CN103915661A - Method for direct recovery and restoration of lithium ion battery positive electrode material - Google Patents
Method for direct recovery and restoration of lithium ion battery positive electrode material Download PDFInfo
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- CN103915661A CN103915661A CN201310007896.1A CN201310007896A CN103915661A CN 103915661 A CN103915661 A CN 103915661A CN 201310007896 A CN201310007896 A CN 201310007896A CN 103915661 A CN103915661 A CN 103915661A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a method for direct recovery and restoration of a lithium ion battery positive electrode material, and belongs to the field of resource recycling. According to the method, waste positive electrode pieces of lithium cobaltate or lithium nickel manganese cobalt multi-element layered oxide or a positive electrode piece leftover material and defective products are used as a positive electrode material; the materials are classified according to the type of binder by component analysis, the binder is directly damaged, cleaning and separation of the positive electrode material and a current collector are realized; by use of a heavy liquid separation principle, the positive electrode and a conductive agent are separated; the positive electrode failure mechanism is studied by use of SEM (scanning electron microscope), XRD (X-ray diffraction), STEM (scanning transmission electron microscope), XPS (X-ray photoelectron spectroscopy) and other analysis means; chemical components of the positive electrode material with the layered structure not damaged can be repaired by high temperature roasting, the layered structure of the positive electrode material with disordered and defective crystal lattice can be repaired by dissolving with a hydrothermal reaction and then precipitation, and the positive electrode material with good charge discharge performances can be again obtained. The method avoids the dissolving leaching process, reduces waste liquid generation, and simplifies the technological process.
Description
Technical field
The invention belongs to resource circulation utilization field, provide a kind of apply materials branch of science directly to repair the method for waste lithium ion cell anode material.
Background technology
Since nineteen ninety Sony company successfully develops lithium ion battery and realizes commercialization, because lithium ion battery has the series of advantages such as operating voltage is high, specific energy is high, have extended cycle life, fail safe is good, be widely used in fields such as communication information, energy traffic, Aero-Space, military affairs and medical science, be called as " the most promising chemical power source ".The demand of the lithium ion battery to various uses significantly rose year by year in the last few years, and especially, in portable type electronic product fields such as mobile phone, notebook computer, video camera and electric tools, lithium ion battery, as first-selected power supply, has huge market.In the today of advocating energetically low-carbon economy and energy-saving and emission-reduction, new-energy automobile will become the main development direction of automobile industry, and the industrialization of hybrid-electric car and pure electric automobile will directly drive the rapid growth again in lithium ion battery market.Follow the extensive use of lithium ion battery, waste and old lithium-ion electric pool count also rises year by year, becomes the electronic waste can not be ignored.
Positive electrode occupies significant proportion in lithium ion battery cost, the commercial lithium-ion batteries positive electrode of China is still take cobalt acid lithium as main at present, follow the expansion of lithium ion battery purposes, positive electrode is being multivariant oxide fast development to lithium nickel cobalt manganese, therefore can alleviate to waste and old positive electrode recycling the problem that China's cobalt resource is in short supply, there is great strategic importance.In addition, the recycling of waste and old positive electrode also can significantly be saved mineral resources, preserves the ecological environment, and the recycling of anode material for lithium-ion batteries becomes lithium electricity industry and have the important step of great economic benefit and wide market prospects.
Countries in the world are all in development anode material for lithium-ion batteries recycling technology, all concentrate at present and utilize hydrometallurgy industrial technology to reclaim the metallic element in positive electrode, Xu J Q, Thomas H R, Franciset R W.A review of processes and technologies for the recycling of lithium-ion secondary batteries.Journal of Power Sources, 2008, 177 (2): in 512-527, summed up the basic procedure that lithium ion battery reclaims, first that electrode slice is broken apart, then battery material is dissolved to the metallic element in separation recovery leachate after leaching, maybe by directly synthetic positive electrode of this leachate.The domestic recovery for positive electrode is still in the starting stage, relatively ripe is also hydrometallurgical processes, multinomial patent of invention is disclosed, as patent CN101450815A, utilize sulfuric acid and hydrogen peroxide system that nickel, cobalt, manganese element are leached, then by processing the synthetic nickel-cobalt lithium manganate cathode material of leachate.But utilize hydrometallurgical processes recycling positive electrode, and all needing to dissolve and leach link, each stage all can produce waste liquid, causes serious secondary pollution, and complex process, and cost is high.In addition, described in patent CN101383442B, utilize NaOH dissolved aluminum to isolate inactivation cobalt acid lithium, directly mend lithium roasting recycling positive electrode, although simplified technological process, but in electrode slice separation process, still have waste liquid to produce, positive electrode reclaims and still belongs to rough formula development model.
Summary of the invention
A kind of method that the object of the present invention is to provide direct recovery and repair waste lithium ion cell anode material.Material science subject is applied to resource circulation utilization field by the present invention, avoid the dissolving in existing technique to leach link, reduce waste liquid generation, simplify technological process, do not need or add little chemical agent, without considering secondary pollution problem, have broad application prospects in today of advocate thriftiness energetically resource and cleaner production.
For achieving the above object, the present invention has adopted following technical scheme:
Fig. 1 is Technology Roadmap of the present invention.
As shown in Figure 1, the present invention selects professional equipment to disassemble waste and old lithium ion battery, and it is cobalt acid lithium (LiCoO that sorting obtains positive electrode
2) or the polynary layered oxide of lithium nickel cobalt manganese (Li (Ni
1-x-yco
xmn
y) O
2) positive plate or positive plate leftover pieces and the defect ware of battery production producer; By constituent analysis, according to the classification of binding agent kind, directly destroy binding agent, realize the clean separation of positive electrode and collector; Then utilize heavy-fluid separation principle that positive electrodes different density is separated with conductive agent, obtain positive electrode powder; Utilize the material analysis means research positive electrode inefficacy mechanisms such as SEM, XRD, STEM, XPS, EELS, ICP; According to inefficacy mechanism difference, layer structure is destroyed, directly adopt high-temperature roasting to repair chemical composition, and material lattice has chaotic and defect, adopt hydro-thermal reaction to dissolve and separate out again reparation layer structure, regain the positive electrode with good charge-discharge performance.
Direct recovery a method of repairing waste lithium ion cell anode material, described method comprises the steps:
(1) disassemble, to obtain positive electrode be cobalt acid lithium or the positive plate of the polynary layered oxide of lithium nickel cobalt manganese or positive plate leftover pieces and the defect ware of battery production producer in sorting;
(2) remove successively binding agent, collector and conductive agent, obtain positive electrode powder;
(3) the positive electrode powder inefficacy mechanism that research step (2) obtains, check positive electrode powder chemistry composition, when inefficacy mechanism is the loss of lithium and transition metal, when layer structure remains intact, carry out step (4), when inefficacy mechanism is transition metal valence transition, cause phase transformation, when layer structure causes confusion with defect, carry out step (4 ');
(4) according to the composition of positive electrode before losing efficacy, in the positive electrode powder obtaining in step (2), sneak into the compound of the metal of loss, sintering obtains the positive electrode of repairing;
(4 '), according to the composition of positive electrode before losing efficacy, sneaks into the transition metal oxide of solution loss in step (2) in the positive electrode powder obtaining, add the LiOH aqueous solution fully to stir, and hydro-thermal reaction obtains the positive electrode of repairing.
Based lithium-ion battery positive plate is made up of positive electrode, conductive agent, adhesive and collector.The positive plate of proportioning all can be used for the present invention arbitrarily, described positive plate can be both the positive plate to waste and old lithium ion battery is disassembled, sorting obtains, also can be positive plate leftover pieces or the defect ware of battery production producer, the positive electrode active materials that only needs described positive plate be cobalt acid lithium or the polynary layered oxide of lithium nickel cobalt manganese.Exemplary positive plate is as the positive plate of waste and old lithium ion battery, this positive plate is that positive electrode even roller is pressed on to the aluminum foil current collector two sides that thickness is about 20 μ m, positive electrode is made up of approximately 85% cobalt acid lithium or the polynary layered oxide isoreactivity of lithium nickel cobalt manganese material, 10% acetylene black conductor and 5% organic binder bond composition.The waste and old positive plate binding agent difference used of different manufacturers, mainly contains two kinds of polytetrafluoroethylene (PTFE) and Kynoar (PVDF).
In the present invention, the clean separation of positive electrode and collector, according to binding agent kind difference, adopts distinct methods to destroy binding agent.
In the time that binding agent is PTFE, adopt high-temperature decomposition, make binder decomposed, separate with collector thereby realize positive electrode, reach the object of removing binding agent and collector.By positive plate high-temperature roasting under inert atmosphere, PTFE is decomposed, the positive plate after roasting is taken out, mechanical friction makes positive electrode separate with collector, and sieve as required, remove the collector existing in positive electrode, obtain the mixed-powder of positive electrode and conductive agent.
Described high-temperature roasting is carried out under inert atmosphere, and the temperature of high-temperature roasting is 500 ~ 600 ℃, and for example 505 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 585 ℃, 590 ℃, 595 ℃, preferably 500 ~ 550 ℃.The time of described high-temperature roasting is 2 ~ 5h, for example 2.2h, 2.4h, 2.7h, 2.9h, 3.1h, 3.4h, 3.7h, 3.9h, 4.2h, 4.6h, 4.9h, preferably 2.3 ~ 4.5h, further preferred 3h.Because PTFE high-temperature split product is poisonous, now need waste gas to reclaim.
In the time that binding agent is PVDF, adopt solvent soaking to dissolve and make adhesive failure, thereby realize separating of positive electrode and collector, reach the object of removing binding agent and collector.
Soak temperature while dissolving and be controlled at 60 ~ 80 ℃ with accelerate dissolution, for example 61 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 79 ℃ of described temperature, preferably 61.5 ~ 78.5 ℃.Soak after dissolving, filter, washing, is dried, and obtains the mixed-powder of positive electrode and conductive agent.
Described solvent is selected from 1-METHYLPYRROLIDONE, N, the mixture of any one or at least two kinds in dinethylformamide, DMA or dimethyl sulfoxide (DMSO), such as N of described mixture, dinethylformamide and N, the mixture of N-dimethylacetylamide, the mixture of dimethyl sulfoxide (DMSO) and 1-METHYLPYRROLIDONE, N, dinethylformamide and N, the mixture of N-dimethylacetylamide, the mixture of dimethyl sulfoxide (DMSO) and 1-METHYLPYRROLIDONE, preferably 1-METHYLPYRROLIDONE.Dirty useless solvent can reuse by decompression distillation.
In the present invention, adopt heavy liquid separation method to remove the conductive agent in positive plate, filter, washing, the dry positive electrode powder that obtains.
Because the density of water is between conductive agent and positive electrode, therefore selects water to can be used as heavy-fluid and realize separating of conductive agent and positive electrode.Water is as heavy-fluid nontoxic pollution-free, reusable edible.
The method that exemplary heavy liquid separation method is removed the conductive agent in positive plate is: be added to the water removing binding agent and the positive electrode of collector and the mixed-powder of conductive agent, stir, leave standstill, the conductive agent that density is less than water is suspended in side waterborne, the positive electrode that density is greater than water is sunken to side under water, the positive electrode of below is flowed out, filter, the dry positive electrode powder that obtains.
By above method, can complete the recovery of positive electrode, be recycled positive electrode powder.
The present invention is by material analysis means research positive electrode inefficacy mechanisms such as SEM, XRD, STEM, XPS, EELS, ICP, the chemical composition of the positive electrode powder that checking procedure (2) obtains, determine the inefficacy mechanism that it is concrete, and then select suitable restorative procedure.
The positive electrode powder chemistry composition that checking procedure (2) obtains, when inefficacy mechanism is the loss of lithium and transition metal, when layer structure is intact, carry out step (4): according to the composition of positive electrode before losing efficacy, in the positive electrode powder obtaining in step (2), sneak into the compound of the metal of loss, sintering obtains the positive electrode of repairing.Before losing efficacy, positive electrode, as being cobalt acid lithium, was repaired as cobalt acid lithium; Before losing efficacy, positive electrode was the polynary layered oxide of lithium nickel cobalt manganese, repaired as the polynary layered oxide of lithium nickel cobalt manganese.
For the solution loss of the loss of cobalt acid lithium or the polynary layered oxide positive electrode of lithium nickel cobalt manganese charge and discharge process transition metal oxide interlayer lithium and transition metals cobalt, nickel etc., utilize high-temperature roasting method to repair chemical composition.According to the chemical composition analysis of the positive electrode before losing efficacy, the composition of the positive electrode powder obtaining according to step (3), determine metallic element and the loss amount of loss, then in the positive electrode powder obtaining in step (2), sneak into the compound of the metal of loss, sintering obtains the positive electrode of revising.The loss of lithium can obtain by sneaking into lithium salts in the positive electrode powder obtaining in step (2), and described lithium salts is for example Li
2cO
3, LiOH etc.The loss of cobalt, nickel and manganese can obtain by the oxide of sneaking into this metallic element in the positive electrode powder obtaining in step (2), the oxide of for example cobalt, the oxide of nickel, the oxide of manganese.For example work as cobalt and nickel and all damage and miss the season, can be by sneaking into the oxide of cobalt and the hopcalite of nickel in the positive electrode powder obtaining in step (2).The preparation method of the oxide of the oxide of described cobalt, the oxide of nickel and manganese is prior art.
The preparation method of the oxide of exemplary cobalt is: by cobalt salt, precipitant mix, there is precipitation reaction, precipitated product filtered, and washing, dry, then sintering, obtains the oxide of cobalt.Cobalt salt is replaced with to nickel salt or manganese salt can prepare the oxide of nickel or the oxide of manganese.If while obtaining mixed oxide, add corresponding salt, then salt, precipitation reagent and complexing agent are mixed, coprecipitation reaction, then carries out subsequent reactions, can prepare mixed oxide.Described precipitation reagent is as NaOH or Na
2cO
3, described complexing agent is as ammoniacal liquor.Described baking temperature is as 120 ℃, and described drying time is as 8h.Described sintering temperature is as 500 ~ 900 ℃, and preferably 700 ~ 900 ℃, further preferably 700 ℃, sintering time is 3 ~ 5h.XRD result shows that more than 700 ℃ roasting gained oxide crystal formation is better, when temperature is lower crystallization incomplete, when excess Temperature there is sintering in oxide, therefore optimum calcination temperature should be controlled at 700 ℃.
In step (4), in positive electrode powder, sneak into the compound of the metal of loss, making Li/ (Ni+Co+Mn) mol ratio is 1.05 ~ 1.15:1, for example 1.06:1,1.07:1,1.08:1,1.09:1,1.11:1,1.12:1,1.13:1,1.14:1, preferably 1.08 ~ 1.12:1, further preferred 1.1:1.In the time that positive electrode is cobalt acid lithium, n (Ni) and n (Mn) are 0, n and represent amount of substance.
Described sintering temperature is 750 ~ 950 ℃, for example 760 ℃, 780 ℃, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃, 900 ℃, 920 ℃, 940 ℃, and preferably 770 ~ 930 ℃, further preferably 750 ~ 870 ℃, most preferably 850 ℃.
Described roasting time is 10 ~ 20h, for example 10.5h, 11h, 11.5h, 12.5h, 13.5h, 14.5h, 15.5h, 16.5h, 17.5h, 18.5h, 19.5h, preferably 10.8 ~ 19.7h, further preferred 11.2 ~ 18.8h.
Preferably, in step (4), in positive electrode powder, sneak into the compound of the metal of loss, making Li/ (Ni+Co+Mn) mol ratio is 1.05 ~ 1.15:1,850 ℃ of sintering 10 ~ 20h obtain the positive electrode of repairing, in the time that positive electrode is cobalt acid lithium, n (Ni) and n (Mn) are 0, n and represent amount of substance.
The positive electrode powder chemistry composition that checking procedure (2) obtains, when inefficacy mechanism is transition metal valence transition, cause phase transformation, when layer structure causes confusion with defect, carry out step (4 '): according to the composition of positive electrode before losing efficacy, in the positive electrode powder obtaining in step (2), sneak into the transition metal oxide of solution loss, add the LiOH aqueous solution fully to stir, hydro-thermal reaction obtains the positive electrode of repairing.Before losing efficacy, positive electrode, as being cobalt acid lithium, was repaired as cobalt acid lithium; Before losing efficacy, positive electrode was the polynary layered oxide of lithium nickel cobalt manganese, repaired as the polynary layered oxide of lithium nickel cobalt manganese.
For cobalt or the transformation of nickel equivalent state occur in cobalt acid lithium or the polynary layered oxide positive electrode of lithium nickel cobalt manganese charge and discharge process, cause phase transformation, cause losing efficacy.The present invention separates out principle again according to dissolving, the positive electrode that utilizes hydro-thermal reaction reparation to lose efficacy.The composition of the positive electrode powder obtaining according to step (3), the positive electrode powder that step (2) is obtained mixes with the oxide ball milling of the metal of the generation valence transition of respective amount, add the LiOH aqueous solution fully to stir, move into autoclave, hydro-thermal reaction, utilize to dissolve and separate out again principle, obtain the positive electrode of repairing.
In step (4 '), in positive electrode powder, sneak into the transition metal oxide of solution loss, add the LiOH aqueous solution fully to stir, making Li/ (Ni+Co+Mn) mol ratio is 1.05 ~ 1.15:1, for example 1.06:1,1.07:1,1.08:1,1.09:1,1.11:1,1.12:1,1.13:1,1.14:1, preferably 1.08 ~ 1.12:1, further preferred 1.1:1.In the time that positive electrode is cobalt acid lithium, n (Ni) and n (Mn) are 0, n and represent amount of substance.
The temperature of described hydro-thermal reaction is 150 ~ 250 ℃, for example 155 ℃, 165 ℃, 175 ℃, 185 ℃, 195 ℃, 205 ℃, 215 ℃, 225 ℃, 235 ℃, 245 ℃, and preferably 160 ~ 240 ℃, further preferably 170 ~ 230 ℃, most preferably 200 ℃.
The time of described hydro-thermal reaction is 10 ~ 20h, for example 10.5h, 11h, 11.5h, 12.5h, 13.5h, 14.5h, 15.5h, 16.5h, 17.5h, 18.5h, 19.5h, preferably 10.8 ~ 19.7h, further preferably 11.2 ~ 18.8h, most preferably 15h.
The oxide of the oxide of described cobalt, the oxide of nickel and manganese be prepared as prior art.
Preferably, in the positive electrode powder obtaining in step (2) in step (4 '), sneak into the transition metal oxide of solution loss, add the LiOH aqueous solution fully to stir, making Li/ (Ni+Co+Mn) mol ratio is 1.05 ~ 1.15:1, moves into autoclave, hydro-thermal reaction 15h at 200 ℃, utilize to dissolve and separate out again principle, obtain the positive electrode of reparation, in the time that positive electrode is cobalt acid lithium, n (Ni) and n (Mn) are 0, n and represent amount of substance.
Exemplary example is as follows:
Before losing efficacy, positive electrode was cobalt acid lithium (LiCoO
2) time, by material analysis means research positive electrode inefficacy mechanisms such as SEM, XRD, STEM, XPS, EELS, ICP, the chemical composition of the positive electrode powder that checking procedure (2) obtains, inefficacy mechanism is the loss of lithium, according to the composition of positive pole material of lithium cobalt acid before losing efficacy, in the positive electrode powder obtaining in step (2), sneak into Li
2cO
3, sintering obtains the positive electrode of repairing; Inefficacy mechanism is the loss of lithium and cobalt, according to the composition of positive pole material of lithium cobalt acid before losing efficacy, by cobalt salt solution and NaOH or Na
2cO
3the slow injecting reactor generation of precipitation reagent precipitation reaction, by sediment filtration washing, 120 ℃ of vacuumize 8h, then 500 ~ 900 ℃ of roasting 3 ~ 5h make cobalt/cobalt oxide.Then take corresponding Li
2cO
3and this cobalt/cobalt oxide obtains positive electrode powder ball milling with step (2) and mix, making Li/Co mol ratio is 1.05 ~ 1.15:1, and 850 ℃ of high-temperature roasting 10 ~ 20h, obtain repairing positive electrode.
Before losing efficacy, positive electrode was the polynary layered oxide of lithium nickel cobalt manganese (Li (Ni
1-x-yco
xmn
y) O
2) time, by material analysis means research positive electrode inefficacy mechanisms such as SEM, XRD, STEM, XPS, EELS, ICP, the chemical composition of the positive electrode powder that checking procedure (2) obtains, inefficacy mechanism is the loss of lithium, according to the composition of anode material of lithium nickel-cobalt-manganese multi layered oxide before losing efficacy, in the positive electrode powder obtaining in step (2), sneak into Li
2cO
3, sintering obtains the positive electrode of repairing; Inefficacy mechanism is the loss of lithium, cobalt and nickel, according to the composition of anode material of lithium nickel-cobalt-manganese multi layered oxide before losing efficacy, cobalt salt and nickel salt solution is mixed, then by mixed solution and NaOH or Na
2cO
3precipitation reagent, the slow injecting reactor generation of ammoniacal liquor complexing agent coprecipitation reaction, by sediment filtration washing, 120 ℃ of vacuumize 8h, then 500 ~ 900 ℃ of roasting 3 ~ 5h make cobalt nickel mixed oxide.Then take corresponding Li
2cO
3and this cobalt nickel mixed oxide obtains positive electrode powder ball milling with step (2) and mixes, making Li/ (Ni+Co+Mn) mol ratio is 1.05 ~ 1.15:1,850 ℃ of high-temperature roasting 10 ~ 20h, regenerate enough lithiums and are distributed in the layer structure of transition metal oxide interlayer.
Before losing efficacy, positive electrode was cobalt acid lithium (LiCoO
2) time, pass through SEM, XRD, STEM, XPS, EELS, the material analysis means research positive electrode inefficacy mechanisms such as ICP, the chemical composition of the positive electrode powder that checking procedure (2) obtains, inefficacy mechanism is transition metals cobalt valence transition, cause phase transformation, layer structure is destroyed, and the solution loss of Co, according to the composition of positive pole material of lithium cobalt acid before losing efficacy, in the positive electrode powder obtaining in step (2), sneak into the oxide of cobalt, add the LiOH aqueous solution fully to stir, making Li/Co mol ratio is 1.05 ~ 1.15:1, move into autoclave, hydro-thermal reaction 15h at 200 ℃, utilize to dissolve and separate out again principle, obtain the positive electrode of repairing.
Before losing efficacy, positive electrode was the polynary layered oxide of lithium nickel cobalt manganese (Li (Ni
1-x-yco
xmn
y) O
2) time, pass through SEM, XRD, STEM, XPS, EELS, the material analysis means research positive electrode inefficacy mechanisms such as ICP, the chemical composition of the positive electrode powder that checking procedure (2) obtains, inefficacy mechanism is the valence transition of transition metals cobalt and/or nickel, cause phase transformation, and the solution loss of cobalt and/or nickel etc., according to the composition of anode material of lithium nickel-cobalt-manganese multi layered oxide before losing efficacy, in the positive electrode powder obtaining in step (2), sneak into cobalt and/oxide of nickel, add the LiOH aqueous solution fully to stir, making Li/ (Co+Ni+Mn) mol ratio is 1.05 ~ 1.15:1, move into autoclave, hydro-thermal reaction 15h at 200 ℃, utilize to dissolve and separate out again principle, obtain the positive electrode of repairing.
Described active material is positive electrode.
Compared with prior art, the present invention has following beneficial effect:
Material science subject is applied to resource circulation utilization field by the present invention, chemical property inefficacy mechanism and Principles thereof from microcosmic angle research positive electrode charge and discharge process, instruct recycling technology to macroscopic perspective again, avoid using acid solution to leach the link of metallic element, significantly reduce the discharge of secondary pollution, directly reclaim and repair positive electrode, avoid later separation and extraction to metallic element, simplify technique, compared with existing technology, technological process is short, energy consumption is low, environmental friendliness, be applicable to cobalt acid lithium and the polynary layered oxide recycling of lithium nickel cobalt manganese simultaneously.
Accompanying drawing explanation
Further illustrate technical scheme of the present invention below in conjunction with accompanying drawing and by embodiment.
Fig. 1: Technology Roadmap of the present invention;
Fig. 2: NMP soaks separating obtained waste and old Li (Ni
1/3co
1/3mn
1/3) O
2positive electrode XRD collection of illustrative plates;
Fig. 3: the separating obtained waste and old Li (Ni of high-temperature roasting
1/3co
1/3mn
1/3) O
2positive electrode XRD collection of illustrative plates;
Fig. 4: repair embodiment 1 gained positive electrode 0.1C multiplying power first charge-discharge curve;
Fig. 5: repair embodiment 1 gained positive electrode 1C rate charge-discharge cyclic curve;
Fig. 6: repair embodiment 2 gained positive electrode XRD collection of illustrative plates;
Fig. 7: repair embodiment 2 gained positive electrode 0.1C multiplying power first charge-discharge curves;
Fig. 8: repair embodiment 2 gained positive electrode 1C rate charge-discharge cyclic curves.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
Positive electrode is Li (Ni
1/3co
1/3mn
1/3) O
2lithium ion battery is after disassembling, and selecting binding agent is the positive plate 100g of PVDF, is soaked in the NMP of 60 ℃, treats that active material powder separates with aluminum foil current collector, filter, and washing, vacuumize is recycled powder, and organic solvent NMP can be recycled after treatment.Above-mentioned powder is added to the water, pours separatory funnel into and leave standstill 30min, the acetylene black conductor side of floating on the water, positive electrode is sunken to bottom, and the powder of bottom is flowed out, and filters, dryly obtains positive electrode powder, and Fig. 2 is shown in by XRD collection of illustrative plates.ICP constituent analysis shows that this positive electrode chemical composition is containing lithium amount 7.01%, and nickel content is 20.90%, is 20.80% containing cobalt amount, and manganese content is 19.86%.
Embodiment 2
Positive electrode is Li (Ni
1/3co
1/3mn
1/3) O
2lithium ion battery is after disassembling, and selecting binding agent is the positive plate 100g of PTFE, N at 550 ℃
2in the tube-type atmosphere furnace of protection, process 3h, tail gas needs collection and treatment.After stove is cold, positive plate is taken out, mechanical friction makes active material separate with collector, adopts 400 mesh standard sieve screenings, extracting screen underflow, and heavy-fluid method separates, and obtains positive electrode powder X-ray RD collection of illustrative plates and sees Fig. 3.ICP constituent analysis shows that this positive electrode chemical composition is containing lithium amount 6.47%, and nickel content is 18.51%, is 18.73% containing cobalt amount, and manganese content is 19.30%.
Embodiment 3
The embodiment illustrated in fig. 21 positive electrode powder X-ray RD collection of illustrative plates that reclaims can be seen and α-NaFeO
2standard diffraction maximum correspondence, shows to reclaim positive electrode powder and still has typical α-NaFeO
2structure, belongs to
space group and hexagonal crystal system.In XRD collection of illustrative plates, can observe significantly (006)/(012) and division peak, (018)/(110), show to reclaim positive electrode powder and still there is good layer structure.Contrast its chemical composition and Li (Ni
1/3co
1/3mn
1/3) O
2theoretical composition, finds that lithium content has a small amount of loss, according to stoicheiometry, takes Li
2cO
3with recovery powder mixing and ball milling, Li/ (Ni+Co+Mn) mol ratio is 1.1:1, is then placed in 850 ℃ of Muffle furnace roasting 10h and repairs salvage materials.ICP constituent analysis shows to repair rear positive electrode powder chemistry composition for containing lithium amount 7.18%, and nickel content is 20.34%, is 20.24% containing cobalt amount, and manganese content is 19.06%, approaches with theoretical composition.By this reparation positive electrode, acetylene black and PVDF binding agent in mass ratio 85:10:5 evenly mix, be applied to and on aluminium foil, prepare positive plate.In the glove box of argon gas atmosphere by this positive plate, lithium sheet, the LiPF of barrier film and electrolyte 1mol/L
6vinyl carbonic ester (EC)-dimethyl carbonate (DMC) (volume ratio 1:1) solution, be assembled into CR2032 battery, carry out charge-discharge performance test.2.8-4.3V(vs Li/Li
+) in voltage range, with current density (0.1C) constant current charge-discharge of 18mA/g, Fig. 4 is cycle charge-discharge curve first.Can see that first discharge specific capacity is 160.3mAh/g, discharging efficiency is 88.9% first.Fig. 5 is 2.8 ~ 4.3V (vs Li/Li
+) in voltage range, with current density (1C) the discharge cycles performance curve of 180mA/g, the condition of discharging and recharging is that current density constant current charge to the voltage of 180mA/g is 4.3V, then 4.3V constant voltage charge, be less than 10mA/g to current density, take the current density constant-current discharge of 180mA/g to voltage as 2.8V, circulate 100 times again.Influenced by ambient temperature, specific capacity periodic undulations, except being subject to this fluctuating affects, impulse discharge efficiency is all more than 99.4%, and specific discharge capacity is 126.2mAh/g after 100 times, and capability retention is 94.3%.
Embodiment 4
Embodiment illustrated in fig. 32 reclaim positive electrode powder X-ray RD collection of illustrative plates shows that salvage material is also layer structure, but (006) peak dies down by force, and illustrative material lattice has confusion and defect, and the analysis means such as STEM also can prove this point.Chemical composition and theoretical value deviation are larger, part material undergoes phase transition, also may there is solution loss in transition metals cobalt and nickel, the mixed hydroxides of cobalt nickel is prepared in co-precipitation, then the mixed oxide of 900 ℃ of roasting generation cobalt nickel, according to chemical composition proportioning, take corresponding recovery positive electrode powder, cobalt nickel mixed oxide, be dissolved in finite concentration LiOH solution, Li/ (Ni+Co+Mn) mol ratio is 1.1:1,200 ℃ of hydro-thermal reaction 20h, filtration, oven dry obtain repairing positive electrode.The result of XRD shown in Fig. 6 shows, the strong grow in (006) peak after hydro-thermal reaction reparation, and salvage material has recovered good layer structure.Be assembled into button cell according to method described in embodiment 3, carry out electrochemical property test, Fig. 7 is 2.8 ~ 4.3V(vs Li/Li
+) in voltage range, with current density (0.1C) constant current charge-discharge of 18mA/g, cycle charge-discharge curve first, can see that first discharge specific capacity is 143.7mAh/g, discharging efficiency is 78.4% first.
Fig. 8 is in 2.8 ~ 4.3V (vs Li/Li+) voltage range, with current density (1C) the discharge cycles performance curve of 180mA/g, discharges and recharges condition identical with embodiment 3.The specific discharge capacity after 100 times that circulates is 125.6mAh/g, and capability retention is 98.8%.
Embodiment 5
Positive electrode is cobalt acid lithium (LiCoO
2) lithium ion battery is after disassembling, selecting binding agent is the positive plate 100g of PVDF, be soaked in the N of 80 ℃, in dinethylformamide, treat that active material powder separates with aluminum foil current collector, filter, washing, vacuumize is recycled powder, and organic solvent DMF can be recycled after treatment.Above-mentioned powder is added to the water, pours separatory funnel into and leave standstill 30min, the acetylene black conductor side of floating on the water, positive electrode is sunken to bottom, the powder of bottom is flowed out to filtration, the dry positive electrode powder that obtains.ICP constituent analysis shows that this positive electrode chemical composition is 6.46% containing lithium amount, is 61.35% containing cobalt amount.Contrast its chemical composition and LiCoO
2theoretical composition, finds that lithium content has a small amount of loss, according to stoicheiometry, takes Li
2cO
3with recovery positive electrode powder mixing and ball milling, Li/Co mol ratio is 1.05:1, is then placed in 750 ℃ of Muffle furnace roasting 20h and repairs salvage materials.ICP constituent analysis shows to repair rear positive electrode powder chemistry composition for containing lithium amount 7.06%, containing cobalt amount 59.82%, approaches with theoretical composition.
Embodiment 6
Positive electrode is cobalt acid lithium (LiCoO
2) lithium ion battery is after disassembling, selecting binding agent is the positive plate 100g of PVDF, be soaked in the N of 70 ℃, in dinethylformamide, treat that active material powder separates with aluminum foil current collector, filter, washing, vacuumize is recycled powder, and organic solvent DMF can be recycled after treatment.Above-mentioned powder is added to the water, pours separatory funnel into and leave standstill 30min, the acetylene black conductor side of floating on the water, positive electrode is sunken to bottom, the powder of bottom is flowed out to filtration, the dry positive electrode powder that obtains.ICP constituent analysis shows that this positive electrode chemical composition is 6.51% containing lithium amount, is 61.3% containing cobalt amount.Contrast its chemical composition and LiCoO
2theoretical composition, finds that lithium content has a small amount of loss, according to stoicheiometry, takes Li
2cO
3with recovery positive electrode powder mixing and ball milling, Li/Co mol ratio is 1.15:1, is then placed in 950 ℃ of Muffle furnace roasting 10h and repairs salvage materials.ICP constituent analysis shows to repair rear positive electrode powder chemistry composition for containing lithium amount 7.05%, is 60.1% containing cobalt amount, approaches with theoretical composition.
Embodiment 7
Positive electrode is cobalt acid lithium (LiCoO
2) lithium ion battery is after disassembling, selecting binding agent is the positive plate 100g of PTFE, N at 500 ℃
2in the tube-type atmosphere furnace of protection, process 5h, tail gas needs collection and treatment.After stove is cold, positive plate is taken out, mechanical friction makes active material separate with collector, adopts 400 mesh standard sieve screenings, and extracting screen underflow, obtains powder.Powder is added to the water, pours separatory funnel into and leave standstill 30min, the acetylene black conductor side of floating on the water, positive electrode is sunken to bottom, the powder of bottom is flowed out to filtration, the dry positive electrode powder that obtains.ICP constituent analysis shows that this positive electrode chemical composition is 6.12% containing lithium amount, is 56.8% containing cobalt amount., contrast its chemical composition and theoretical value deviation is larger, there is solution loss in transition metals cobalt, it is carried out to STEM and XPS analysis, layer structure causes confusion and defect, prepares the hydroxide of cobalt, then the oxide of 900 ℃ of roasting generation cobalts, according to chemical composition proportioning, take corresponding recovery positive electrode powder, cobalt/cobalt oxide, is dissolved in finite concentration LiOH solution, making Li/Co mol ratio is 1.05:1,150 ℃ of hydro-thermal reaction 20h.Filtration, oven dry obtain repairing positive electrode.ICP constituent analysis shows to repair rear positive electrode powder chemistry composition for containing lithium amount 7.08%, is 59.9% containing cobalt amount, approaches with theoretical composition.
Embodiment 8
Positive electrode is cobalt acid lithium (LiCoO
2) lithium ion battery is after disassembling, selecting binding agent is the positive plate 100g of PTFE, N at 600 ℃
2in the tube-type atmosphere furnace of protection, process 2h, tail gas needs collection and treatment.After stove is cold, positive plate is taken out, mechanical friction makes active material separate with collector, adopts 400 mesh standard sieve screenings, and extracting screen underflow, obtains powder.Powder is added to the water, pours separatory funnel into and leave standstill 30min, the acetylene black conductor side of floating on the water, positive electrode is sunken to bottom, the powder of bottom is flowed out to filtration, the dry positive electrode powder that obtains.ICP constituent analysis shows that this positive electrode chemical composition is 6.11% containing lithium amount, is 56.8% containing cobalt amount.It is carried out to inefficacy mechanism judgement, contrast its chemical composition and theoretical value deviation is larger, part material undergoes phase transition, and solution loss also may occur transition metals cobalt, prepares the hydroxide of cobalt, then the oxide of 900 ℃ of roasting generation cobalts, according to chemical composition proportioning, take corresponding recovery positive electrode powder, cobalt/cobalt oxide, be dissolved in finite concentration LiOH solution, Li/Co mol ratio is 1.15:1,250 ℃ of hydro-thermal reaction 10h.Filtration, oven dry obtain repairing positive electrode.ICP constituent analysis shows to repair rear positive electrode powder chemistry composition for containing lithium amount 7.09%, is 60.0% containing cobalt amount, approaches with theoretical composition.
Embodiment 9
Positive electrode is Li (Ni
1/3co
1/3mn
1/3) O
2lithium ion battery is after disassembling, and selecting binding agent is the positive plate 100g of PVDF, is soaked in the NMP of 80 ℃, treats that active material powder separates with aluminum foil current collector, filter, and washing, vacuumize is recycled powder, and organic solvent NMP can be recycled after treatment.Above-mentioned powder is added to the water, pours separatory funnel into and leave standstill 30min, the acetylene black conductor side of floating on the water, positive electrode is sunken to bottom, the powder of bottom is flowed out to filtration, the dry positive electrode powder that obtains.ICP constituent analysis shows that this positive electrode chemical composition is containing lithium amount 7.01%, and nickel content is 20.90%, is 20.80% containing cobalt amount, and manganese content is 19.86%.It is carried out to inefficacy mechanism judgement, contrast its chemical composition and Li (Ni
1/3co
1/3mn
1/3) O
2theoretical composition, finds that lithium content has a small amount of loss, according to stoicheiometry, takes Li
2cO
3with recovery powder mixing and ball milling, Li/ (Ni+Co+Mn) mol ratio is 1.05:1, is then placed in 750 ℃ of Muffle furnace roasting 20h and repairs salvage materials.ICP constituent analysis shows to repair rear positive electrode powder chemistry composition for containing lithium amount 7.18%, and nickel content is 20.34%, is 20.24% containing cobalt amount, and manganese content is 19.06%, approaches with theoretical composition.
Embodiment 10
Positive electrode is Li (Ni
1/3co
1/3mn
1/3) O
2lithium ion battery is after disassembling, and selecting binding agent is the positive plate 100g of PVDF, is soaked in the NMP of 70 ℃, treats that active material powder separates with aluminum foil current collector, filter, and washing, vacuumize is recycled powder, and organic solvent NMP can be recycled after treatment.Above-mentioned powder is added to the water, pours separatory funnel into and leave standstill 30min, the acetylene black conductor side of floating on the water, positive electrode is sunken to bottom, the powder of bottom is flowed out to filtration, washing, the dry positive electrode powder that obtains.ICP constituent analysis shows that this positive electrode chemical composition is containing lithium amount 7.01%, and nickel content is 20.90%, is 20.80% containing cobalt amount, and manganese content is 19.86%.It is carried out to inefficacy mechanism judgement, contrast its chemical composition and Li (Ni
1/3co
1/3mn
1/3) O
2theoretical composition, finds that lithium and cobalt content have a small amount of loss, according to stoicheiometry, take Li
2cO
3, cobalt oxide and reclaim positive electrode powder mixing and ball milling, Li/ (Ni+Co+Mn) mol ratio is 1.15:1, is then placed in 950 ℃ of Muffle furnace roasting 10h and repairs salvage materials.ICP constituent analysis shows to repair rear positive electrode powder chemistry composition for containing lithium amount 7.18%, and nickel content is 20.34%, is 20.24% containing cobalt amount, and manganese content is 19.06%, approaches with theoretical composition.
Embodiment 11
Positive electrode is Li (Ni
1/3co
1/3mn
1/3) O
2lithium ion battery is after disassembling, and selecting binding agent is the positive plate 100g of PTFE, N at 500 ℃
2in the tube-type atmosphere furnace of protection, process 5h, tail gas needs collection and treatment.After stove is cold, positive plate is taken out, mechanical friction makes active material separate with collector, adopts 400 mesh standard sieve screenings, extracting screen underflow, and heavy-fluid method separates, and obtains positive electrode powder.ICP constituent analysis shows that this positive electrode chemical composition is containing lithium amount 6.27%, and nickel content is 17.57%, is 17.76% containing cobalt amount, and manganese content is 17.77%.Carry out inefficacy mechanism judgement, chemical composition and theoretical value deviation are larger, and solution loss also may occur for transition metals cobalt and nickel, and it is carried out to STEM and XPS analysis, and layer structure causes confusion and defect.The mixed hydroxides of cobalt nickel is prepared in co-precipitation, then the mixed oxide of 900 ℃ of roasting generation cobalt nickel, according to chemical composition proportioning, take corresponding recovery positive electrode powder, cobalt nickel mixed oxide, be dissolved in finite concentration LiOH solution, Li/ (Ni+Co+Mn) mol ratio is 1.05:1,150 ℃ of hydro-thermal reaction 20h, and filtration, oven dry obtain repairing positive electrode.ICP constituent analysis shows to repair rear positive electrode powder chemistry composition for containing lithium amount 7.19%, and nickel content is 19.28%, is 19.41% containing cobalt amount, and manganese content is 19.01%, approaches with theoretical composition.
Embodiment 12
Positive electrode is Li (Ni
1/3co
1/3mn
1/3) O
2lithium ion battery is after disassembling, and selecting binding agent is the positive plate 100g of PTFE, N at 600 ℃
2in the tube-type atmosphere furnace of protection, process 2h, tail gas needs collection and treatment.After stove is cold, positive plate is taken out, mechanical friction makes active material separate with collector, adopts 400 mesh standard sieve screenings, extracting screen underflow, and heavy-fluid method separates, and obtains positive electrode powder.ICP constituent analysis shows that this positive electrode chemical composition is containing lithium amount 6.25%, and nickel content is 17.89%, is 17.45% containing cobalt amount, and manganese content is 17.78%.Carry out inefficacy mechanism judgement, chemical composition and theoretical value deviation are larger, part material undergoes phase transition, also may there is solution loss in transition metals cobalt and nickel, the mixed hydroxides of cobalt nickel is prepared in co-precipitation, then the mixed oxide of 900 ℃ of roasting generation cobalt nickel, according to chemical composition proportioning, take corresponding recovery positive electrode powder, cobalt nickel mixed oxide, be dissolved in finite concentration LiOH solution, Li/ (Ni+Co+Mn) mol ratio is 1.15:1,250 ℃ of hydro-thermal reaction 10h, and filtration, oven dry obtain repairing positive electrode.ICP constituent analysis shows to repair rear positive electrode powder chemistry composition for containing lithium amount 7.15%, and nickel content is 20.05%, is 20.44% containing cobalt amount, and manganese content is 18.79%, approaches with theoretical composition.
Applicant's statement, the present invention illustrates detailed method of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed method, does not mean that the present invention must rely on above-mentioned detailed method and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of auxiliary element, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a method that directly reclaims and repair waste lithium ion cell anode material, is characterized in that, described method comprises the steps:
(1) disassemble, to obtain positive electrode be cobalt acid lithium or the positive plate of the polynary layered oxide of lithium nickel cobalt manganese or positive plate leftover pieces and the defect ware of battery production producer in sorting;
(2) remove successively binding agent, collector and conductive agent, obtain positive electrode powder;
(3) the positive electrode powder inefficacy mechanism that research step (2) obtains, check positive electrode powder chemistry composition, when inefficacy mechanism is the loss of lithium and transition metal, when layer structure remains intact, carry out step (4), when inefficacy mechanism is transition metal valence transition, cause phase transformation, when layer structure causes confusion with defect, carry out step (4 ');
(4) according to the composition of positive electrode before losing efficacy, in the positive electrode powder obtaining in step (2), sneak into the compound of the metal of loss, sintering obtains the positive electrode of repairing;
(4 '), according to the composition of positive electrode before losing efficacy, sneaks into the transition metal oxide of solution loss in step (2) in the positive electrode powder obtaining, add the LiOH aqueous solution fully to stir, and hydro-thermal reaction obtains the positive electrode of repairing.
2. the method for claim 1, is characterized in that, in the time that the binding agent in positive plate is PTFE, adopts high-temperature decomposition, makes binder decomposed, separates with collector thereby realize positive electrode, reaches the object of removing binding agent and collector;
Preferably, by positive plate high-temperature roasting under inert atmosphere, PTFE is decomposed, positive plate after roasting is taken out, and mechanical friction makes positive electrode separate with collector, screening, remove the collector existing in positive electrode, obtain the mixed-powder of positive electrode and conductive agent.
3. method as claimed in claim 2, is characterized in that, described high-temperature roasting is carried out under inert atmosphere, and the temperature of high-temperature roasting is 500 ~ 600 ℃, preferably 500 ~ 550 ℃;
Preferably, the time of described high-temperature roasting is 2 ~ 5h, preferably 2.3 ~ 4.5h, further preferred 3h.
4. the method for claim 1, is characterized in that, in the time that the binding agent in positive plate is PVDF, adopts solvent soaking to dissolve and makes adhesive failure, thereby realize separating of positive electrode and collector, reaches the object of removing binding agent and collector;
Preferably, soak temperature while dissolving and be controlled at 60 ~ 80 ℃, preferably 61.5 ~ 78.5 ℃;
Preferably, described solvent is selected from 1-METHYLPYRROLIDONE, DMF, DMA or dimethyl sulfoxide (DMSO) the mixture of any one or at least two kinds, preferably 1-METHYLPYRROLIDONE;
Preferably, described solvent reuses by decompression distillation.
5. the method as described in one of claim 1-4, is characterized in that, adopts heavy liquid separation method to remove the conductive agent in positive plate, filters washing, the dry positive electrode powder that obtains;
Preferably, select water as density the heavy-fluid between conductive agent and positive electrode.
6. method as claimed in claim 5, it is characterized in that, the method that heavy liquid separation method is removed the conductive agent in positive plate is: positive electrode and the conductive agent mixed-powder of removing binding agent and collector are added to the water, stir, leave standstill, density is less than the conductive agent side of floating on the water of water, the positive electrode that density is greater than water sinks to side under water, the positive electrode that is sunken to bottom is flowed out, filter, the dry positive electrode powder that obtains.
7. the method as described in one of claim 1-6, in step (4), in positive electrode powder, sneak into the compound of the metal of loss, making Li/ (Ni+Co+Mn) mol ratio is 1.05 ~ 1.15:1, preferably 1.08 ~ 1.12:1, further preferred 1.1:1, in the time that positive electrode is cobalt acid lithium, n (Ni) and n (Mn) are 0.
8. the method as described in one of claim 1-7, is characterized in that, described sintering temperature is 750 ~ 950 ℃, preferably 770 ~ 930 ℃, and further preferably 750 ~ 870 ℃, most preferably 850 ℃;
Preferably, described roasting time is 10 ~ 20h, preferably 10.8 ~ 19.7h, further preferred 11.2 ~ 18.8h;
Preferably, in step (4), in positive electrode powder, sneak into the compound of the metal of loss, making Li/ (Ni+Co+Mn) mol ratio is 1.05 ~ 1.15:1,850 ℃ of sintering 10 ~ 20h obtain the positive electrode of repairing, in the time that positive electrode is cobalt acid lithium, n (Ni) and n (Mn) are 0.
9. the method as described in one of claim 1-8, it is characterized in that, in step (4 '), in positive electrode powder, sneak into the transition metal oxide of solution loss, add the LiOH aqueous solution fully to stir, making Li/ (Ni+Co+Mn) mol ratio is 1.05 ~ 1.15:1, preferably 1.08 ~ 1.12:1, further preferred 1.1:1, in the time that positive electrode is cobalt acid lithium, n (Ni) and n (Mn) are 0;
Preferably, the temperature of described hydro-thermal reaction is 150 ~ 250 ℃, preferably 160 ~ 240 ℃, and further preferably 170 ~ 230 ℃, most preferably 200 ℃;
Preferably, the time of described hydro-thermal reaction is 10 ~ 20h, preferably 10.8 ~ 19.7h, further preferably 11.2 ~ 18.8h, most preferably 15h.
10. the method as described in one of claim 1-9, it is characterized in that, in step (4 '), in positive electrode powder, sneak into the transition metal oxide of solution loss, add the LiOH aqueous solution fully to stir, making Li/ (Ni+Co+Mn) mol ratio is 1.05 ~ 1.15:1, moves into autoclave, hydro-thermal reaction 15h at 200 ℃, obtain the positive electrode of repairing, in the time that positive electrode is cobalt acid lithium, n (Ni) and n (Mn) are 0.
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