CN106992328B - The waste lithium iron phosphate positive electrode method that recycling recycles in Hawkins cell - Google Patents

The waste lithium iron phosphate positive electrode method that recycling recycles in Hawkins cell Download PDF

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CN106992328B
CN106992328B CN201610041754.0A CN201610041754A CN106992328B CN 106992328 B CN106992328 B CN 106992328B CN 201610041754 A CN201610041754 A CN 201610041754A CN 106992328 B CN106992328 B CN 106992328B
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iron phosphate
waste
iron
positive electrode
lithium iron
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CN106992328A (en
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上官恩波
郭利坦
李晶
宁飒爽
王芹
李菲
常照荣
李全民
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Henan Hengming New Energy Co ltd
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Henan Normal University
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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
    • 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
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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 method that recycling that the invention discloses a kind of waste lithium iron phosphate positive electrodes in Hawkins cell recycles, belongs to waste and old lithium ion battery lithium iron phosphate positive material recovery technology and alkaline secondary cell field.Technical solution of the present invention main points are as follows: the waste lithium iron phosphate positive electrode method that recycling recycles in Hawkins cell, using waste lithium iron phosphate positive electrode as raw material, will saturation iron salt solutions be added it is mixed uniformly after under an inert atmosphere by calcination processing be made LiFePO4 based composites, the LiFePO4 based composites are then used to prepare Hawkins cell cathode.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 cathode.

Description

The waste lithium iron phosphate positive electrode method that recycling recycles in Hawkins cell
Technical field
The invention belongs to waste and old lithium ion battery lithium iron phosphate positive material recovery technology and alkaline secondary cell field, tools Body is related to a kind of waste lithium iron phosphate positive electrode method that recycling recycles in Hawkins cell.
Background technique
In recent years, have benefited from the continuous support on policy of the Chinese government, the gradually reinforcement of society environmental consciousness, and Domestic a batch colleges and universities, the ongoing effort of R&D institution and enterprise in terms of power battery, the research and development of battery management system etc., The electric automobile market in China is developed rapidly.With the quick industrialization of new energy vehicle, sales volume will advance by leaps and bounds, and The ownership of lithium-ion-power cell will also increase by geometric progression therewith.And at the same time, applying waste lithium ionic power battery Problem of environmental pollution and reasonable resourceization the problem of recycling become current or even domestic and international common concern from now on and urgently The problem of solution.The solution of the problem not only contributes to the protection of environment, is more advantageous to recycling for resource, has great Realistic meaning.
In recent years, both at home and abroad to waste and old power battery recovery technology pay attention to day by day, and gradually carry out correlative study.Lithium from Sub- battery types are different, and recovery method is also variant.Since waste lithium iron phosphate material does not contain the precious metals such as cobalt nickel, It is relatively low to recycle value, no economic benefit is recycled using existing cobalt acid lithium recovery process, for waste and old phosphoric acid The research of iron lithium material recovery process is still in development phase.According to current document report, waste and old LiFePO4The recycling of battery Method mainly has two major classes, and one is hydrometallurgical, another kind is reparative regeneration method.Hydrometallurgical processes are using machinery side Method abolishes metal battery case, after take the methods of leaching, precipitating, ion exchange, absorption to obtain metallic compound, recycle The metal degree of purity arrived is higher, but to use a large amount of acid, and alkali is not only at high cost, but also be easy to cause secondary pollution.It is more important , LiFePO4Cobalt is free of in battery, the noble elements such as nickel, recycling certain element merely, the economic benefit is not high.Therefore wet process smelting Golden method recycling lithium iron phosphate dynamic battery is extremely not applicable, the mainstream that reparative regeneration method is handled at current waste lithium iron phosphate battery Method has very high recycling benefit, comprehensive resource utilization rate highest.
Reparative regeneration method generally includes following steps: first disassembling the waste lithium iron phosphate battery being recovered to, uses object Reason method or chemical means separate positive electrode with pole plate.It is added remaining in sodium hydroxide solution removing LiFePO 4 material Aluminium, heat treatment removal later remaining conductive agent and binder.Add source of iron, lithium source or P source compound appropriate by iron, lithium, The molar ratio of phosphorus is adjusted to 1:1:1.It is eventually adding carbon source, obtains new iron phosphate lithium positive pole through calcining in ball milling, inert atmosphere Material.Simple supplement lithium and ferro element can be successfully passed in spite of document report to repair positive electrode, and these are tested It is usually all half-cell test, and cycle-index is shorter.Inventor once ground the method for solid phase reparation and hydro-thermal reparation To study carefully, discovery this method is difficult to realize repairing again completely for the electro-chemical activity of positive electrode, the reason is as follows that: recycle the anode come Situation when material is due to using is different (including cycle-index and whether there is or not fill to put excessively excessively to use), will cause salvage material Nature difference is very big (including partial size, processing performance, specific surface area, carbon content etc.).It is well known that lithium iron phosphate dynamic battery is logical Often the various aspects technical indicator of positive electrode is required higher, its simple reparative regeneration is reused for power battery, Inventor is considered difficult to realize.Therefore, new waste and old lithium ion battery lithium iron phosphate positive material recycling and reusing is developed Technology is particularly important, can not only economize on resources, and reduces cost, and can protect environment.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of waste lithium iron phosphate positive electrode resources in Hawkins cell Change the method recycled, this method simple process realizes the utilization again of LiFePO 4 material in waste and old lithium iron battery, effectively Ground reduces resource consumption, reduces battery operating cost.
The present invention adopts the following technical scheme that waste lithium iron phosphate positive electrode is in iron nickel electricity to solve above-mentioned technical problem The method that recycling recycles in pond, it is characterised in that: using waste lithium iron phosphate positive electrode as raw material, iron salt solutions will be saturated Be added it is mixed uniformly after under an inert atmosphere by calcination processing be made LiFePO4 based composites, then by the phosphoric acid Iron lithium based composites are used to prepare Hawkins cell cathode.
The waste lithium iron phosphate positive electrode of the present invention method that recycling recycles in Hawkins cell, feature Be the following steps are included:
(1) dipping pretreatment will impregnate 10-60 points from the positive plate separated in waste and old lithium ion battery in lye Then clock rinses 10-60 minutes in deionized water；
(2) precalcining separates, and the positive plate after dipping pretreatment is calcined 0.5-3 under 400-550 DEG C of hot conditions Hour, separate positive active material with aluminium foil, dry, grinding obtains positive active material after screening；
(3) it is saturated ferrous solution mixed processing, soluble ferric iron salt is dissolved in deionized water and is made into molysite saturated solution, and will Molysite saturated solution is added in the positive active material being stirred continuously in spraying mode, is uniformly mixed；
(4) secondary clacining is handled, and the mixture that step (3) obtains is passed through 550-800 DEG C of height under inert gas protection After temperature processing 1-4 hours, crushes, obtain LiFePO 4 material after screening；
(5) preparation of active material slurry, LiFePO 4 material, the weight percent for being 50%-85% by weight percent The conductive agent that additive and weight percent for 10%-40% are 3%-10% is uniformly mixed, and is then added to by weight percent It in adhesive solution for the binder making of 1%-3%, stirs evenly, active material slurry is made；
(6) active material slurry obtained is coated on cathode matrix by the preparation of iron phosphate lithium electrode, by drying, The iron phosphate lithium electrode for Hawkins cell cathode is made in tabletting, punching, soldering polar ear.
It further limits, lye as described in step (1) is molten for the sodium hydroxide that molar concentration is respectively 0.05-1mol/L One of liquid, potassium hydroxide solution or lithium hydroxide solution are a variety of.
It further limits, soluble ferric iron salt described in step (3) is ferric nitrate, ferrous sulfate, ferrous acetate, sulfuric acid Asia One of iron ammonium or frerrous chloride are a variety of.
It further limits, the mass ratio of soluble ferric iron salt described in step (3) and positive active material is 0.05-1:1.
It further limits, additive described in step (4) is nickel sulfate, nickel sulfide, vulcanizes sub- cobalt, bismuth oxide, vulcanization Bismuth, ferrous sulfide, carbonyl iron dust, ferroso-ferric oxide, zinc oxide, yttrium oxide, erbium oxide, stannous oxide, ceria, titanium dioxide At least two in titanium or staple fiber.
Further limit, conductive agent described in step (4) be electrically conductive graphite, Ketjen black, conductive black, carbon nanotube, One of graphene or oxidation titanous are a variety of.
Further limit, binder described in step (4) be polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, butadiene-styrene rubber, One of polyvinyl alcohol or hydroxypropyl methyl cellulose are a variety of.
It further limits, cathode matrix described in step (5) is perforated steel ribbon, 3 D stereo steel band, stainless (steel) wire, hair Steep nickel, foam copper, foaming iron or copper mesh.
Compared with the prior art, the invention has the following beneficial effects: the present invention is innovatively by the waste and old ferric phosphate of recycling Lithium material is handled as presoma by the uniform cladding of molysite saturated solution, using carbon material extra in presoma, is passed through High-temperature process, synthesizing is suitable for the composite material for doing alkaline secondary cell negative electrode, to realize that the material resourcesization recycle.It should Simple process is easy to large-scale industrial production, and material recovery is at low cost, and the rate of recovery is high, has excellent performance.The present invention not only proposes The new recovery scheme of waste lithium iron phosphate material, and for alkaline secondary cell provide a kind of cathode of excellent electrical property. The composite material of recycling has excellent electro-chemical activity and cyclic reversibility, and 0.2C discharge capacity reaches 300mAh/g or more, 5C discharge capacity reaches 260mAh/g or more, and capacity retention ratio is 90.0% or more after lower 200 circulations of 1C multiplying power.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair Bright range.
Embodiment 1
The preparation of LiFePO4 based composites: by the iron phosphate lithium positive pole piece isolated from waste and old lithium ion battery according to It is secondary to be impregnated 20 minutes in the sodium hydroxide solution that molar concentration is 0.2mol/L, it rinses 10 minutes in deionized water, then exists Under nitrogen atmosphere, is calcined 2 hours under 450 DEG C of hot conditions, separate positive active material with aluminium foil, dry, grinding, after screening Obtain pretreated LiFePO 4 material；100 grams of ferric nitrates are dissolved in deionization by 1000 grams of LiFePO 4 material for fetching receipts It is made into molysite saturated solution in water, molysite saturated solution is added to the pretreated phosphoric acid being stirred continuously in spraying mode In iron lithium material, it is uniformly mixed；By resulting mixture under nitrogen protection by 600 DEG C after high-temperature process 2 hours, after cooling It crushes, LiFePO4 based composites is obtained after screening.
The preparation of LiFePO4 based composites cathode: the iron phosphate lithium-based composite wood for being first 68% by weight percent Material, weight percent are that (weight percent is 10% ferroso-ferric oxide to 19% additive, weight percent is 5% bismuth sulfide, weight hundred Point than being 2% zinc oxide for 2% ferrous sulfide and weight percent) and weight percent be that 10% electrically conductive graphite mechanical mixture is uniform Obtain negative electrode material mixture；Then negative electrode material mixture is added to by weight percent is the viscous of 3% polyvinyl alcohol preparation It ties in agent aqueous solution, stirs evenly, active material slurry is made；Then it is Ni-based active material slurry obtained to be coated in foaming Body two sides, by drying, tabletting, punching, soldering polar ear, obtained iron phosphate lithium electrode.
Electric performance test: it for the electrical property for examining LiFePO4 based composites made from the present embodiment, is made with above-mentioned Iron phosphate lithium electrode as cathode, using sintered nickel electrode as anode, with 6M potassium hydroxide solution (Na containing 0.1M2S and 0.4M LiOH) it is electrolyte, positive and negative interpolar places polyalkene diaphragm, is prepared into iron nickel simulated battery, has carried out related charge and discharge Test.Battery was stopped 20 minutes with 0.2C charging 6 hours, is put with 0.2C, 1C or 5C to 0.8V, is calculated active material in iron electrode Gram volume.Test result shows that the iron nickel simulated battery 0.2C charge efficiency reaches 91.2%, 0.2C discharge capacity and is 316mAh/g or more, 5C discharge capacity reach 279mAh/g；Capacity retention ratio is 95.2% after lower 200 circulations of 1C multiplying power.
Embodiment 2
The preparation of LiFePO4 based composites: by the iron phosphate lithium positive pole piece isolated from waste and old lithium ion battery according to It is secondary to be impregnated 15 minutes in the sodium hydroxide solution that molar concentration is 0.05mol/L, it rinses 15 minutes in deionized water, then exists Under nitrogen atmosphere, is calcined 1.5 hours under 550 DEG C of hot conditions, separate positive active material with aluminium foil, it is dry, it grinds, screening After obtain pretreated LiFePO 4 material；1000 grams of LiFePO 4 material for fetching receipts, 200 grams of ferrous sulfate are dissolved in Molysite saturated solution is made into ionized water, molysite saturated solution is added in spraying mode be stirred continuously it is pretreated In LiFePO 4 material, it is uniformly mixed；It is cold by resulting mixture under nitrogen protection by 700 DEG C after high-temperature process 1 hour But it crushes afterwards, LiFePO4 based composites is obtained after screening.
The preparation of LiFePO4 based composites cathode: the iron phosphate lithium-based composite wood for being first 60% by weight percent Material, weight percent are that (weight percent is 15% ferrous sulfide to 30% additive, weight percent is 8% ferroso-ferric oxide, again Amount percentage is 4% nickel sulfate, weight percent is 2% yttrium oxide and weight percent is 1% stannous oxide) and weight percent Negative electrode material mixture is uniformly obtained for 7% Ketjen black mechanical mixture；Then negative electrode material mixture is added to by weight percent Than matching for 3% binder (weight percent is 2.5% hydroxypropyl methyl cellulose and weight percent is 0.5% polytetrafluoroethylene (PTFE)) It in the adhesive solution of system, stirs evenly, active material slurry is made；Then active material slurry obtained is passed through into slurry Coated in perforated steel ribbon two sides, by drying, tabletting, punching, soldering polar ear, obtained iron phosphate lithium electrode.
Electric performance test: it for the electrical property for examining LiFePO4 based composites made from the present embodiment, is made with above-mentioned Iron phosphate lithium electrode as cathode, using sintered nickel electrode as anode, with 6M potassium hydroxide solution (Na containing 0.1M2S and 0.4M LiOH) it is electrolyte, positive and negative interpolar places polyalkene diaphragm, prepares iron nickel simulated battery, carried out related charge and discharge electrical measurement Examination.Battery was stopped 20 minutes with 0.2C charging 6 hours, was put with 0.2C, 1C or 5C to 0.8V, and active material in iron electrode is calculated Gram volume.It is 312mAh/ that test result, which shows that the iron nickel simulated battery 0.2C charge efficiency reaches 91.2%, 0.2C discharge capacity, G or more, 5C discharge capacity reach 249mAh/g；Capacity retention ratio is 96.5% after lower 200 circulations of 1C multiplying power.
Embodiment 3
The preparation of LiFePO4 based composites: by the iron phosphate lithium positive pole piece isolated from waste and old lithium ion battery according to It is secondary to be impregnated 30 minutes in the sodium hydroxide solution that molar concentration is 0.1mol/L, it rinses 20 minutes in deionized water, then exists Under nitrogen atmosphere, is calcined 1 hour under 500 DEG C of hot conditions, separate positive active material with aluminium foil, dry, grinding, after screening Obtain pretreated LiFePO 4 material；1000 grams of LiFePO 4 material for fetching receipts, by 300 grams of ferrous acetates be dissolved in from It is made into molysite saturated solution in sub- water, molysite saturated solution is added to the pretreated phosphorus being stirred continuously in spraying mode In sour iron lithium material, it is uniformly mixed；It is cooling by resulting mixture under nitrogen protection by 600 DEG C after high-temperature process 2 hours After crush, LiFePO4 based composites are obtained after screening.
The preparation of LiFePO4 based composites cathode: the iron phosphate lithium-based composite wood for being first 75% by weight percent Material, weight percent are that (weight percent is 10% ferrous sulfide to 15% additive, weight percent is 4% bismuth sulfide and weight hundred Point ratio is 1% ceria) and weight percent be that 7% electrically conductive graphite mechanical mixture uniformly obtains negative electrode material mixture；Then By negative electrode material mixture be added to by weight percent be 3% binder (weight percent be 2.5% sodium carboxymethylcellulose and Weight percent be 0.5% polytetrafluoroethylene (PTFE)) prepare adhesive solution in, stir evenly, active material slurry be made；So Active material slurry obtained is coated in foaming iron two sides afterwards, by drying, tabletting, punching, soldering polar ear, obtained ferric phosphate Lithium electrode.
Electric performance test: it for the electrical property for examining LiFePO4 based composites made from the present embodiment, is made with above-mentioned Iron phosphate lithium electrode as cathode, anode is done with sintered nickel electrode, with 6M potassium hydroxide solution (Na containing 0.1M2S and 0.4M It LiOH) is electrolyte, positive and negative interpolar places polyalkene diaphragm, prepares iron nickel simulated battery, carried out related charge-discharge test.Electricity Pond was stopped 20 minutes with 0.2C charging 6 hours, was put with 0.2C, 1C or 5C to 0.8V, and gram appearance of active material in iron electrode is calculated Amount.Test result shows that the iron nickel simulated battery 0.2C discharge capacity is 302mAh/g or more, and 5C discharge capacity reaches 268mAh/g；Capacity retention ratio is 93.5% after lower 200 circulations of 1C multiplying power.
Embodiment 4
The preparation of LiFePO4 based composites: by the iron phosphate lithium positive pole piece isolated from waste and old lithium ion battery according to It is secondary to be impregnated 10 minutes in the sodium hydroxide solution that molar concentration is 0.1mol/L, it rinses 10 minutes in deionized water, then exists Under nitrogen atmosphere, is calcined 1 hour under 500 DEG C of hot conditions, separate positive active material with aluminium foil, dry, grinding, after screening Obtain pretreated LiFePO 4 material；1000 grams of LiFePO 4 material for fetching receipts, by 500 grams of ferrous sulfate be dissolved in from It is made into molysite saturated solution in sub- water, molysite saturated solution is added to the pretreated phosphorus being stirred continuously in spraying mode In sour iron lithium material, it is uniformly mixed；It is cooling by resulting mixture under nitrogen protection by 700 DEG C after high-temperature process 2 hours After crush, LiFePO4 based composites are obtained after screening.
The preparation of LiFePO4 based composites cathode: the iron phosphate lithium-based composite wood for being first 80% by weight percent Material, weight percent are that (weight percent is 5% ferroso-ferric oxide to 10% additive, weight percent is 1% titanium oxide, weight hundred Point than being 1% nickel sulfide and weight percent is 2% erbium oxide) and weight percent be that 8% electrically conductive graphite mechanical mixture uniformly obtains Negative electrode material mixture；Then negative electrode material mixture is added to by weight percent is that (weight percent is 2% binder 1.5% hydroxypropyl methyl cellulose and weight percent are 0.5% butadiene-styrene rubber) in the adhesive solution prepared, stir evenly, Active material slurry is made；Then active material slurry obtained 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: it for the electrical property for examining LiFePO4 based composites made from the present embodiment, is made with above-mentioned Iron phosphate lithium electrode as cathode, using sintered nickel electrode as anode, with 6M potassium hydroxide solution (Na containing 0.1M2S and 0.4M LiOH) it is electrolyte, positive and negative interpolar places polyalkene diaphragm, prepares iron nickel simulated battery, carried out related charge and discharge electrical measurement Examination.Battery was stopped 20 minutes with 0.2C charging 6 hours, was put with 0.2C, 1C or 5C to 0.8V, and active material in iron electrode is calculated Gram volume.Test result shows that the iron nickel simulated battery 0.2C discharge capacity is 326mAh/g or more, and 5C discharge capacity reaches 289mAh/g；Capacity retention ratio is 94.9% after lower 200 circulations of 1C multiplying power.
Embodiment 5
The preparation of LiFePO4 based composites: by the iron phosphate lithium positive pole piece isolated from waste and old lithium ion battery according to It is secondary to be impregnated 10 minutes in the sodium hydroxide solution that molar concentration is 1.0mol/L, it rinses 30 minutes in deionized water, then exists Under nitrogen atmosphere, is calcined 1 hour under 500 DEG C of hot conditions, separate positive active material with aluminium foil, dry, grinding, after screening Obtain pretreated LiFePO 4 material；1000 grams of LiFePO 4 material for fetching receipts, by 350 grams of ferric sulfate solutions in deionization It is made into molysite saturated solution in water, molysite saturated solution is added to the pretreated phosphoric acid being stirred continuously in spraying mode In iron lithium material, it is uniformly mixed；By resulting mixture under nitrogen protection by 550 DEG C after high-temperature process 2 hours, after cooling It crushes, LiFePO4 based composites is obtained after screening.
The preparation of LiFePO4 based composites cathode: the iron phosphate lithium-based composite wood for being first 84% by weight percent Material, weight percent are that (weight percent is 3% bismuth oxide to 10.5% additive, weight percent is 5% ferrous sulfide, weight hundred Point than for 1% vulcanization Asia cobalt and weight percent be 1.5% zinc oxide) and weight percent be that 3% conductive graphene mechanical mixture is equal It is even to obtain negative electrode material mixture；Then negative electrode material mixture is added to by weight percent is 2.5% binder (weight Percentage is 2.0% sodium carboxymethylcellulose and weight percent is 0.5% polytetrafluoroethylene (PTFE)) prepare adhesive solution in, It stirs evenly, active material slurry is made；Then active material slurry obtained is coated in 3 D stereo steel band two sides, passed through Iron phosphate lithium electrode is made in drying, tabletting, punching, soldering polar ear.
Electric performance test: it for the electrical property for examining LiFePO4 based composites made from the present embodiment, is made with above-mentioned Iron phosphate lithium electrode as cathode, using sintered nickel electrode as anode, with 6M potassium hydroxide solution (Na containing 0.1M2S and 0.4M LiOH) it is electrolyte, positive and negative interpolar places polyalkene diaphragm, prepares iron nickel simulated battery, carried out related charge and discharge electrical measurement Examination.Battery was stopped 20 minutes with 0.2C charging 6 hours, was put with 0.2C, 1C or 5C to 0.8V, and active material in iron electrode is calculated Gram volume.Test result shows that the iron nickel simulated battery 0.2C discharge capacity is 296mAh/g or more, and 5C discharge capacity reaches 269mAh/g；Capacity retention ratio is 95.2% after lower 200 circulations of 1C multiplying power.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (8)

1. the waste lithium iron phosphate positive electrode method that recycling recycles in Hawkins cell, it is characterised in that: with waste and old phosphorus Sour iron lithium anode material be raw material, will saturation iron salt solutions be added it is mixed uniformly after under an inert atmosphere pass through calcination processing LiFePO4 based composites are made, the LiFePO4 based composites are then used to prepare Hawkins cell cathode；
Specifically includes the following steps:
(1) dipping pretreatment will impregnate 10-60 minutes from the positive plate separated in waste and old lithium ion battery in lye, Then it rinses 10-60 minutes in deionized water；
(2) precalcining separates, and the positive plate after dipping pretreatment is calcined 0.5-3 hours under 400-550 DEG C of hot conditions, Separate positive active material with aluminium foil, dry, grinding obtains positive active material after screening；
(3) it is saturated ferrous solution mixed processing, soluble ferric iron salt is dissolved in deionized water and is made into molysite saturated solution, and by molysite Saturated solution is added in the positive active material being stirred continuously in spraying mode, is uniformly mixed；
(4) secondary clacining is handled, and the mixture that step (3) obtains is passed through under inert gas protection at 550-800 DEG C of high temperature Reason crushes after 1-4 hours, obtains LiFePO 4 material after screening；
(5) preparation of active material slurry weighs raw material according to following weight percent proportion respectively: LiFePO 4 material 50%- 85%, additive 10%-40%, conductive agent 3%-10% and binder are 1%-3%, by weighed LiFePO 4 material, additive and are led Electric agent is uniformly mixed, and is then added in the adhesive solution by weighed binder making, is stirred evenly, and active matter is made Chylema material；
(6) active material slurry obtained is coated on cathode matrix by the preparation of iron phosphate lithium electrode, by drying, tabletting, The iron phosphate lithium electrode for Hawkins cell cathode is made in punching, soldering polar ear.
2. the waste lithium iron phosphate positive electrode according to claim 1 method that recycling recycles in Hawkins cell, It is characterized by: it is respectively the sodium hydroxide solution of 0.05-1mol/L, hydrogen-oxygen that lye as described in step (1), which is molar concentration, Change one of potassium solution or lithium hydroxide solution or a variety of.
3. the waste lithium iron phosphate positive electrode according to claim 1 method that recycling recycles in Hawkins cell, It is characterized by: soluble ferric iron salt described in step (3) is ferric nitrate, ferrous sulfate, ferrous acetate, iron ammonium sulfate or chlorine Change one of ferrous iron or a variety of.
4. the waste lithium iron phosphate positive electrode according to claim 1 method that recycling recycles in Hawkins cell, It is characterized by: the mass ratio of soluble ferric iron salt described in step (3) and positive active material is 0.05-1:1.
5. the waste lithium iron phosphate positive electrode according to claim 1 method that recycling recycles in Hawkins cell, It is characterized by: additive described in step (5) is nickel sulfate, nickel sulfide, vulcanizes sub- cobalt, bismuth oxide, bismuth sulfide, vulcanization Asia In iron, carbonyl iron dust, ferroso-ferric oxide, zinc oxide, yttrium oxide, erbium oxide, stannous oxide, ceria or titanium dioxide extremely It is two kinds few.
6. the waste lithium iron phosphate positive electrode according to claim 1 method that recycling recycles in Hawkins cell, It is characterized by: conductive agent described in step (5) be electrically conductive graphite, Ketjen black, conductive black, carbon nanotube, graphene or Aoxidize one of titanous or a variety of.
7. the waste lithium iron phosphate positive electrode according to claim 1 method that recycling recycles in Hawkins cell, It is characterized by: binder described in step (5) is polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, butadiene-styrene rubber, polyvinyl alcohol Or one of hydroxypropyl methyl cellulose or a variety of.
8. the waste lithium iron phosphate positive electrode according to claim 1 method that recycling recycles in Hawkins cell, It is characterized by: cathode matrix described in step (6) is perforated steel ribbon, 3 D stereo steel band, stainless (steel) wire, Foamed Nickel, hair Blister copper, foaming iron or copper mesh.
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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
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
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CN113716541B (en) * 2021-07-28 2023-02-17 株洲冶炼集团股份有限公司 High-carbon low-rate lithium iron phosphate decarburization reconstruction method
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101359756A (en) * 2007-07-31 2009-02-04 比亚迪股份有限公司 Method for recycling lithium iron phosphate anode material from lithium ionic cell waste
CN103449395A (en) * 2013-08-28 2013-12-18 北京科技大学 Method for recycling positive material from water-system waste lithium iron phosphate battery
CN104810566A (en) * 2014-07-01 2015-07-29 万向A一二三系统有限公司 Environmentally friendly recovery and treatment method of waste and old lithium iron phosphate power cells

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101359756A (en) * 2007-07-31 2009-02-04 比亚迪股份有限公司 Method for recycling lithium iron phosphate anode material from lithium ionic cell waste
CN103449395A (en) * 2013-08-28 2013-12-18 北京科技大学 Method for recycling positive material from water-system waste lithium iron phosphate battery
CN104810566A (en) * 2014-07-01 2015-07-29 万向A一二三系统有限公司 Environmentally friendly recovery and treatment method of waste and old lithium iron phosphate power cells

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