obtained LiPF
6concentration is the electrolyte of 1 mol/L.
B. the assembling of battery:
In the glove box being full of argon gas, the product obtained by embodiment 1 is as battery anode slice, with diameter be 18 millimeters, the metal lithium sheet of purity 97% is as to electrode, the polypropylene diaphragm paper being 19 millimeters with diameter forms battery battery core, add 0.2 milliliter of electrolyte, make experiment fastening lithium ionic cell.
Performance test
The lithium ion battery prepared by embodiment 6-10 is placed on test cashier's office in a shop respectively, first carries out constant current charge with 0.05C, charging upper limit to 4.5 volt, the charging capacity of record battery; 1.5 volts are discharged to from 4.5 volts again, the discharge capacity of record battery, cycle charge-discharge n time in this manner with the electric current of 0.05C.
Calculate each charging and discharging capacity of battery according to the following equation:
Charging and discharging capacity=battery charging and discharging capacity (MAH)/positive electrode weight (gram)
Test result is as shown in table 3 below.
Table 3
| Embodiment | Discharge and recharge number of times | Charge specific capacity (mAh/g) | Specific discharge capacity (mAh/g) |
| Embodiment 6 | The 4th | 202.5 | 202.1 |
| Embodiment 7 | The 4th | 193.2 | 191.8 |
| Embodiment 8 | The 4th | 185.94 | 180.02 |
| Embodiment 9 | 2nd time | 175.1 | 173.2 |
| Embodiment 10 | 2nd time | 185.2 | 183.1 |
Table 3 shows the chemical property of the lithium ion battery excellence of lithium ion cell positive of the present invention assembling.
For embodiment 6, the 2 to 5 charging and discharging curve figure of prepared lithium ion battery as indicated with 2; The theoretical value of the charging and discharging capacity of the battery that iron borate lithium is prepared as positive electrode is 220mAh/g, the impulse electricity specific capacity of battery prepared by visible the present invention closely theoretical value.
For embodiment 6, the cycle performance curve chart of prepared lithium ion battery under different multiplying as shown in Figure 4.Under the multiplying power of 0.1C, after 30 charge and discharge cycles, its specific discharge capacity is still stabilized in more than 195mAh/g, and the cyclical stability of the battery of lithium ion cell positive assembling prepared by visible the present invention is good.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned execution mode, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible compound mode.
In addition, also can carry out combination in any between various different execution mode of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (14)
1. a preparation method for lithium ion cell positive, is characterized in that, the method comprises the following steps:
(1) the lithium source aqueous solution or suspension, the ferric iron source aqueous solution or suspension and the boron source aqueous solution or suspension are added in the carbon source aqueous solution successively, obtain mixed solution;
(2) by dry for the mixed solution obtained in step (1), iron borate lithium presoma is obtained;
(3) the iron borate lithium presoma obtained in step (2) is mixed with organic substance, obtain LiFeBO
3/ C presoma;
(4) LiFeBO will obtained in step (3)
3/ C presoma is shaped to bulk, obtains LiFeBO
3/ C block type electrode presoma;
(5) LiFeBO will obtained in step (4)
3/ C block type electrode presoma is calcined under inert atmosphere protection, obtains lithium ion cell positive.
2. preparation method according to claim 1, wherein, in element, the mol ratio of described boron source, lithium source and ferric iron source is (1.05-1.15): (1-1.1): 1, is preferably (1.1-1.15): (1-1.05): 1; In compound, the mol ratio of described ferric iron source and described carbon source is 1:(0.5-2), described ferric iron source and described organic mol ratio are 1:(0.2-0.5).
3. preparation method according to claim 1 and 2, wherein, described boron source be selected from boric acid, ammonium borate and diboron trioxide one or more; Described lithium source be selected from lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate and lithium nitrate one or more; Described ferric iron source be selected from di-iron trioxide, ferric nitrate, ferric oxalate and ironic citrate one or more.
4. preparation method according to claim 1 and 2, wherein, described carbon source is organic substance;
Under preferable case, described carbon source be selected from glucose, citric acid, sucrose, Glycolic acid, tartaric acid and ascorbic acid one or more.
5. preparation method according to claim 1 and 2, wherein, described organic substance be selected from glucose, sucrose and ascorbic acid one or more.
6. preparation method according to claim 1 and 2, wherein, in step (2), the temperature of described drying is 60-80 DEG C, and the time is 12-20h.
7. preparation method according to claim 1 and 2, wherein, in step (2), described drying is dry for carrying out twice in atmosphere.
8. preparation method according to claim 7, wherein, temperature dry is for the first time 60-80 DEG C, and the time is 12-20h, and the temperature of second time drying is 120-220 DEG C, and the time is 4-8h.
9. preparation method according to claim 1 and 2, wherein, mixing described in step (3) adopts ball-milling treatment, and the speed of ball milling is 200-300r/min, and the time of ball milling is 1.5-2.5h.
10. preparation method according to claim 1 and 2, wherein, shaping employing cold pressing treatment described in step (4), the pressure of colding pressing is 1-100MPa, and the time of colding pressing is 120-600 second.
11. preparation methods according to claim 1 and 2, wherein, in step (5), the temperature of described calcining is 600-750 DEG C, and the time of calcining is 6-24h.
12. preparation methods according to claim 1 and 2, wherein, in step (5), before described calcining, also comprise described LiFeBO
3/ C block type electrode presoma carries out preliminary treatment under inert atmosphere protection, and this pretreated temperature is 300-400 DEG C, and the time is 2-24h.
13. preparation methods according to claim 1 and 2, wherein, described inert atmosphere is Dynamic Atmosphere, and gas flow rate is 2-50mL/min.
14. lithium ion cell positives prepared by the method in claim 1-13 described in any one.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104835959A (en) * | 2015-04-30 | 2015-08-12 | 奇瑞汽车股份有限公司 | Lithium ferrous borate anode material of lithium ion battery and preparation method thereof |
| CN108751216A (en) * | 2018-07-11 | 2018-11-06 | 方嘉城 | A kind of preparation method of iron borate lithium |
| CN110299515A (en) * | 2018-03-23 | 2019-10-01 | 比亚迪股份有限公司 | A kind of positive electrode active materials and preparation method thereof, Anode and battery |
| CN111547734A (en) * | 2020-05-11 | 2020-08-18 | 蒋达金 | Preparation method of carbon-doped lithium iron borate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020047112A1 (en) * | 2000-08-30 | 2002-04-25 | Sony Corporation | Cathode active material, method for preparation thereof, non-aqueous electrolyte cell and method for preparation thereof |
| CN101777648A (en) * | 2010-01-26 | 2010-07-14 | 中国科学院宁波材料技术与工程研究所 | Preparation method of monodisperse lithium iron phosphate nanometer material and lithium-ion secondary battery |
| CN101955190A (en) * | 2010-09-20 | 2011-01-26 | 四川久远环通电源有限责任公司 | Method for preparing lithium iron borate anode material of lithium ion battery |
| CN102079530A (en) * | 2009-11-29 | 2011-06-01 | 宁波大学 | Method for preparing lithium iron borate serving as positive material of lithium ion battery by sol-gel technology |
-
2013
- 2013-09-09 CN CN201310406639.5A patent/CN104425799B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020047112A1 (en) * | 2000-08-30 | 2002-04-25 | Sony Corporation | Cathode active material, method for preparation thereof, non-aqueous electrolyte cell and method for preparation thereof |
| CN102079530A (en) * | 2009-11-29 | 2011-06-01 | 宁波大学 | Method for preparing lithium iron borate serving as positive material of lithium ion battery by sol-gel technology |
| CN101777648A (en) * | 2010-01-26 | 2010-07-14 | 中国科学院宁波材料技术与工程研究所 | Preparation method of monodisperse lithium iron phosphate nanometer material and lithium-ion secondary battery |
| CN101955190A (en) * | 2010-09-20 | 2011-01-26 | 四川久远环通电源有限责任公司 | Method for preparing lithium iron borate anode material of lithium ion battery |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104835959A (en) * | 2015-04-30 | 2015-08-12 | 奇瑞汽车股份有限公司 | Lithium ferrous borate anode material of lithium ion battery and preparation method thereof |
| CN106450301A (en) * | 2015-04-30 | 2017-02-22 | 奇瑞汽车股份有限公司 | Lithium iron borate (LiFeBO3) anode material for lithium ion battery and preparation method thereof |
| CN106450301B (en) * | 2015-04-30 | 2019-02-22 | 奇瑞汽车股份有限公司 | A kind of lithium ion battery boric acid ferrous iron lithium anode material and preparation method thereof |
| CN110299515A (en) * | 2018-03-23 | 2019-10-01 | 比亚迪股份有限公司 | A kind of positive electrode active materials and preparation method thereof, Anode and battery |
| CN110299515B (en) * | 2018-03-23 | 2023-08-08 | 比亚迪股份有限公司 | Positive electrode active material, preparation method thereof, positive electrode and battery |
| CN108751216A (en) * | 2018-07-11 | 2018-11-06 | 方嘉城 | A kind of preparation method of iron borate lithium |
| CN108751216B (en) * | 2018-07-11 | 2019-11-22 | 方嘉城 | A kind of preparation method of iron borate lithium |
| CN111547734A (en) * | 2020-05-11 | 2020-08-18 | 蒋达金 | Preparation method of carbon-doped lithium iron borate |
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