CN113571699A - Conductive phosphate anode material and preparation method thereof - Google Patents
Conductive phosphate anode material and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention relates to a conductive phosphate anode material and a preparation method thereof, wherein nano zinc oxide is added in the process of preparing a lithium iron phosphate anode material, an aluminum-doped zinc oxide conductive agent is generated in situ, and the chemical composition of the conductive agent is LiFePO4·x ZnO·(0.01‑0.03)Al2O3Wherein x =0.25-0.5, the internal resistance of the prepared lithium iron phosphate anode material is controlled byThe specific capacity of the conductive agent is increased from 130mAh/g to 150-160mAh/g when the conductive agent is not doped. The coated and doped conductive material not only increases the conductivity and specific capacity of the lithium iron phosphate, but also eliminates the adverse effect of aluminum impurities. The aluminum-doped zinc oxide conductive material has good conductivity and low price, can replace the existing graphite and conductive carbon materials, and has industrial application prospect.
Description
Technical Field
The invention relates to a conductive phosphate anode material and a preparation method thereof, in particular to a lithium iron phosphate conductive anode material prepared by taking a waste lithium iron phosphate battery anode material as a raw material and a preparation method thereof, belonging to the field of chemical industry and new energy materials.
Background
The lithium iron phosphate battery has the outstanding advantages of long cycle life, good safety performance, environmental protection and the like, and is widely applied to the fields of passenger cars, energy storage and the like. After the positive electrode of the lithium iron phosphate battery is repeatedly charged and discharged, the electrode material is separated from a current collector through repeated expansion and contraction, so that poor contact is caused; in addition, the dendrite grows up after the crystal form of the anode material is repeatedly charged and discharged, so that lithium ions cannot be freely inserted and removed in the crystal structure, and the capacity is greatly reduced, so that the lithium iron phosphate battery needs to be intensively scrapped and recycled after being used for 5-7 years. One recycling mode is to disassemble the waste water and process the waste water into basic raw materials of lithium salt, ferric salt and phosphate and then process the basic raw materials again for production; the other physical recycling mode is to disassemble the lithium iron phosphate, remove impurities in the anode material by roasting, and repair and use the lithium iron phosphate after replenishing lost lithium, iron or phosphorus elements. Although the cost of physical repair of the positive electrode of the lithium iron phosphate battery is low, the performance of the repaired lithium iron phosphate battery only reaches 90% -93% of the initial performance, and can only meet the low-end application requirements, and the method has a great difference from the ever-increasing demand and expectation of the society. The lithium iron phosphate battery is mainly used as a power battery in the early stage, and the proportion of the lithium iron phosphate battery in the currently scrapped lithium ion power battery reaches more than 70%. The lithium iron phosphate battery does not contain high-value nickel-cobalt metal, and the lithium salt is difficult to recover, so that the profit margin for recovering the lithium iron phosphate battery is smaller than that of a ternary lithium ion battery, and the technical and economic requirements on the recycling technology are higher.
In recent years, a number of patents for recycling methods of waste lithium iron phosphate batteries exist, for example, chinese patent CN112794300A (2021-05-14) discloses a method for separating, recovering and regenerating positive plates of waste lithium iron phosphate batteries, which is disassembled after high-temperature treatment, and then re-sintered into lithium iron phosphate positive materials after lithium and iron are supplemented. Chinese patent CN112310499A (2021-02-02) discloses a method for recovering waste lithium iron phosphate material and the obtained recovery liquid, which reduces the introduction of aluminum impurity in the acidic leaching solution by controlling the dissolution rate of aluminum at low temperature. Chinese patent CN111270072B (2021-09-03) discloses a recycling method of a waste lithium iron phosphate battery positive electrode material, which uses sodium hydroxide solution to dissolve and remove aluminum, and uses pyrophosphate to dissolve the positive electrode material. Chinese patent CN110828887A (2020-02-21) discloses a method for recovering and regenerating waste lithium iron phosphate positive electrode materials and the obtained lithium iron phosphate positive electrode materials, which adopts a chemical and mechanical combination mode to prepare the positive electrode materials by supplementing lost lithium, iron and phosphorus sources and then re-sintering the recovered raw materials. Chinese patent CN111924819A (2020-11-13) discloses a method for recycling waste disassembled lithium iron phosphate positive electrode material, wherein 0.1% -0.8% of aluminum is contained in the recovered positive electrode powder, and the iron phosphate and lithium salt are recovered after the sulfuric acid is dissolved. Chinese patent CN108110357B (2020-07-17) discloses a method for recovering valuable metals from waste lithium iron phosphate battery positive electrode materials.
0.2% -3% of impurity aluminum from an aluminum collector is introduced into the waste lithium iron phosphate battery positive electrode material in the disassembling and crushing process, the performance of the regenerated lithium iron phosphate battery is seriously influenced, the material is usually separated and removed by adopting a method of dissolving with an alkaline aqueous solution, and the formed aluminum hydroxide is colloid, so that the filtering and separating process is difficult, and lithium salt loss is caused by easy adsorption and entrainment. New methods for improving the conductivity of lithium iron phosphate and eliminating the effects of aluminum impurities are needed.
Disassembling the waste lithium iron phosphate battery, and processing the positive electrode material into battery-grade iron phosphate and battery-grade lithium carbonate by a wet method after acid dissolution. Because the waste lithium iron phosphate material is a low-valence solid solution, the acid dissolution speed is very slow, and the waste lithium iron phosphate material is converted into lithium salt and iron phosphate which are easy to dissolve in an industrially high-temperature oxidation mode. And finally, after the iron phosphate and the lithium salt are re-proportioned according to a metering ratio, sintering the mixture in a reducing atmosphere to obtain the lithium iron phosphate anode material.
Because the conductivity of the lithium iron phosphate is poor, a certain proportion of conductive carbon powder needs to be added, the lithium iron phosphate can be coated on the surface of the lithium iron phosphate to increase the conductivity, and the lithium iron phosphate can also be used as a reducing agent for carbothermic reaction to create a reducing atmosphere required by the regeneration of the lithium iron phosphate. Although the conductivity of the lithium iron phosphate coated by a large amount of conductive carbon powder can be improved, the increase of the specific capacitance of the anode material is limited by the huge volume and weight. The patent discloses that the conductivity of lithium iron phosphate is increased by using expensive carbon nanotubes, graphene or conductive polymer materials, but the practicability is not strong. For example, chinese patent CN102136576B (2013-05-01) discloses a conductive agent for lithium iron phosphate battery and a preparation method thereof, which uses carbon nanotubes and conductive carbon composite material as the conductive agent. Chinese patent CN1061159265B (2019-04-09) discloses a preparation method of a positive electrode slurry of a lithium iron phosphate battery containing a graphene composite conductive agent. Chinese patent CN104795569B (2017-03-15) discloses a conductive polymer composite conductive agent for a lithium iron phosphate battery and a preparation method thereof. There are also many patent publications and research reports on lithium iron phosphate coated and doped nano-oxides. For example, chinese patent CN108539132B (2021-05-11) discloses a method for preparing a zinc oxide composite lithium iron phosphate positive electrode material, which can only refine crystal grains and stabilize the cycle performance of lithium iron phosphate. Chinese patent CN110620217B (2019-12-27) discloses a zinc-doped lithium iron phosphate/carbon composite material and a preparation method thereof, which mainly rely on a conductive carbon material to function. Although the coating and doping of the semiconductor nano oxide represented by zinc oxide are beneficial and harmless, the zinc oxide can only play a role in stabilizing the cycle performance, and the effect of increasing the conductivity and specific capacity of the lithium iron phosphate is not great.
Disclosure of Invention
The invention aims to provide a conductive phosphate anode material, in particular to a lithium iron phosphate conductive anode material prepared by taking a waste lithium iron phosphate anode material as a raw material and circularly preparing the lithium iron phosphate anode materialThe nano zinc oxide is added in the process, and the aluminum-doped zinc oxide conductive agent is generated in situ, and the chemical composition of the conductive agent is LiFePO4·x ZnO·(0.01-0.03)Al2O3Wherein x =0.25-0.5, the internal resistance of the prepared lithium iron phosphate cathode material is reduced to 4.5-5 omega from 5.5-6.5 omega when the lithium iron phosphate cathode material is not doped with the conductive agent, and the specific capacity is increased to 150-160mAh/g from 130mAh/g when the lithium iron phosphate cathode material is not doped with the conductive agent; the coated and doped conductive material not only increases the conductivity of the lithium iron phosphate, but also eliminates the adverse effects of aluminum impurities.
The conductive lithium iron phosphate anode material coated and doped with the aluminum-doped zinc oxide conductive agent has good conductivity, specific capacity and cycle performance stability, and can be mixed with an adhesive to be coated on an aluminum collector to prepare the conductive lithium iron phosphate anode without doping conductive carbon. The zinc and the compound thereof are non-valence-variable transition metals and salts, the zinc oxide is a semiconductor, and researches show that the conductivity and specific capacity of lithium iron phosphate are not obviously improved only by doping the zinc oxide, and the stability of the electrochemical cycle performance of the lithium iron phosphate can only be improved. The aluminum-doped zinc oxide conductive agent adopted in the invention has essentially different effects with zinc oxide, is a typical transparent conductive oxide, has good conductivity in a film layer with the thickness of dozens of nanometers, and has the resistivity which is 10 the same as that of a graphite material-6In the order of Ω m, but the conductivity is better than that of graphite material.
On the basis of long-term research on conductive films of solar batteries and lithium ion battery materials, the invention creatively applies the aluminum-doped zinc oxide (AZO) sol-gel method technology of the solar batteries to the aspect of improving the conductivity and specific capacity of the lithium iron phosphate positive electrode material, can break through the bottleneck of limiting the electrochemical performance of the lithium iron phosphate, particularly changes the aluminum impurities in the waste lithium iron phosphate batteries into benefits, has substantive characteristics and remarkable progress, and is completely different from the prior art. Aluminum impurities exist in the anode material of the waste lithium ion battery, zinc oxide is doped in the aluminum impurities, and an aluminum-doped zinc oxide conductive oxide is formed in situ, so that the conductivity of the lithium iron phosphate anode material can be improved.
The reason why the AZO conductive material has good conductivity is to have high current carryingSub-concentration, mainly from Al3+Part of Zn in zinc oxide2+Instead, the aluminum-doped zinc oxide needs to be annealed at high temperature to produce good conductivity. AZO conductive oxide formation also requires control of the proportion of aluminum impurities, and if the aluminum impurity content is too high, the formation of a large amount of insulating aluminum oxide will increase the electrical resistivity of AZO. If the proportion of zinc oxide in the lithium iron phosphate anode material is too high, the specific capacity of the lithium iron phosphate anode material is reduced. The method is characterized in that a simple physical method is usually adopted for separating aluminum impurities in the anode material of the waste lithium iron phosphate battery, because the aluminum foil of the collector is soft, most of the aluminum collector material is only crushed into aluminum foil fragments instead of fine aluminum powder in the crushing process of the anode material of the waste lithium iron phosphate battery, the aluminum foil fragments can be separated from fine anode material powder by a simple method of coarse screening, the mass fraction of the aluminum impurities in the lithium iron phosphate anode material is less than 1%, the aluminum impurities can be further separated from the anode material powder by a wind screening mode, the mass fraction of the aluminum impurities in the anode material powder of the waste lithium iron phosphate battery in industrial production is easily controlled to be 0.3% -0.9%, the method is in an application range of the method, and the mass fraction of the aluminum impurities is difficult to further reduce.
The invention also aims to provide a preparation method of the conductive phosphate anode material, in particular to a method for preparing the conductive lithium iron phosphate anode material by taking the waste lithium iron phosphate anode material as a raw material, which comprises the following steps:
(1) the waste lithium iron phosphate anode is subjected to heat treatment at the temperature of 400-550 ℃ for 2-6h, so that the iron in the anode material is oxidized into high-valence iron phosphate, the iron is dissolved by acid, and meanwhile, the adhesive is carbonized, so that the iron can be peeled from an aluminum collector;
(2) crushing and sieving the oxidized anode, sieving and recovering an aluminum collector material, controlling the mass fraction of aluminum in the anode powder to be less than 1%, and then soaking the anode powder in a hydrochloric acid aqueous solution with the mass concentration of 10% -30% at 50-80 ℃ for 8-24h to dissolve and convert the anode powder into a hydrochloric acid aqueous solution of lithium chloride and iron phosphate;
(3) filtering the dissolved anode material aqueous solution while the anode material aqueous solution is hot, separating insoluble residues and conductive carbon materials, cooling the filtrate, neutralizing the filtrate with ammonia water with the mass concentration of 15%, separating out the coprecipitation of ferric phosphate and aluminum hydroxide, filtering and separating precipitates, and washing salt carried in the coprecipitation by deionized water;
(4) adding a saturated sodium carbonate aqueous solution into the filtrate, recovering and separating lithium carbonate precipitate by adopting a precipitation method, washing salt carried in the precipitate by using deionized water, and separating, refining and drying by adopting a conventional method to obtain a battery-grade lithium carbonate product;
(5) dissolving soluble zinc salt into 2mol/L aqueous solution, neutralizing with ammonia water with mass concentration of 15% to pH =10-11, filtering and separating precipitated hydrated zinc oxide sol particles, and cleaning salt carried in the hydrated zinc oxide sol particles; then dispersing in oxalic acid saturated water solution, acid-dissolving for 1-4h at 50-70 ℃, controlling the feed ratio to ensure that the molar ratio of oxalic acid to zinc oxide is 0.6-1:1, and acid-dissolving hydrated zinc oxide sol particles to form zinc hydroxide sol; the soluble zinc salt is one of zinc chloride, zinc sulfate, zinc nitrate or zinc acetate;
(6) dispersing the ferric phosphate precipitate in zinc hydroxide sol, adding lithium carbonate powder, and grinding for 1-2 h; the mixture is dried at 80-110 ℃, roasted at 500-600 ℃ for 1-4h under the protection of nitrogen, cooled to obtain the conductive lithium iron phosphate coated by the aluminum-doped zinc oxide, and the chemical composition of the conductive lithium iron phosphate is LiFePO4·x ZnO·(0.01-0.03)Al2O3Wherein x =0.25-0.5, the internal resistance of the prepared lithium iron phosphate anode is reduced to 4.5-5 omega from 5.5-6.5 omega when the conductive agent is not doped, and the specific capacity is increased to 150-160mAh/g from 130mAh/g when the conductive agent is not doped.
The experimental raw material waste lithium iron phosphate positive electrode material used in the invention is an industrial product purchased on the internet or obtained by self-disassembling waste lithium iron phosphate batteries, and zinc chloride, hydrochloric acid, lithium hydroxide and lithium carbonate are all commercially available chemical pure reagents.
The invention has the beneficial effects that:
(1) according to the invention, aluminum impurities in the waste lithium iron phosphate anode material are converted into the aluminum-doped zinc oxide conductive agent in situ, and the aluminum-doped zinc oxide conductive agent is coated and doped in the lithium iron phosphate anode material, so that the conductivity of the anode material can be improved, and the adverse effect of aluminum impurities can be eliminated;
(2) the specific capacity of the conductive lithium iron phosphate is higher than that of an undoped lithium iron phosphate anode material, and a new direction for improving the performance of the lithium iron phosphate anode material is pointed out;
(3) the aluminum-doped zinc oxide conductive material has good conductivity and low price, can replace graphite and conductive carbon materials, and has industrial application prospect.
Detailed Description
Example 1
The method comprises the following steps of (1) carrying out heat treatment on 100g of waste lithium iron phosphate positive electrode material at 550 ℃ for 2h to oxidize iron in the positive electrode material into high-valence-state iron phosphate, and simultaneously carbonizing an adhesive to be convenient for stripping from a collector; and crushing and sieving the anode cooled after oxidation by a 100-mesh sieve to recover the residual aluminum collector material. 79g of the sieved positive electrode powder was taken out, and the mass content of aluminum was measured to be 0.5%, and the powder was immersed in a 30% aqueous hydrochloric acid solution at 50 ℃ for 8 hours to be dissolved and converted into an aqueous hydrochloric acid solution of lithium chloride and iron phosphate. And (3) filtering the dissolved anode material aqueous solution while the solution is hot, cooling the filtrate, neutralizing the cooled filtrate with ammonia water with the mass concentration of 15%, separating out the coprecipitation of the iron phosphate and the aluminum hydroxide, filtering and separating precipitates, and washing salt carried in the coprecipitation by deionized water. And adding a saturated sodium carbonate aqueous solution into the mother liquor, recovering and separating lithium carbonate precipitate by a precipitation method, washing salt carried in the precipitate by deionized water, concentrating the mother liquor, refining and drying to obtain 15.9g of a battery-grade lithium carbonate product.
Dissolving 34g of anhydrous zinc chloride into 2mol/L aqueous solution, neutralizing the solution to pH =10-11 by using ammonia water with the mass concentration of 15%, filtering and separating precipitated hydrated zinc oxide sol particles, and cleaning salt carried in the hydrated zinc oxide sol particles; then dispersing in 0.25mol oxalic acid saturated water solution, and acid-dissolving at 70 ℃ for 2h to form zinc hydroxide sol by acid-dissolving hydrated zinc oxide sol particles. Dispersing the iron phosphate precipitate in zinc hydroxide sol, adding 18.5g (0.25 mol) of lithium carbonate powder, and grinding for 1 h; the mixture is dried at 110 ℃, roasted for 2h at 600 ℃ under the protection of nitrogen, and cooled to obtain 100.5g of conductive lithium iron phosphate coated with aluminum-doped zinc oxide, wherein the chemical composition of the conductive lithium iron phosphate is LiFePO4·0.5ZnO·0.015Al2O3The internal resistance of the prepared lithium iron phosphate anode is made of undoped lithium iron phosphateThe 6.5 omega of the conductive agent is reduced to 5 omega, and the specific capacity is increased to 155mAh/g from 130mAh/g of the undoped conductive agent.
Claims (2)
1. A conductive phosphate anode material is characterized in that a waste lithium iron phosphate anode material is used as a raw material to prepare the lithium iron phosphate conductive anode material, nano zinc oxide is added in the process of circularly preparing the lithium iron phosphate anode material, an aluminum-doped zinc oxide conductive agent is generated in situ, and the chemical composition of the conductive lithium iron phosphate anode material is LiFePO4·x ZnO·(0.01-0.03)Al2O3Wherein x =0.25-0.5, the internal resistance of the prepared lithium iron phosphate cathode material is reduced to 4.5-5 omega from 5.5-6.5 omega when the lithium iron phosphate cathode material is not doped with the conductive agent, and the specific capacity is increased to 150-160mAh/g from 130mAh/g when the lithium iron phosphate cathode material is not doped with the conductive agent.
2. A preparation method of a conductive phosphate cathode material is characterized by comprising the following steps:
(1) the waste lithium iron phosphate anode is subjected to heat treatment at the temperature of 400-550 ℃ for 2-6h, so that the iron in the anode material is oxidized into high-valence iron phosphate, the iron is dissolved by acid, and meanwhile, the adhesive is carbonized, so that the iron can be peeled from an aluminum collector;
(2) crushing and sieving the oxidized anode, sieving and recovering an aluminum collector material, controlling the mass fraction of aluminum in the anode powder to be less than 1%, and then soaking the anode powder in a hydrochloric acid aqueous solution with the mass concentration of 10% -30% at 50-80 ℃ for 8-24h to dissolve and convert the anode powder into a hydrochloric acid aqueous solution of lithium chloride and iron phosphate;
(3) filtering the dissolved anode material aqueous solution while the anode material aqueous solution is hot, separating insoluble residues and conductive carbon materials, cooling the filtrate, neutralizing the filtrate with ammonia water with the mass concentration of 15%, separating out the coprecipitation of ferric phosphate and aluminum hydroxide, filtering and separating precipitates, and washing salt carried in the coprecipitation by deionized water;
(4) adding a saturated sodium carbonate aqueous solution into the filtrate, recovering and separating lithium carbonate precipitate by adopting a precipitation method, washing salt carried in the precipitate by using deionized water, and separating, refining and drying by adopting a conventional method to obtain a battery-grade lithium carbonate product;
(5) dissolving soluble zinc salt into 2mol/L aqueous solution, neutralizing with ammonia water with mass concentration of 15% to pH =10-11, filtering and separating precipitated hydrated zinc oxide sol particles, and cleaning salt carried in the hydrated zinc oxide sol particles; then dispersing in oxalic acid saturated water solution, acid-dissolving for 1-4h at 50-70 ℃, controlling the feed ratio to ensure that the molar ratio of oxalic acid to zinc oxide is 0.6-1:1, and acid-dissolving hydrated zinc oxide sol particles to form zinc hydroxide sol; the soluble zinc salt is one of zinc chloride, zinc sulfate, zinc nitrate or zinc acetate;
(6) dispersing the ferric phosphate precipitate in zinc hydroxide sol, adding lithium carbonate powder, and grinding for 1-2 h; the mixture is dried at 80-110 ℃, roasted at 500-600 ℃ for 1-4h under the protection of nitrogen, cooled to obtain the conductive lithium iron phosphate coated by the aluminum-doped zinc oxide, and the chemical composition of the conductive lithium iron phosphate is LiFePO4·x ZnO·(0.01-0.03)Al2O3Wherein x =0.25-0.5, the internal resistance of the prepared lithium iron phosphate anode is reduced to 4.5-5 omega from 5.5-6.5 omega when the conductive agent is not doped, and the specific capacity is increased to 150-160mAh/g from 130mAh/g when the conductive agent is not doped.
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