CN101916860A - Method for manufacturing electrochemical active material - Google Patents
Method for manufacturing electrochemical active material Download PDFInfo
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- CN101916860A CN101916860A CN2010102569042A CN201010256904A CN101916860A CN 101916860 A CN101916860 A CN 101916860A CN 2010102569042 A CN2010102569042 A CN 2010102569042A CN 201010256904 A CN201010256904 A CN 201010256904A CN 101916860 A CN101916860 A CN 101916860A
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- phosphate
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000011149 active material Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 41
- 230000008569 process Effects 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- -1 phosphor salt compounds Chemical class 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229940116007 ferrous phosphate Drugs 0.000 claims description 8
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 8
- 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 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000007600 charging Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000013016 damping Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- OYTKINVCDFNREN-UHFFFAOYSA-N amifampridine Chemical compound NC1=CC=NC=C1N OYTKINVCDFNREN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 claims description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 2
- 238000003836 solid-state method Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 8
- 239000001569 carbon dioxide Substances 0.000 abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000007306 turnover Effects 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 description 2
- ZVKRVGZVXQYLPZ-UHFFFAOYSA-N [Li].[V].P(O)(O)(O)=O Chemical compound [Li].[V].P(O)(O)(O)=O ZVKRVGZVXQYLPZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010325 electrochemical charging Methods 0.000 description 1
- 238000010326 electrochemical discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- FNLJLQUTIUDEHI-UHFFFAOYSA-N phosphoric acid vanadium Chemical compound [V].OP(O)(O)=O FNLJLQUTIUDEHI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/36—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
-
- 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
-
- 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)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for manufacturing an electrochemical active material. The method is characterized by comprising the following steps of: (1) smashing and mixing ferric salt, lithium salt or phosphor salt compounds in a vibrating ball mill according to the molar ratio of ferrum element to lithium element to phosphor element of 1:1:1; and circulating the operation; and (2) after the uniformly mixing process in the step (1), putting a mixture into a ball milling rotary furnace and sintering the mixture in an inert atmosphere. The method has the characteristics of short processing reaction time, low energy consumption and excellent performance of processed product, simultaneously improves material purity, reduces the emission of carbon dioxide and contributes to environmental protection by adopting a carbon-free processing process.
Description
Technical field
The present invention relates to a kind of method of making electrochemical active material, particularly design a kind of continous way that circulates and do not have the synthetic method for preparing electrochemical active material of carbon reduction-low temperature.
Background technology
Outstanding lithium ion battery should have the following advantages at least: high and stable operating voltage, high specific energy, high energy density, the cycle life of growing and memory-less effect etc.The commercialization lithium ion battery that Sony Corporation released in nineteen ninety satisfies above-mentioned condition substantially, and therefore, this lithium ion battery is able to rapid popularization, becomes the main product on the secondary cell market.Mobile phone, notebook computer and some other portable electric equipment use lithium ion battery as power supply mostly at present, and to its demand also with sustainable growth. in the future, electric automobile and large-scale energy-storage battery all may use lithium ion battery, and this makes the theory of lithium ion battery and the stage that application study enters accelerated development.
The material that uses in the lithium ion battery mainly comprises positive electrode (containing active material and conductive materials etc.), negative material, collector and barrier film etc.At present, the positive active material that uses in the commercial lithium ion battery remains with LiCoO
2Be main, this positive active material has excellent chemical property.Yet, cobalt resource rareness, costliness, poisonous, biology safety is poor, is not suitable for large-scale application.Therefore, the researcher is devoted to study new positive active material always, as LiFePO 4 (LiFePO
4), phosphoric acid vanadium lithium (Li
3V
2(PO
4)
3) etc.
LiFePO 4 (LiFePO
4), it has stable crystal structure, fail safe is good, cycle performance is good especially, do not use strategic resource nickel cobalt, low, the material non-toxic environmental protection of price, because its crystal structure is stable, overcharging resisting and to cross the ability of putting strong is acknowledged as the best positive electrode of making high safety, low-cost, long life lithium batteries.Phosphoric acid vanadium lithium (Li
3V
2(PO
4)
3) be a kind of high performance lithium ion battery anode material.It has higher discharge platform; Higher charge/discharge capacity, theoretical capacity are 197mAh/g, than other anode material for lithium-ion batteries, have than macro-energy density, and good security performance, and cheap is considered to one of the most promising anode material for lithium-ion batteries in future.
Patent CN 101172597A has proposed the employing iron powder as source of iron, but adopts ammonium dihydrogen phosphate synthetic, and it is exhaust emission gas also.Patent CN101172599 proposes to adopt the method reducing iron oxides of carbon coating and the presoma that phosphoric acid is formed, synthesizing lithium ferrous phosphate, but this technology of preparing technology in early stage is comparatively complicated, cost is higher, and carbon coats can't reach stable homogeneous, the synthetic great amount of carbon dioxide that produces is disposed in the atmosphere and pollutes.
The preparation method that patent application CN101106194 discloses a kind of cathode material lithium vanadium phosphate of lithium ion battery 2008 month January 16, the phosphoric acid vanadium lithium matrix of preparation, matrix is coated with material with carbon element, utilize nano particle post forming liquid phase method to synthesize anode material vanadium lithium phosphate, simplified operation sequence, cause a batch poor stability but liquid phase is synthetic, production cost is higher.
What the present suitability for industrialized production of ferrousphosphate lithium material adopted is wet-mixed and spray-dired method, carries out high temperature subsequently and synthesizes.This technology, early stage, operation was loaded down with trivial details, problem such as cost is higher, and the process control instability causes batch property difference big, and the inhomogeneous sintering reaction that causes of mixing of materials is incomplete, consumes a large amount of electric energy, and production efficiency is low.The present invention comes therefrom.
Summary of the invention
The object of the invention provides a kind of manufacture method of electrochemical active material, and the processing reaction time is short, and energy consumption is few, the properties of product that process are good, can adopt carbon-free synthesis technique simultaneously, improved the purity of material, reduce the discharge of carbon dioxide, helped environmental protection.
Incomplete in order to solve sintering reaction of the prior art, consume a large amount of electric energy, problem such as production efficiency is low, technical scheme provided by the invention is:
A kind of method of making electrochemical active material is characterized in that said method comprising the steps of:
(1) with molysite, lithium salts or microcosmic salt compound in ferro element: elemental lithium: the P elements mol ratio is that 1: 1: 1 ratio is pulverized in vibrator, mixed, and circulation is operation as above;
(2) after step (1) mixing operation, change in the ball milling rotary furnace and under inert atmosphere, burn till.
Preferably, molysite described in the described method step (1) is selected from one or more following compound: ferrous phosphate, tri-iron tetroxide, di-iron trioxide, ferrous oxide, iron hydroxide, ferrous oxalate; Described lithium salts is selected from one or more following compound: lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, phosphoric acid hydrogen two lithiums, lithium phosphate; Described microcosmic salt is selected from one or more following compound: ferrous phosphate, ammonium di-hydrogen phosphate, DAP, lithium dihydrogen phosphate, phosphorus pentoxide.
Preferably, described vibrator comprises mill tube, be provided with ball-milling medium in the described mill tube, described mill tube two ends are provided with charging aperture and discharging opening, described mill tube discharging opening connects described mill tube charging aperture by the circulation material conveying pipe, the mill tube lower end is provided with the support that supports mill tube, between described support and mill tube damping spring is set.
Preferably, described mill tube is one or more vibration stavings with ball-milling medium, and the vibration generator that vibration staving arranged outside drive motors drives makes abrasive media resonance grinding material in the mill tube after described vibration generator starts.
Preferably, described ball-milling medium is a kind of or its combination in metal, the pottery; Described ball-milling medium is a kind of or its combination of cylindricality, sphere, clavate, and size dimension is the combination of single size or multiple size.
Preferably, inert atmosphere is selected from a kind of of argon gas, nitrogen, helium in the described method step (2).
Preferably, firing process described in the described method adopts high temperature solid-state method synthetic, and heating-up temperature and time are controlled separately by the PID controller, and calcining heat is controlled at 200 ℃～900 ℃, calcination time 1h～6h.
The present invention adopt vibrator to material circulate, mix, dry, described vibrator comprises one or more vibration stavings with ball-milling medium, the staving outside has heater, realizes the circulation, mixed, dry of material.Material is pulverized and mixed by ball-milling medium, make material particles constantly be pulverized, mix thoroughly evenly, and then make material synthetic fast, fully, the finished product high conformity.
Further, described material is mainly ferrous salt, lithium salts and phosphatic mixture, and described ferrous salt, lithium salts and phosphatic mol ratio are 1: 1: 1, and described electrochemical active material is a LiFePO 4.Different with general employing trivalent iron salt processing LiFePO 4, it is carbon-free synthetic adopting ferrous salt, need not to add carbon again and carries out redox reaction, can not produce great amount of carbon dioxide and be unfavorable for environmental protection, the LiFePO 4 phosphorus content of finished product is few simultaneously, the purity height, and performance is better.
Further, described firing process is controlled separately by PID (proportional-integral-differential) controller, and synthetic district of low temperature and the synthetic district of high temperature can be set, and effectively controls material reaction time, temperature.The storehouse that connects material that is connected with discharge system has the cold water cooling system, is used for the active material that processes is cooled off.The discharging opening of boiler tube can also be provided with material return system, with the loopback of material that also needs to process to ball milling heating interval, cyclic process.
Further, described ball-milling medium is one or more in metal, the pottery; Being shaped as of ball-milling medium is spherical or cylindrical; Described ball-milling medium is single size or a plurality of size, and promptly ball-milling medium is same dimensions, or ball-milling medium is that the ball-milling medium of multiple dimensions mixes.The material of ball-milling medium, shape and size can be chosen as required, to satisfy the material grinding needs.
Further, the course of processing is as follows: material is fully mixed, and add continuously in the ball milling rotary furnace by feed system under inert gas (preferably nitrogen) protective condition; in the low temperature building-up process; temperature is controlled at 200～900 degree, is incubated 1～6 hour, subsequently cooling.
With respect to scheme of the prior art, advantage of the present invention is:
1, the present invention is in the man-hour that adds of carrying out electrochemical active material, by vibrator material is carried out limit pulverizing, limit mixing, limit reaction, make mixing of materials abundant, be beneficial to material and fully react synthetic, the appearance structure of synthetic material, particle size distribution, tap density, specific area and chemical property are good.
2. the present invention can select for use the environmental friendliness material to carry out the carbon-free processing of LiFePO 4, satisfies the environmental protection needs; Improved the purity of LiFePO 4 simultaneously.
3. the present invention compares existing static sintering and dynamic sinter, aggregate velocity, temperature, time that it can effectively control the material in the body of heater, make product to show to have good electrochemical stability, and charge/discharge capacity height, high rate performance are good.
4. the reaction time of the present invention is short, effectively cuts down the consumption of energy, and reduces product cost.
Description of drawings
Below in conjunction with drawings and Examples the present invention is further described:
Fig. 1 is the structural representation of specific embodiment of the invention vibrator;
Fig. 2 is the structural representation of specific embodiment of the invention ball milling rotary furnace;
Fig. 3 is the specific embodiment of the invention one gained material electrochemical charging and discharging curve figure.
Wherein: 1 is mill tube; 2 is ball-milling medium, and 3 is damping spring, and 4 is the ball milling rotary furnace; 42 boiler tubes; 43 ball milling heating intervals; 45 conventional heating intervals; 47 baffle plates; 48 feed systems; 49 discharge systems.
Embodiment
Below in conjunction with specific embodiment such scheme is described further.Should be understood that these embodiment are used to the present invention is described and are not limited to limit the scope of the invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.
The preparation of embodiment 1 LiFePO 4
Adopt vibrator to carry out material grinding, mixing, circulation among this embodiment, vibrator comprises mill tube 1, be provided with ball-milling medium 2 in the described mill tube 1, described mill tube two ends are provided with charging aperture 11 and discharging opening 12, described mill tube discharging opening 12 connects described mill tube charging aperture 11 by the circulation material conveying pipe, the mill tube lower end is provided with the support that supports mill tube 1, and 1 of described support and mill tube are provided with damping spring 3.
Adopt the ball milling rotary furnace synthetic then, the structure of ball milling rotary furnace 4 comprises feed system, discharge system and boiler tube 42 as shown in Figure 2, is provided with the ball milling heating interval 43 that at least one has ball-milling medium 2 in the boiler tube 42 of described ball milling rotary furnace 4.Boiler tube 42 an inner conventional heating interval 45 and two ball milling heating intervals 43 that distribute.Heating-up temperature that each is interval and time adopt PID to control separately.In each ball milling heating interval both sides baffle plate 47 is arranged, there is ball-milling medium 2 centre, baffle shapes is identical with the body of heater cross section, be fixed on boiler tube 42 inner supports, baffle plate 47 diameters are less than the boiler tube caliber, the sieve aperture that distributing on the baffle plate, the space between body of heater and the baffle plate 47 and the aperture of sieve aperture are less than the minimum diameter of ball-milling medium 2.Ball-milling medium 2 is spherical or cylindrical.Ball-milling medium 2 is one or more in metal, the pottery.Ball-milling medium 2 can be a single-size, also can be a plurality of sizes.
With ferrous phosphate and lithium carbonate or lithium hydroxide 1: 1 in molar ratio after vibrator fully mixes; under the nitrogen protection condition, material is entered in the ball milling rotary furnace continuously; in the low temperature building-up process; temperature control 200～400 degree; be incubated 1～4 hour; high-temperature region control temperature is incubated 1～4 hour speed of gyration 1 turnover/per minute when 400～800 spend, room temperature cooling subsequently.Through powder process, test, be packaged to be the product LiFePO 4.The electro-chemical test process is added conductive carbon black, and binding agent is made pole piece, and electro-chemical test is selected metal lithium sheet for use to electrode.The material tap density that present embodiment is prepared is greater than 1.3g/cm
3, electrode substance electrochemical discharge gram volume is greater than 150mAh/g, as shown in Figure 3.
The preparation of embodiment 2 LiFePO 4s
Vibrator and ball milling rotary furnace are as described in the embodiment 1.
Iron oxide and ammonium di-hydrogen phosphate and lithium carbonate or lithium hydroxide 1: 1: 1 are in molar ratio fully mixed at vibrator; after adding the conductive carbon black mixing subsequently; under the nitrogen protection condition, material is entered the ball milling rotary furnace continuously; in the low temperature building-up process; temperature control 200～400 degree are incubated 1～4 hour, and high-temperature region control temperature is when 400～800 spend; be incubated 1～4 hour speed of gyration 1 turnover/per minute, room temperature cooling subsequently.Through powder process, test, be packaged to be the product LiFePO 4.In the electro-chemical test process, add conductive agent, binding agent is made pole piece, and test is selected metal lithium sheet for use to electrode.The material tap density that present embodiment is prepared is greater than 1.2g/cm
3, electrode substance electrochemical discharge gram volume is greater than 150mAh/g.
The preparation of embodiment 3 LiFePO 4s
Vibrator and ball milling rotary furnace are as described in the embodiment 1.
The oxide of iron and lithium phosphate 1: 1 are in molar ratio fully mixed at vibrator; after adding the conductive carbon black mixing subsequently; under the nitrogen protection condition, material is entered the ball milling rotary furnace continuously; in the low temperature building-up process; temperature control 200～400 degree are incubated 1～4 hour, and high-temperature region control temperature is when 400～800 spend; be incubated 1～4 hour speed of gyration 1 turnover/per minute, room temperature cooling subsequently.Through powder process, test, be packaged to be the product LiFePO 4.In the electro-chemical test process, add conductive agent, binding agent is made pole piece, and test is selected metal lithium sheet for use to electrode.The material tap density that present embodiment is prepared is greater than 1.2g/cm
3, electrode substance electrochemical discharge gram volume is greater than 150mAh/g.
As can be seen, ferrous ferrous phosphate that specific embodiment one adopts when reacting, need not to add conductive carbon black as reaction raw materials in the ball milling rotary furnace, and the course of processing does not produce great amount of carbon dioxide, environmental protection more, product purity height simultaneously; To prepare the tap density of material big than specific embodiment two and three for specific embodiment one as can be seen.
The present invention processes the reaction time weak point, and energy consumption is few, and the properties of product that process are good, can adopt carbon-free processing technology simultaneously, has improved the purity of material, has reduced the discharge of carbon dioxide, helps environmental protection.
Above-mentioned example only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the people who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.
Claims (7)
1. method of making electrochemical active material is characterized in that said method comprising the steps of:
(1) with molysite, lithium salts or microcosmic salt compound in ferro element: elemental lithium: the P elements mol ratio is that 1: 1: 1 ratio is pulverized in vibrator, mixed, and circulation is operation as above;
(2) after step (1) mixing operation, change in the ball milling rotary furnace and under inert atmosphere, burn till.
2. method according to claim 1 is characterized in that molysite described in the described method step (1) is selected from one or more following compound: ferrous phosphate, tri-iron tetroxide, di-iron trioxide, ferrous oxide, iron hydroxide, ferrous oxalate; Described lithium salts is selected from one or more following compound: lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, phosphoric acid hydrogen two lithiums, lithium phosphate; Described microcosmic salt is selected from one or more following compound: ferrous phosphate, ammonium di-hydrogen phosphate, DAP, lithium dihydrogen phosphate, phosphorus pentoxide.
3. method according to claim 1, it is characterized in that described vibrator comprises mill tube (1), be provided with ball-milling medium (2) in the described mill tube (1), described mill tube two ends are provided with charging aperture (11) and discharging opening (12), described mill tube discharging opening (12) connects described mill tube charging aperture (11) by the circulation material conveying pipe, the mill tube lower end is provided with the support that supports mill tube (1), and damping spring (3) is set between described support and mill tube (1).
4. method according to claim 3, it is characterized in that described mill tube (1) is one or more vibration stavings with ball-milling medium, the vibration generator that vibration staving arranged outside drive motors drives makes abrasive media resonance grinding material in the mill tube after described vibration generator starts.
5. method according to claim 3 is characterized in that described ball-milling medium is a kind of or its combination in metal, the pottery; Described ball-milling medium is a kind of or its combination of cylindricality, sphere, clavate, and size dimension is the combination of single size or multiple size.
6. method according to claim 1 is characterized in that inert atmosphere in the described method step (2) is selected from a kind of of argon gas, nitrogen, helium.
7. method according to claim 1 is characterized in that firing process described in the described method adopts high temperature solid-state method synthetic, and heating-up temperature and time are controlled separately by the PID controller, and calcining heat is controlled at 200 ℃～900 ℃, calcination time 1h～6h.
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| CN2010102569042A CN101916860A (en) | 2010-08-19 | 2010-08-19 | Method for manufacturing electrochemical active material |
| PCT/CN2011/078568 WO2012022264A1 (en) | 2010-08-19 | 2011-08-18 | Method for producing electrochemical active material |
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| CN2010102569042A CN101916860A (en) | 2010-08-19 | 2010-08-19 | Method for manufacturing electrochemical active material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012022264A1 (en) * | 2010-08-19 | 2012-02-23 | 恒正科技（苏州）有限公司 | Method for producing electrochemical active material |
| CN102522526A (en) * | 2011-12-13 | 2012-06-27 | 济宁市无界科技有限公司 | Production equipment and technology for cathode or anode material of converter-type lithium battery |
| CN108483061A (en) * | 2018-05-21 | 2018-09-04 | 埃肯有机硅（上海）有限公司 | Non- explosion-proof workshop viscosifies agent feeding device with low-flash |
| CN113130875A (en) * | 2021-04-19 | 2021-07-16 | 浙江浩越能源科技有限公司 | Lithium vanadium phosphate battery positive electrode material and preparation process thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114887719B (en) * | 2022-04-12 | 2024-06-21 | 临沂大学 | A mechanochemical method for producing nanopowder |
| CN116177513A (en) * | 2022-12-08 | 2023-05-30 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing lithium vanadium phosphate lithium battery positive electrode material by two-stage roasting |
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| CN201407891Y (en) * | 2009-05-19 | 2010-02-17 | 恒正科技（苏州）有限公司 | rotary furnace for ball mill |
| CN101916860A (en) * | 2010-08-19 | 2010-12-15 | 恒正科技（苏州）有限公司 | Method for manufacturing electrochemical active material |
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| CN101152959A (en) * | 2006-09-30 | 2008-04-02 | 中南大学 | Preparation method of lithium iron phosphate composite oxide |
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| CN102522526B (en) * | 2011-12-13 | 2013-11-20 | 济宁市无界科技有限公司 | Production equipment and technology for cathode or anode material of converter-type lithium battery |
| CN108483061A (en) * | 2018-05-21 | 2018-09-04 | 埃肯有机硅（上海）有限公司 | Non- explosion-proof workshop viscosifies agent feeding device with low-flash |
| CN113130875A (en) * | 2021-04-19 | 2021-07-16 | 浙江浩越能源科技有限公司 | Lithium vanadium phosphate battery positive electrode material and preparation process thereof |
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| WO2012022264A1 (en) | 2012-02-23 |
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