CN106992328A - The waste lithium iron phosphate positive electrode method that recycling is recycled in Hawkins cell - Google Patents
The waste lithium iron phosphate positive electrode method that recycling is recycled in Hawkins cell Download PDFInfo
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- CN106992328A CN106992328A CN201610041754.0A CN201610041754A CN106992328A CN 106992328 A CN106992328 A CN 106992328A CN 201610041754 A CN201610041754 A CN 201610041754A CN 106992328 A CN106992328 A CN 106992328A
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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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- 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
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/248—Iron electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/26—Processes of manufacture
- H01M4/28—Precipitating active material on the carrier
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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 kind of waste lithium iron phosphate positive electrode method that recycling is recycled in Hawkins cell, belong to waste and old lithium ion battery lithium iron phosphate positive material recovery technology and alkaline secondary cell field.Technical scheme main points are：The waste lithium iron phosphate positive electrode method that recycling is recycled in Hawkins cell, using waste lithium iron phosphate positive electrode as raw material, by saturation iron salt solutions add it is mixed it is uniform after LiFePO4 based composites are made by calcination processing under an inert atmosphere, then the LiFePO4 based composites are used to prepare Hawkins cell negative pole.The present invention can realize the recycling of waste lithium iron phosphate material with high efficiente callback waste and old lithium ion battery LiFePO 4 material and for iron nickel secondary batteries negative pole.
Description
Technical field
The invention belongs to waste and old lithium ion battery lithium iron phosphate positive material recovery technology and alkaline secondary cell field, and in particular to a kind of waste lithium iron phosphate positive electrode method that recycling is recycled in Hawkins cell.
Background technology
In the last few years, the continuous support on policy of the Chinese government, the progressively reinforcement of society environmental consciousness are had benefited from, and domestic a collection of colleges and universities, the ongoing effort of R＆D institution and enterprise in terms of the research and development in terms of electrokinetic cell, battery management system, the electric automobile market of China is developed rapidly.With the quick industrialization of new energy car, its sales volume will advance by leaps and bounds, and the recoverable amount of lithium-ion-power cell will also increase by geometric progression therewith.And at the same time, the problem of problem of environmental pollution and reasonable resource of applying waste lithium ionic electrokinetic cell are recycled is as current or even domestic and international common concern from now on and problem urgently to be resolved hurrily.The solution of the problem not only contributes to the protection of environment, is more beneficial for recycling for resource, is of great immediate significance.
In the last few years, both at home and abroad to waste and old electrokinetic cell recovery technology pay attention to day by day, and correlative study is gradually carried out.Lithium ion battery type is different, and its recovery method is also variant.Because waste lithium iron phosphate material does not contain the precious metals such as cobalt nickel, its recycle value it is relatively low, no economic benefit is reclaimed using existing cobalt acid lithium recovery process, for waste lithium iron phosphate material recovery technique research still in development.According to current document report, waste and old LiFePO4The recovery method of battery mainly has two major classes, and one kind is hydrometallurgical, and another is reparative regeneration method.Hydrometallurgical processes are to abolish metal battery case using mechanical means, after take the methods such as leaching, precipitation, ion exchange, absorption to obtain metallic compound, it is higher that it reclaims obtained metal degree of purity, but use substantial amounts of acid, alkali, not only cost is high, and easily causes secondary pollution.Importantly, LiFePO4Without cobalt in battery, the noble element such as nickel reclaims merely certain element economic benefit not high.Therefore hydrometallurgical reclaims lithium iron phosphate dynamic battery and not applied to extremely, the main stream approach that reparative regeneration method is handled into current waste lithium iron phosphate battery, with very high recovery benefit, comprehensive resource utilization rate highest.
Reparative regeneration method generally includes following steps：The waste lithium iron phosphate battery being recovered to is disassembled first, separated positive electrode with pole plate using physical method or chemical means.Add sodium hydroxide solution and remove aluminium remaining in LiFePO 4 material, heat treatment afterwards removes remaining conductive agent and binding agent.The mol ratio of iron, lithium, phosphorus is adjusted to 1 by addition appropriate source of iron, lithium source or P source compound:1:1.Carbon source is eventually adding, new lithium iron phosphate positive material is obtained through being calcined in ball milling, inert atmosphere.It can successfully pass simple supplement lithium and ferro element to repair positive electrode in spite of document report, and these tests are generally all half-cell tests, and cycle-index is shorter.Inventor once carried out research to the method for solid phase reparation and hydro-thermal reparation, it is found that this method is difficult to realize repairing again completely for the electro-chemical activity of positive electrode, reason is as follows：Situation when reclaiming the positive electrode come due to using is different（Including cycle-index and whether there is and indiscriminate fill indiscriminate put and use）, the nature difference of salvage material can be caused very big（Including particle diameter, processing characteristics, specific surface area, carbon content etc.）.It is well known that lithium iron phosphate dynamic battery requires higher generally for each side technical indicator of positive electrode, its simple reparative regeneration is reused for electrokinetic cell, inventor is considered difficult to realize.Therefore, develop new waste and old lithium ion battery lithium iron phosphate positive material recovery and reuse technology particularly important, can not only economize on resources, reduce cost, and can be with environmental protection.
The content of the invention
Present invention solves the technical problem that there is provided a kind of waste lithium iron phosphate positive electrode method that recycling is recycled in Hawkins cell, this method technique is simple, reusing for LiFePO 4 material in waste and old lithium iron battery is realized, resource consumption is efficiently reduced, battery use cost is reduced.
The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, the waste lithium iron phosphate positive electrode method that recycling is recycled in Hawkins cell, it is characterised in that：Using waste lithium iron phosphate positive electrode as raw material, by saturation iron salt solutions add it is mixed it is uniform after LiFePO4 based composites are made by calcination processing under an inert atmosphere, then the LiFePO4 based composites are used to prepare Hawkins cell negative pole.
The waste lithium iron phosphate positive electrode of the present invention method that recycling is recycled in Hawkins cell, it is characterised in that comprise the following steps：
（1）Dipping pretreatment, the positive plate separated from waste and old lithium ion battery is soaked 10-60 minutes in alkali lye, then rinsed 10-60 minutes in deionized water；
（2）Precalcining is separated, and the positive plate after dipping pretreatment is calcined 0.5-3 hours under 400-550 DEG C of hot conditions, positive active material is separated with aluminium foil, is dried, and grinding obtains positive active material after screening；
（3）Saturation ferrous solution mixed processing, soluble ferric iron salt is dissolved in deionized water and is made into molysite saturated solution, and molysite saturated solution is added in the way of spraying in the positive active material being stirred continuously, and is well mixed；
（4）Secondary clacining processing, by step（3）Obtained mixture after 550-800 DEG C of high-temperature process 1-4 hours, is crushed under inert gas shielding, LiFePO 4 material is obtained after screening；
（5）The preparation of active material slurry, the conductive agent that the additive and percentage by weight that the LiFePO 4 material for being 50%-85% by percentage by weight, percentage by weight are 10%-40% are 3%-10% is well mixed, it is then added in adhesive solution of the percentage by weight for 1%-3% binder making, stir, active material slurry is made；
（6）The preparation of iron phosphate lithium electrode, obtained active material slurry is coated on negative pole matrix, and by drying, tabletting, the iron phosphate lithium electrode for Hawkins cell negative pole is made in punching, soldering polar ear.
Further limit, step（1）Described in alkali lye for molar concentration be respectively one or more in 0.05-1mol/L sodium hydroxide solution, potassium hydroxide solution or lithium hydroxide solution.
Further limit, step（3）Described in soluble ferric iron salt be ferric nitrate, ferrous sulfate, ferrous acetate, iron ammonium sulfate or frerrous chloride in one or more.
Further limit, step（3）Described in soluble ferric iron salt and positive active material mass ratio be 0.05-1:1.
Further limit, step（4）Described in additive be nickel sulfate, at least two in nickel sulfide, the sub- cobalt of vulcanization, bismuth oxide, bismuth sulfide, ferrous sulfide, carbonyl iron dust, ferroso-ferric oxide, zinc oxide, yittrium oxide, erbium oxide, stannous oxide, ceria, titanium dioxide or chopped fiber.
Further limit, step（4）Described in conductive agent for electrically conductive graphite, Ketjen black, conductive black, CNT, graphene or oxidation titanous in one or more.
Further limit, step（4）Described in binding agent be polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, butadiene-styrene rubber, polyvinyl alcohol or hydroxypropyl methyl cellulose in one or more.
Further limit, step（5）Described in negative pole matrix be perforated steel ribbon, 3 D stereo steel band, stainless (steel) wire, Foamed Nickel, foam copper, foaming iron or copper mesh.
The present invention has the advantages that compared with prior art：The present invention innovatively regard the waste lithium iron phosphate material of recovery as presoma, handled by the uniform cladding of molysite saturated solution, utilize carbon material unnecessary in presoma, by high-temperature process, synthesize the composite for suitably doing alkaline secondary cell negative electrode, so as to realize that the material resourcesization are recycled.The technique is simple, it is easy to large-scale industrial production, and material recovery cost is low, and the rate of recovery is high, excellent performance.The present invention not only proposes the new recovery scheme of waste lithium iron phosphate material, and provides a kind of negative pole of excellent electrical property for alkaline secondary cell.The composite of recovery has excellent electro-chemical activity and cyclic reversibility, and 0.2C discharge capacities reach more than 300mAh/g, and 5C discharge capacities reach more than 260mAh/g, and capability retention is more than 90.0% after lower 200 circulations of 1C multiplying powers.
Embodiment
The above of the invention is described in further details by the following examples, but this should not be interpreted as to the scope of above-mentioned theme of the invention and is only limitted to following embodiment, all technologies realized based on the above of the present invention belong to the scope of the present invention.
Embodiment 1
The preparation of LiFePO4 based composites：The iron phosphate lithium positive pole piece isolated from waste and old lithium ion battery is soaked 20 minutes in molar concentration is 0.2mol/L sodium hydroxide solution successively, rinsed 10 minutes in deionized water, then in a nitrogen atmosphere, calcined 2 hours under 450 DEG C of hot conditions, positive active material is set to be separated with aluminium foil, dry, grinding obtains pretreated LiFePO 4 material after screening；1000 grams of the LiFePO 4 material of receipts is fetched, 100 grams of ferric nitrates are dissolved in deionized water and are made into molysite saturated solution, molysite saturated solution is added in the way of spraying in the pretreated LiFePO 4 material being stirred continuously, is well mixed；By the mixture of gained under nitrogen protection after 600 DEG C of high-temperature process 2 hours, crushed after cooling, LiFePO4 based composites are obtained after screening.
The preparation of LiFePO4 based composites negative pole：The LiFePO4 based composites for being first 68% by percentage by weight, percentage by weight are 19% additive（Weight percent is that 10% ferroso-ferric oxide, percentage by weight are that 5% bismuth sulfide, percentage by weight are 2% ferrous sulfide and percentage by weight is 2% zinc oxide）It is that 10% electrically conductive graphite mechanical mixture uniformly obtains negative material mixture with percentage by weight；Then negative material mixture is added in percentage by weight is the adhesive solution that 3% polyvinyl alcohol is prepared, stirs, active material slurry is made；Then obtained active material slurry is coated in foaming Ni substrate two sides, by drying, tabletting, iron phosphate lithium electrode is made in punching, soldering polar ear.
Electric performance test：To examine the electrical property of LiFePO4 based composites made from the present embodiment, with iron phosphate lithium electrode obtained above as negative pole, using sintered nickel electrode as positive pole, with 6M potassium hydroxide solutions（Na containing 0.1M2S and 0.4M LiOH）For electrolyte, positive and negative interpolar places polyalkene diaphragm, is prepared into iron nickel simulated battery, has carried out related charge-discharge test.Battery is charged 6 hours with 0.2C, is stopped 20 minutes, and the gram volume that active material in iron electrode is calculated to 0.8V is put with 0.2C, 1C or 5C.Test result shows that the iron nickel simulated battery 0.2C charge efficiencies reach that 91.2%, 0.2C discharge capacities are more than 316mAh/g, and 5C discharge capacities reach 279mAh/g；Capability retention is 95.2% after lower 200 circulations of 1C multiplying powers.
Embodiment 2
The preparation of LiFePO4 based composites：The iron phosphate lithium positive pole piece isolated from waste and old lithium ion battery is soaked 15 minutes in molar concentration is 0.05mol/L sodium hydroxide solution successively, rinsed 15 minutes in deionized water, then in a nitrogen atmosphere, calcined 1.5 hours under 550 DEG C of hot conditions, positive active material is set to be separated with aluminium foil, dry, grinding obtains pretreated LiFePO 4 material after screening；1000 grams of the LiFePO 4 material of receipts is fetched, 200 grams of ferrous sulfate are dissolved in deionized water and are made into molysite saturated solution, molysite saturated solution is added in the way of spraying in the pretreated LiFePO 4 material being stirred continuously, is well mixed；By the mixture of gained under nitrogen protection after 700 DEG C of high-temperature process 1 hour, crushed after cooling, LiFePO4 based composites are obtained after screening.
The preparation of LiFePO4 based composites negative pole：The LiFePO4 based composites for being first 60% by percentage by weight, percentage by weight are 30% additive（Percentage by weight is that 15% ferrous sulfide, percentage by weight are that 8% ferroso-ferric oxide, percentage by weight are that 4% nickel sulfate, percentage by weight are 2% yittrium oxide and percentage by weight is 1% stannous oxide）It is that 7% Ketjen black mechanical mixture uniformly obtains negative material mixture with percentage by weight；Then it is 3% binding agent negative material mixture to be added to by percentage by weight（Percentage by weight is 2.5% hydroxypropyl methyl cellulose and percentage by weight is 0.5% polytetrafluoroethylene (PTFE)）In the adhesive solution of preparation, stir, active material slurry is made；Then obtained active material slurry is coated in perforated steel ribbon two sides by slurry, by drying, tabletting, iron phosphate lithium electrode is made in punching, soldering polar ear.
Electric performance test：To examine the electrical property of LiFePO4 based composites made from the present embodiment, with iron phosphate lithium electrode obtained above as negative pole, using sintered nickel electrode as positive pole, with 6M potassium hydroxide solutions（Na containing 0.1M2S and 0.4M LiOH）For electrolyte, positive and negative interpolar places polyalkene diaphragm, prepares iron nickel simulated battery, carried out related charge-discharge test.Battery is charged 6 hours with 0.2C, is stopped 20 minutes, and the gram volume that active material in iron electrode is calculated to 0.8V is put with 0.2C, 1C or 5C.Test result shows that the iron nickel simulated battery 0.2C charge efficiencies reach that 91.2%, 0.2C discharge capacities are more than 312mAh/g, and 5C discharge capacities reach 249mAh/g；Capability retention is 96.5% after lower 200 circulations of 1C multiplying powers.
Embodiment 3
The preparation of LiFePO4 based composites：The iron phosphate lithium positive pole piece isolated from waste and old lithium ion battery is soaked 30 minutes in molar concentration is 0.1mol/L sodium hydroxide solution successively, rinsed 20 minutes in deionized water, then in a nitrogen atmosphere, calcined 1 hour under 500 DEG C of hot conditions, positive active material is set to be separated with aluminium foil, dry, grinding obtains pretreated LiFePO 4 material after screening；1000 grams of the LiFePO 4 material of receipts is fetched, 300 grams of ferrous acetates are dissolved in deionized water and are made into molysite saturated solution, molysite saturated solution is added in the way of spraying in the pretreated LiFePO 4 material being stirred continuously, is well mixed；By the mixture of gained under nitrogen protection after 600 DEG C of high-temperature process 2 hours, crushed after cooling, LiFePO4 based composites are obtained after screening.
The preparation of LiFePO4 based composites negative pole：The LiFePO4 based composites for being first 75% by percentage by weight, percentage by weight are 15% additive（Percentage by weight is that 10% ferrous sulfide, percentage by weight are 4% bismuth sulfide and percentage by weight is 1% ceria）It is that 7% electrically conductive graphite mechanical mixture uniformly obtains negative material mixture with percentage by weight；Then it is 3% binding agent negative material mixture to be added to by percentage by weight（Percentage by weight is 2.5% sodium carboxymethylcellulose and percentage by weight is 0.5% polytetrafluoroethylene (PTFE)）In the adhesive solution of preparation, stir, active material slurry is made；Then obtained active material slurry is coated in foaming iron two sides, by drying, tabletting, iron phosphate lithium electrode is made in punching, soldering polar ear.
Electric performance test：To examine the electrical property of LiFePO4 based composites made from the present embodiment, with iron phosphate lithium electrode obtained above as negative pole, positive pole is done with sintered nickel electrode, with 6M potassium hydroxide solutions（Na containing 0.1M2S and 0.4M LiOH）For electrolyte, positive and negative interpolar places polyalkene diaphragm, prepares iron nickel simulated battery, carried out related charge-discharge test.Battery is charged 6 hours with 0.2C, is stopped 20 minutes, and the gram volume that active material in iron electrode is calculated to 0.8V is put with 0.2C, 1C or 5C.Test result shows that iron nickel simulated battery 0.2C discharge capacities are more than 302mAh/g, and 5C discharge capacities reach 268mAh/g；Capability retention is 93.5% after lower 200 circulations of 1C multiplying powers.
Embodiment 4
The preparation of LiFePO4 based composites：The iron phosphate lithium positive pole piece isolated from waste and old lithium ion battery is soaked 10 minutes in molar concentration is 0.1mol/L sodium hydroxide solution successively, rinsed 10 minutes in deionized water, then in a nitrogen atmosphere, calcined 1 hour under 500 DEG C of hot conditions, positive active material is set to be separated with aluminium foil, dry, grinding obtains pretreated LiFePO 4 material after screening；1000 grams of the LiFePO 4 material of receipts is fetched, 500 grams of ferrous sulfate are dissolved in deionized water and are made into molysite saturated solution, molysite saturated solution is added in the way of spraying in the pretreated LiFePO 4 material being stirred continuously, is well mixed；By the mixture of gained under nitrogen protection after 700 DEG C of high-temperature process 2 hours, crushed after cooling, LiFePO4 based composites are obtained after screening.
The preparation of LiFePO4 based composites negative pole：The LiFePO4 based composites for being first 80% by percentage by weight, percentage by weight are 10% additive（Percentage by weight is that 5% ferroso-ferric oxide, percentage by weight are that 1% titanium oxide, percentage by weight are 1% nickel sulfide and percentage by weight is 2% erbium oxide）It is that 8% electrically conductive graphite mechanical mixture uniformly obtains negative material mixture with percentage by weight；Then it is 2% binding agent negative material mixture to be added to by percentage by weight（Percentage by weight is 1.5% hydroxypropyl methyl cellulose and percentage by weight is 0.5% butadiene-styrene rubber）In the adhesive solution of preparation, stir, active material slurry is made；Then obtained active material slurry is coated in foaming Copper substrate two sides, by drying, tabletting, iron phosphate lithium electrode is made in punching, soldering polar ear.
Electric performance test：To examine the electrical property of LiFePO4 based composites made from the present embodiment, with iron phosphate lithium electrode obtained above as negative pole, using sintered nickel electrode as positive pole, with 6M potassium hydroxide solutions（Na containing 0.1M2S and 0.4M LiOH）For electrolyte, positive and negative interpolar places polyalkene diaphragm, prepares iron nickel simulated battery, carried out related charge-discharge test.Battery is charged 6 hours with 0.2C, is stopped 20 minutes, and the gram volume that active material in iron electrode is calculated to 0.8V is put with 0.2C, 1C or 5C.Test result shows that iron nickel simulated battery 0.2C discharge capacities are more than 326mAh/g, and 5C discharge capacities reach 289mAh/g；Capability retention is 94.9% after lower 200 circulations of 1C multiplying powers.
Embodiment 5
The preparation of LiFePO4 based composites：The iron phosphate lithium positive pole piece isolated from waste and old lithium ion battery is soaked 10 minutes in molar concentration is 1.0mol/L sodium hydroxide solution successively, rinsed 30 minutes in deionized water, then in a nitrogen atmosphere, calcined 1 hour under 500 DEG C of hot conditions, positive active material is set to be separated with aluminium foil, dry, grinding obtains pretreated LiFePO 4 material after screening；1000 grams of the LiFePO 4 material of receipts is fetched, 350 grams of ferric sulfate solutions are made into molysite saturated solution in deionized water, molysite saturated solution is added in the way of spraying in the pretreated LiFePO 4 material being stirred continuously, is well mixed；By the mixture of gained under nitrogen protection after 550 DEG C of high-temperature process 2 hours, crushed after cooling, LiFePO4 based composites are obtained after screening.
The preparation of LiFePO4 based composites negative pole：The LiFePO4 based composites for being first 84% by percentage by weight, percentage by weight are 10.5% additive（Percentage by weight is that 3% bismuth oxide, percentage by weight are that 5% ferrous sulfide, percentage by weight are the sub- cobalt of 1% vulcanization and percentage by weight is 1.5% zinc oxide）It is that 3% conductive graphene mechanical mixture uniformly obtains negative material mixture with percentage by weight；Then it is 2.5% binding agent negative material mixture to be added to by percentage by weight（Percentage by weight is 2.0% sodium carboxymethylcellulose and percentage by weight is 0.5% polytetrafluoroethylene (PTFE)）In the adhesive solution of preparation, stir, active material slurry is made；Then obtained active material slurry is coated in 3 D stereo steel band two sides, by drying, tabletting, iron phosphate lithium electrode is made in punching, soldering polar ear.
Electric performance test：To examine the electrical property of LiFePO4 based composites made from the present embodiment, with iron phosphate lithium electrode obtained above as negative pole, using sintered nickel electrode as positive pole, with 6M potassium hydroxide solutions（Na containing 0.1M2S and 0.4M LiOH）For electrolyte, positive and negative interpolar places polyalkene diaphragm, prepares iron nickel simulated battery, carried out related charge-discharge test.Battery is charged 6 hours with 0.2C, is stopped 20 minutes, and the gram volume that active material in iron electrode is calculated to 0.8V is put with 0.2C, 1C or 5C.Test result shows that iron nickel simulated battery 0.2C discharge capacities are more than 296mAh/g, and 5C discharge capacities reach 269mAh/g；Capability retention is 95.2% after lower 200 circulations of 1C multiplying powers.
Embodiment above describes general principle, principal character and the advantage of the present invention; it should be understood by those skilled in the art that; the present invention is not limited to the above embodiments; merely illustrating the principles of the invention described in above-described embodiment and specification; under the scope for not departing from the principle of the invention; various changes and modifications of the present invention are possible, and these changes and improvements are each fallen within the scope of protection of the invention.
Claims (9)
1. the waste lithium iron phosphate positive electrode method that recycling is recycled in Hawkins cell, it is characterised in that：Using waste lithium iron phosphate positive electrode as raw material, by saturation iron salt solutions add it is mixed it is uniform after LiFePO4 based composites are made by calcination processing under an inert atmosphere, then the LiFePO4 based composites are used to prepare Hawkins cell negative pole.
2. the waste lithium iron phosphate positive electrode according to claim 1 method that recycling is recycled in Hawkins cell, it is characterised in that comprise the following steps：
（1）Dipping pretreatment, the positive plate separated from waste and old lithium ion battery is soaked 10-60 minutes in alkali lye, then rinsed 10-60 minutes in deionized water；
（2）Precalcining is separated, and the positive plate after dipping pretreatment is calcined 0.5-3 hours under 400-550 DEG C of hot conditions, positive active material is separated with aluminium foil, is dried, and grinding obtains positive active material after screening；
（3）Saturation ferrous solution mixed processing, soluble ferric iron salt is dissolved in deionized water and is made into molysite saturated solution, and molysite saturated solution is added in the way of spraying in the positive active material being stirred continuously, and is well mixed；
（4）Secondary clacining processing, by step（3）Obtained mixture after 550-800 DEG C of high-temperature process 1-4 hours, is crushed under inert gas shielding, LiFePO 4 material is obtained after screening；
（5）The preparation of active material slurry, the conductive agent that the additive and percentage by weight that the LiFePO 4 material for being 50%-85% by percentage by weight, percentage by weight are 10%-40% are 3%-10% is well mixed, it is then added in adhesive solution of the percentage by weight for 1%-3% binder making, stir, active material slurry is made；
（6）The preparation of iron phosphate lithium electrode, obtained active material slurry is coated on negative pole matrix, and by drying, tabletting, the iron phosphate lithium electrode for Hawkins cell negative pole is made in punching, soldering polar ear.
3. the waste lithium iron phosphate positive electrode according to claim 2 method that recycling is recycled in Hawkins cell, it is characterised in that：Step（1）Described in alkali lye for molar concentration be respectively one or more in 0.05-1mol/L sodium hydroxide solution, potassium hydroxide solution or lithium hydroxide solution.
4. the waste lithium iron phosphate positive electrode according to claim 2 method that recycling is recycled in Hawkins cell, it is characterised in that：Step（3）Described in soluble ferric iron salt be ferric nitrate, ferrous sulfate, ferrous acetate, iron ammonium sulfate or frerrous chloride in one or more.
5. the waste lithium iron phosphate positive electrode according to claim 2 method that recycling is recycled in Hawkins cell, it is characterised in that：Step（3）Described in soluble ferric iron salt and positive active material mass ratio be 0.05-1:1.
6. the waste lithium iron phosphate positive electrode according to claim 2 method that recycling is recycled in Hawkins cell, it is characterised in that：Step（4）Described in additive be nickel sulfate, at least two in nickel sulfide, the sub- cobalt of vulcanization, bismuth oxide, bismuth sulfide, ferrous sulfide, carbonyl iron dust, ferroso-ferric oxide, zinc oxide, yittrium oxide, erbium oxide, stannous oxide, ceria, titanium dioxide or chopped fiber.
7. the waste lithium iron phosphate positive electrode according to claim 2 method that recycling is recycled in Hawkins cell, it is characterised in that：Step（4）Described in conductive agent for electrically conductive graphite, Ketjen black, conductive black, CNT, graphene or oxidation titanous in one or more.
8. the waste lithium iron phosphate positive electrode according to claim 2 method that recycling is recycled in Hawkins cell, it is characterised in that：Step（4）Described in binding agent be polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, butadiene-styrene rubber, polyvinyl alcohol or hydroxypropyl methyl cellulose in one or more.
9. the waste lithium iron phosphate positive electrode according to claim 2 method that recycling is recycled in Hawkins cell, it is characterised in that：Step（5）Described in negative pole matrix be perforated steel ribbon, 3 D stereo steel band, stainless (steel) wire, Foamed Nickel, foam copper, foaming iron or copper mesh.
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| CN201610041754.0A CN106992328B (en) | 2016-01-21 | 2016-01-21 | The waste lithium iron phosphate positive electrode method that recycling recycles in Hawkins cell |
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Cited By (6)
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| CN107352524A (en) * | 2017-08-03 | 2017-11-17 | 清华大学 | A kind of recovery method of waste lithium iron phosphate positive electrode |
| CN109638228A (en) * | 2018-11-27 | 2019-04-16 | 扬州大学 | A kind of preparation method of Hawkins cell negative electrode material |
| CN110690446A (en) * | 2019-09-29 | 2020-01-14 | 蔚蓝(广东)新能源科技有限公司 | Preparation method of carbon-coated ferroferric oxide for iron-nickel battery |
| CN112599766A (en) * | 2020-12-14 | 2021-04-02 | 台州市宸明新能源科技有限公司 | Regeneration process of waste lithium iron phosphate battery positive electrode material |
| CN113716541A (en) * | 2021-07-28 | 2021-11-30 | 株洲冶炼集团股份有限公司 | High-carbon low-rate lithium iron phosphate decarburization reconstruction method |
| CN114975893A (en) * | 2022-05-16 | 2022-08-30 | 天能新能源(湖州)有限公司 | Preparation method of lithium iron phosphate positive plate for energy storage |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107352524A (en) * | 2017-08-03 | 2017-11-17 | 清华大学 | A kind of recovery method of waste lithium iron phosphate positive electrode |
| CN109638228A (en) * | 2018-11-27 | 2019-04-16 | 扬州大学 | A kind of preparation method of Hawkins cell negative electrode material |
| CN109638228B (en) * | 2018-11-27 | 2021-02-05 | 扬州大学 | Preparation method of iron-nickel battery negative electrode material |
| CN110690446A (en) * | 2019-09-29 | 2020-01-14 | 蔚蓝(广东)新能源科技有限公司 | Preparation method of carbon-coated ferroferric oxide for iron-nickel battery |
| CN112599766A (en) * | 2020-12-14 | 2021-04-02 | 台州市宸明新能源科技有限公司 | Regeneration process of waste lithium iron phosphate battery positive electrode material |
| CN113716541A (en) * | 2021-07-28 | 2021-11-30 | 株洲冶炼集团股份有限公司 | High-carbon low-rate lithium iron phosphate decarburization reconstruction method |
| CN114975893A (en) * | 2022-05-16 | 2022-08-30 | 天能新能源(湖州)有限公司 | Preparation method of lithium iron phosphate positive plate for energy storage |
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