CN111710882A - Process for preparing lithium battery negative electrode material by using waste zinc-manganese battery - Google Patents
Process for preparing lithium battery negative electrode material by using waste zinc-manganese battery Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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 process for preparing a lithium battery cathode material by using waste zinc-manganese batteries, which comprises the steps of crushing the waste zinc-manganese batteries, collecting a cathode zinc compound, then adding the zinc compound into a 10% dilute hydrochloric acid solution, magnetically stirring until the zinc compound is dissolved, and filtering to prepare a zinc chloride solution; adding trisodium citrate into deionized water, stirring at constant speed until the trisodium citrate is completely dissolved, adding the prepared zinc chloride solution, magnetically stirring for 30min, and adding absolute ethanol to obtain a mixed solution A; in the preparation process, the zinc citrate precipitate is washed and carbonized to prepare a product B, the product B is substantially a mixture of zinc oxide and nano carbon, and then the product B is mixed with porous nano carbon in the step S3, the porous nano carbon can bridge carbon channels among zinc oxide particles to further promote the transfer of ions and electrons, and can limit the reaction of the zinc oxide and lithium in an electrolyte when the zinc oxide is used as a negative electrode material, so that the charging and discharging effects of the battery are influenced.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a process for preparing a lithium battery cathode material by using a waste zinc-manganese battery.
Background
The zinc-manganese cell is a common primary cell which can be stored for a long time, is widely used as a power supply of low-power electric appliances, such as various electronic clocks, stove ignition power supplies, emergency storage power supplies and the like, and can be stored for years without deterioration. Generally, zinc-manganese batteries can be divided into two categories: the acid zinc-manganese battery (also called carbon battery in the market) which is extremely cheap and the alkaline zinc-manganese battery which is more expensive but has much larger electricity storage capacity and much better power characteristics. The acid zinc-manganese battery uses a carbon rod as a positive current collector. The carbon rod is surrounded by paste formed by electrochemical activity MnO2 mineral powder, graphite powder and ammonium chloride aqueous solution to form the anode of the battery, the anode and a metal zinc cylinder used as the cathode are separated by a diaphragm, and an organic material used for separating the anode and the cathode and sealing the battery is added, so that the acid (or carbon) zinc-manganese dry battery is formed.
Chinese patent CN110752384A discloses a method for recycling waste zinc-manganese batteries, comprising the following steps: (1) Putting the waste batteries into a sorting machine to obtain zinc-manganese batteries with different specifications; (2) Breaking shells, magnetically separating and screening the materials to obtain battery powder; (3) Adding water into the battery powder to completely dissolve the electrolyte, filtering to obtain an electrolyte solution, and then evaporating, concentrating and performing fractional crystallization to obtain pure ammonia water, KCl and KOH; (4) Adding water, dilute sulfuric acid and a reducing agent into the obtained solid, and stirring for reaction to obtain a mixed solution of zinc sulfate and manganese sulfate; (5) Adding the zinc skin obtained in the step (2) into the mixed solution to remove impurities, filtering out solids, and then directly electrolyzing to obtain manganese dioxide at the anode and zinc at the cathode; (6) The resulting zinc and manganese dioxide are used to make new alkaline zinc-manganese batteries. The invention can recycle 100% of materials in the waste zinc-manganese batteries, so that the zinc-manganese batteries are produced circularly, and the energy consumption, material consumption and pollution risk are greatly reduced.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a process for preparing a lithium battery cathode material by using a waste zinc-manganese battery.
The technical problems to be solved by the invention are as follows:
in the prior art, zinc oxide is used as a negative electrode material of a lithium battery, but the zinc oxide can react with lithium in electrolyte to influence the charging and discharging effects of the battery, and the zinc oxide and the nano-carbon are limited by the nano-carbon when being mixed for use, so that the zinc oxide and the nano-carbon cannot be stably combined to influence the service performance of the lithium battery.
The purpose of the invention can be realized by the following technical scheme:
a process for preparing a lithium battery cathode material by using a waste zinc-manganese battery is characterized by comprising the following steps:
s1, crushing the waste zinc-manganese battery, collecting a negative zinc compound, adding the zinc compound into a dilute hydrochloric acid solution with the mass fraction of 10%, magnetically stirring until the zinc compound is dissolved, and filtering to obtain a zinc chloride solution; adding trisodium citrate into deionized water, stirring at constant speed until the trisodium citrate is completely dissolved, adding the prepared zinc chloride solution, magnetically stirring for 30min, and adding absolute ethyl alcohol to obtain a mixed solution A;
s2, heating the mixed solution A in a water bath at 55-60 ℃, stirring at a constant speed for 1h, standing for 20min after stirring is finished, filtering, washing with deionized water and absolute ethyl alcohol for three times respectively, freeze-drying, transferring to a vacuum tube furnace for carbonization treatment, controlling the carbonization temperature to be 700-750 ℃ and the carbonization time to be 4h, and obtaining a product B;
and S3, mixing the product B with porous nanocarbon, adding the mixture into deionized water, performing ultrasonic and magnetic stirring for 30min to obtain a mixed solution C, transferring the mixed solution C into a reaction kettle, performing hydrothermal treatment, performing suction filtration, drying a filter cake at 80 ℃ for 5h, and grinding to obtain the lithium battery cathode material, wherein the weight ratio of the product B to the porous nanocarbon is controlled to be 1: 0.5-0.8.
The method comprises the following steps of S1, crushing the waste zinc-manganese battery, recovering a negative zinc compound in the battery, adding the negative zinc compound into a dilute hydrochloric acid solution to prepare a zinc chloride solution, preparing a trisodium citrate aqueous solution, mixing the trisodium citrate aqueous solution with the zinc chloride solution, and reacting to generate a zinc citrate precipitate; and in the step S2, washing and carbonizing the zinc citrate precipitate to obtain a product B, wherein the product B is substantially a mixture of zinc oxide and nanocarbon, and then, in the step S3, mixing the product B with porous nanocarbon, wherein the porous nanocarbon can be used for erecting carbon channels among zinc oxide particles, further promoting the transfer of ions and electrons, and limiting the reaction of zinc oxide and lithium in electrolyte when the zinc oxide is used as a negative electrode material, so that the charging and discharging effects of the battery are influenced.
Further, the ratio of the amount of the zinc chloride to the amount of the trisodium citrate is controlled to be 1: 1.2-1.5.
Further, in the step S3, the temperature of the hydrothermal treatment is controlled to be 110-120 ℃, and the time of the hydrothermal treatment is 10-12h.
Further, the porous nanocarbon is prepared by the following method:
adding glucose into deionized water, adding sodium carboxymethylcellulose, heating in a water bath at 40-45 ℃ and magnetically stirring for 20min to obtain a mixed solution D, transferring the mixed solution D into a reaction kettle, heating to 180-200 ℃ at a heating rate of 10 ℃/min, reacting for 20h at the temperature, filtering, and washing with absolute ethyl alcohol for three times to obtain carbon nano microspheres;
and secondly, mixing the carbon nano-microspheres and the carbon black according to the weight ratio of 2: 1 to prepare a mixture, then adding a pore-forming agent, uniformly mixing, heating to 750 ℃ at the heating rate of 15 ℃/min under the argon atmosphere, preserving heat for 4h at the temperature, heating to 980-1100 ℃ at the heating rate of 10 ℃/min, preserving heat for 2h, and cooling to prepare the porous nano-carbon, wherein the weight ratio of the pore-forming agent to the mixture is controlled to be 1.5-1.8: 2.
Glucose is added into deionized water in the first step, sodium carboxymethyl cellulose is added later, a carbon nano microsphere is prepared by water bath heating, the particle size of the prepared carbon nano microsphere can be controlled by controlling the time and the temperature of the water bath heating, the carbon microsphere and carbon black are mixed according to the weight ratio of 2: 1 in the second step later, a pore-forming agent is added for continuous sectional calcination, the sodium carboxymethyl cellulose can be coated on the surfaces of the carbon microsphere and the carbon black and can serve as a lubricant, the friction force among mixed particles is reduced, the prepared carbon nano microsphere has higher density, the sodium carboxymethyl cellulose is decomposed in the continuous temperature rising process to generate a large number of pores, the formed nano carbon generates pores, the pore-forming agent is added, and the specific surface area of the nano carbon can be further increased.
Further, the weight ratio of the glucose, the sodium carboxymethylcellulose and the deionized water is controlled to be 1: 0.02: 100.
Further, in the second step, the pore-forming agent is one or two of ammonium bicarbonate powder and TW-series pore-forming agent.
Further, the porosity of the porous nanocarbon is 28% to 30%.
The invention has the beneficial effects that:
(1) The invention relates to a process for preparing a lithium battery cathode material by using a waste zinc-manganese battery, which comprises the steps of S1, crushing the waste zinc-manganese battery, recovering a cathode zinc compound in the battery, adding the cathode zinc compound into a dilute hydrochloric acid solution to prepare a zinc chloride solution, preparing a trisodium citrate aqueous solution, mixing the trisodium citrate aqueous solution with the zinc chloride solution for reaction, and generating a zinc citrate precipitate; and in the step S2, washing and carbonizing the zinc citrate precipitate to obtain a product B, wherein the product B is substantially a mixture of zinc oxide and nanocarbon, and then, in the step S3, mixing the product B with porous nanocarbon, wherein the porous nanocarbon can be used for erecting carbon channels among zinc oxide particles, further promoting the transfer of ions and electrons, and limiting the reaction of zinc oxide and lithium in electrolyte when the zinc oxide is used as a negative electrode material, so that the charging and discharging effects of the battery are influenced.
(2) The invention also discloses a porous nanocarbon, which is prepared by adding glucose into deionized water in the first step in the preparation process, then adding sodium carboxymethyl cellulose, preparing a carbon nano microsphere by heating in a water bath, controlling the time and temperature of the heating in the water bath, mixing the carbon nano microsphere and carbon black according to the weight ratio of 2: 1 in the second step, then adding a pore-forming agent to continuously calcine in a segmented manner, wherein the sodium carboxymethyl cellulose can coat the surfaces of the carbon microsphere and the carbon black and can serve as a lubricant, so that the friction force between mixed particles is reduced, the prepared carbon nano microsphere has high density, the sodium carboxymethyl cellulose is decomposed during the continuous temperature rise process to generate a large number of pores, the formed nano carbon generates pores, the pore-forming agent is added, the specific surface area of the nano carbon can be further increased, when the porous nanocarbon is mixed with zinc oxide, the porous nano carbon can be stably compounded with zinc oxide, and the problem that the usability of the lithium battery can not be influenced by the combination of the lithium battery when the zinc oxide and the nano carbon is mixed with the zinc oxide is used is solved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A process for preparing a lithium battery cathode material by using a waste zinc-manganese battery is characterized by comprising the following steps:
s1, crushing the waste zinc-manganese battery, collecting a negative zinc compound, adding the zinc compound into a 10% dilute hydrochloric acid solution, magnetically stirring until the zinc compound is dissolved, and filtering to obtain a zinc chloride solution; adding trisodium citrate into deionized water, stirring at constant speed until the trisodium citrate is completely dissolved, adding the prepared zinc chloride solution, magnetically stirring for 30min, and adding absolute ethanol to obtain a mixed solution A, wherein the mass ratio of zinc chloride to trisodium citrate is controlled to be 1: 1.2;
s2, heating the mixed solution A in a water bath at 55 ℃, stirring at a constant speed for 1h, standing for 20min after stirring is finished, filtering, washing with deionized water and absolute ethyl alcohol for three times respectively, freeze-drying, transferring to a vacuum tube furnace for carbonization treatment, controlling the carbonization temperature to be 700 ℃ and the carbonization time to be 4h, and obtaining a product B;
and S3, mixing the product B with porous nanocarbon, adding the mixture into deionized water, performing ultrasonic and magnetic stirring for 30min to obtain a mixed solution C, transferring the mixed solution C into a reaction kettle, performing hydrothermal treatment, performing suction filtration, drying a filter cake at 80 ℃ for 5h, and grinding to obtain the lithium battery cathode material, wherein the weight ratio of the product B to the porous nanocarbon is controlled to be 1: 0.5.
The porous nano carbon is prepared by the following method:
adding glucose into deionized water, adding sodium carboxymethylcellulose, heating in a water bath at 40 ℃ and magnetically stirring for 20min to prepare a mixed solution D, transferring the mixed solution D into a reaction kettle, heating to 180 ℃ at a heating rate of 10 ℃/min, reacting for 20h at the temperature, filtering, washing with absolute ethyl alcohol for three times to prepare carbon nano microspheres, and controlling the weight ratio of the glucose, the sodium carboxymethylcellulose and the deionized water to be 1: 0.02: 100;
and secondly, mixing the carbon nano-microspheres and the carbon black according to the weight ratio of 2: 1 to prepare a mixture, then adding ammonium bicarbonate powder, uniformly mixing, heating to 750 ℃ at the heating rate of 15 ℃/min under the argon atmosphere, preserving heat for 4h at the temperature, heating to 1000 ℃ at the heating rate of 10 ℃/min, preserving heat for 2h, and cooling to prepare the porous nano-carbon, wherein the weight ratio of the ammonium bicarbonate powder to the mixture is controlled to be 1.5: 2.
Example 2
A process for preparing a lithium battery cathode material by using waste zinc-manganese batteries is characterized by comprising the following steps:
s1, crushing the waste zinc-manganese battery, collecting a negative zinc compound, adding the zinc compound into a 10% dilute hydrochloric acid solution, magnetically stirring until the zinc compound is dissolved, and filtering to obtain a zinc chloride solution; adding trisodium citrate into deionized water, stirring at uniform speed until the trisodium citrate is completely dissolved, adding the prepared zinc chloride solution, magnetically stirring for 30min, and adding absolute ethanol to obtain a mixed solution A, wherein the mass ratio of zinc chloride to trisodium citrate is controlled to be 1: 1.3;
s2, heating the mixed solution A in a water bath at 55 ℃, stirring at a constant speed for 1h, standing for 20min after stirring is finished, filtering, washing with deionized water and absolute ethyl alcohol for three times respectively, freeze-drying, transferring to a vacuum tube furnace for carbonization treatment, controlling the carbonization temperature to be 700 ℃ and the carbonization time to be 4h, and obtaining a product B;
and S3, mixing the product B with porous nanocarbon, adding the mixture into deionized water, performing ultrasonic and magnetic stirring for 30min to obtain a mixed solution C, transferring the mixed solution C into a reaction kettle, performing hydrothermal treatment, performing suction filtration, drying a filter cake at 80 ℃ for 5h, and grinding to obtain the lithium battery cathode material, wherein the weight ratio of the product B to the porous nanocarbon is controlled to be 1: 06.
The rest is the same as example 1.
Example 3
A process for preparing a lithium battery cathode material by using a waste zinc-manganese battery is characterized by comprising the following steps:
s1, crushing the waste zinc-manganese batteries, collecting a negative zinc compound, then adding the zinc compound into a 10% dilute hydrochloric acid solution, magnetically stirring until the zinc compound is dissolved, and filtering to obtain a zinc chloride solution; adding trisodium citrate into deionized water, stirring at constant speed until the trisodium citrate is completely dissolved, adding the prepared zinc chloride solution, magnetically stirring for 30min, and adding absolute ethanol to obtain a mixed solution A, wherein the mass ratio of zinc chloride to trisodium citrate is controlled to be 1: 1.4;
s2, heating the mixed solution A in a water bath at 55 ℃, stirring at a constant speed for 1h, standing for 20min after stirring is finished, filtering, washing with deionized water and absolute ethyl alcohol for three times respectively, freeze-drying, transferring to a vacuum tube furnace for carbonization treatment, controlling the carbonization temperature to be 700 ℃ and the carbonization time to be 4h, and obtaining a product B;
and S3, mixing the product B with porous nanocarbon, adding the mixture into deionized water, performing ultrasonic and magnetic stirring for 30min to obtain a mixed solution C, transferring the mixed solution C into a reaction kettle, performing hydrothermal treatment, performing suction filtration, drying a filter cake at 80 ℃ for 5h, and grinding to obtain the lithium battery cathode material, wherein the weight ratio of the product B to the porous nanocarbon is controlled to be 1: 0.6.
The rest is the same as example 1.
Example 4
A process for preparing a lithium battery cathode material by using a waste zinc-manganese battery is characterized by comprising the following steps:
s1, crushing the waste zinc-manganese batteries, collecting a negative zinc compound, then adding the zinc compound into a 10% dilute hydrochloric acid solution, magnetically stirring until the zinc compound is dissolved, and filtering to obtain a zinc chloride solution; adding trisodium citrate into deionized water, stirring at uniform speed until the trisodium citrate is completely dissolved, adding the prepared zinc chloride solution, magnetically stirring for 30min, and adding absolute ethanol to obtain a mixed solution A, wherein the mass ratio of zinc chloride to trisodium citrate is controlled to be 1: 1.5;
s2, heating the mixed solution A in a water bath at 55 ℃, stirring at a constant speed for 1h, standing for 20min after stirring, filtering, washing with deionized water and absolute ethyl alcohol for three times respectively, freeze-drying, transferring to a vacuum tube furnace for carbonization treatment, controlling the carbonization temperature to be 700 ℃ and the carbonization time to be 4h, and obtaining a product B;
and S3, mixing the product B with porous nanocarbon, adding the mixture into deionized water, performing ultrasonic and magnetic stirring for 30min to obtain a mixed solution C, transferring the mixed solution C into a reaction kettle, performing hydrothermal treatment, performing suction filtration, drying a filter cake at 80 ℃ for 5h, and grinding to obtain the lithium battery cathode material, wherein the weight ratio of the product B to the porous nanocarbon is controlled to be 1: 0.8.
The rest is the same as example 1.
Comparative example 1
In comparison with example 1, the preparation method of the comparative example is as follows without adding porous nanocarbon:
a process for preparing a lithium battery cathode material by using waste zinc-manganese batteries is characterized by comprising the following steps:
s1, crushing the waste zinc-manganese battery, collecting a negative zinc compound, adding the zinc compound into a 10% dilute hydrochloric acid solution, magnetically stirring until the zinc compound is dissolved, and filtering to obtain a zinc chloride solution; adding trisodium citrate into deionized water, stirring at constant speed until the trisodium citrate is completely dissolved, adding the prepared zinc chloride solution, magnetically stirring for 30min, and adding absolute ethanol to obtain a mixed solution A, wherein the mass ratio of zinc chloride to trisodium citrate is controlled to be 1: 1.2;
s2, heating the mixed solution A in a water bath at 55 ℃, stirring at a constant speed for 1h, standing for 20min after stirring, filtering, washing with deionized water and absolute ethyl alcohol for three times respectively, freeze-drying, transferring to a vacuum tube furnace for carbonization treatment, controlling the carbonization temperature to be 700 ℃ and the carbonization time to be 4h, and obtaining a product B;
and S3, adding the product B into deionized water, performing ultrasonic and magnetic stirring for 30min to obtain a mixed solution C, transferring the mixed solution C into a reaction kettle, performing hydrothermal treatment, performing suction filtration, drying a filter cake at 80 ℃ for 5h, and grinding to obtain the lithium battery cathode material.
Comparative example 2
Compared with example 1, the preparation method of the comparative example, which replaces the porous nanocarbon with the nanocarbon, is as follows:
a process for preparing a lithium battery cathode material by using waste zinc-manganese batteries is characterized by comprising the following steps:
s1, crushing the waste zinc-manganese battery, collecting a negative zinc compound, adding the zinc compound into a 10% dilute hydrochloric acid solution, magnetically stirring until the zinc compound is dissolved, and filtering to obtain a zinc chloride solution; adding trisodium citrate into deionized water, stirring at uniform speed until the trisodium citrate is completely dissolved, adding the prepared zinc chloride solution, magnetically stirring for 30min, and adding absolute ethanol to obtain a mixed solution A, wherein the mass ratio of zinc chloride to trisodium citrate is controlled to be 1: 1.2;
s2, heating the mixed solution A in a water bath at 55 ℃, stirring at a constant speed for 1h, standing for 20min after stirring, filtering, washing with deionized water and absolute ethyl alcohol for three times respectively, freeze-drying, transferring to a vacuum tube furnace for carbonization treatment, controlling the carbonization temperature to be 700 ℃ and the carbonization time to be 4h, and obtaining a product B;
and S3, mixing the product B with nanocarbon, adding the mixture into deionized water, performing ultrasonic and magnetic stirring for 30min to obtain a mixed solution C, transferring the mixed solution C into a reaction kettle, performing hydrothermal treatment, performing suction filtration, drying a filter cake at 80 ℃ for 5h, and grinding to obtain the lithium battery cathode material, wherein the weight ratio of the product B to the nanocarbon is controlled to be 1: 0.5.
Comparative example 3
The comparative example is that the anode material of the lithium battery is prepared by utilizing the waste zinc-manganese battery in the prior art.
Specific discharge capacity of the negative electrode materials of the batteries of examples 1 to 4 and comparative examples 1 to 3,
It can be seen from the above table that the specific discharge capacity of examples 1 to 4 is 688.5 to 705.1mAh/g, the battery expansion rate is 0.75 to 0.80%, the primary coulombic efficiency is 92.8 to 93.0%, the specific discharge capacity of comparative examples 1 to 3 is 554.2 to 602.2mAh/g, the battery expansion rate is 1.05 to 1.2%, and the primary coulombic efficiency is 81.2 to 85.8%. Therefore, the zinc citrate precipitate is washed and carbonized in the step S2 to obtain a product B, the product B is substantially a mixture of zinc oxide and nano carbon, and then the product B is mixed with porous nano carbon in the step S3, the porous nano carbon can span carbon channels between nano zinc ferrite particles, thereby further promoting the transfer of ions and electrons, and limiting the reaction of zinc oxide and lithium in an electrolyte when the zinc oxide is used as a negative electrode material, so that the charging and discharging effects of the battery are influenced.
In the description herein, references to the description of "one embodiment," "an example," "a specific example," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only, and it will be appreciated by those skilled in the art that various modifications, additions and substitutions can be made to the embodiments described without departing from the scope of the invention as defined in the appended claims.
Claims (7)
1. A process for preparing a lithium battery cathode material by using a waste zinc-manganese battery is characterized by comprising the following steps:
s1, crushing the waste zinc-manganese batteries, collecting a negative zinc compound, then adding the zinc compound into a 10% dilute hydrochloric acid solution, magnetically stirring until the zinc compound is dissolved, and filtering to obtain a zinc chloride solution; adding trisodium citrate into deionized water, stirring at constant speed until the trisodium citrate is completely dissolved, adding the prepared zinc chloride solution, magnetically stirring for 30min, and adding absolute ethanol to obtain a mixed solution A;
s2, heating the mixed solution A in a water bath at 55-60 ℃, stirring at a constant speed for 1h, standing for 20min after stirring, filtering, washing with deionized water and absolute ethyl alcohol for three times respectively, freeze-drying, transferring to a vacuum tube furnace for carbonization treatment, controlling the carbonization temperature to be 700-750 ℃ and the carbonization time to be 4h, and obtaining a product B;
and S3, mixing the product B with porous nanocarbon, adding the mixture into deionized water, performing ultrasonic and magnetic stirring for 30min to obtain a mixed solution C, transferring the mixed solution C into a reaction kettle, performing hydrothermal treatment, performing suction filtration, drying a filter cake at 80 ℃ for 5h, and grinding to obtain the lithium battery cathode material, wherein the weight ratio of the product B to the porous nanocarbon is controlled to be 1: 0.5-0.8.
2. The process for preparing the negative electrode material of the lithium battery by using the waste zinc-manganese dioxide battery as claimed in claim 1, wherein the amount ratio of the zinc chloride to the trisodium citrate is controlled to be 1: 1.2-1.5.
3. The process for preparing the negative electrode material of the lithium battery by using the waste zinc-manganese dioxide battery as claimed in claim 1, wherein the temperature of the hydrothermal treatment in the step S3 is controlled to be 110-120 ℃, and the time of the hydrothermal treatment is 10-12h.
4. The process for preparing the negative electrode material of the lithium battery by using the waste zinc-manganese dioxide battery as claimed in claim 1, wherein the porous nanocarbon is prepared by the following method:
adding glucose into deionized water, adding sodium carboxymethylcellulose, heating in a water bath at 40-45 ℃ and magnetically stirring for 20min to obtain a mixed solution D, transferring the mixed solution D into a reaction kettle, heating to 180-200 ℃ at a heating rate of 10 ℃/min, reacting for 20h at the temperature, filtering, and washing with absolute ethyl alcohol for three times to obtain carbon nano microspheres;
and secondly, mixing the carbon nano-microspheres and the carbon black according to the weight ratio of 2: 1 to prepare a mixture, then adding a pore-forming agent, uniformly mixing, heating to 750 ℃ at the heating rate of 15 ℃/min under the argon atmosphere, preserving heat for 4h at the temperature, heating to 980-1100 ℃ at the heating rate of 10 ℃/min, preserving heat for 2h, and cooling to prepare the porous nano-carbon, wherein the weight ratio of the pore-forming agent to the mixture is controlled to be 1.5-1.8: 2.
5. The process for preparing the negative electrode material of the lithium battery by using the waste zinc-manganese dioxide battery as claimed in claim 4, wherein the weight ratio of the glucose to the sodium carboxymethylcellulose to the deionized water is controlled to be 1: 0.02: 100.
6. The process for preparing the negative electrode material of the lithium battery by using the waste zinc-manganese dioxide battery as claimed in claim 4, wherein the pore-forming agent in the second step is one or two of ammonium bicarbonate powder and TW-series pore-forming agent.
7. The process for preparing the negative electrode material of the lithium battery by using the waste zinc-manganese dioxide battery as claimed in claim 4, wherein the porosity of the porous nanocarbon is 28-30%.
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