CN110752384B - Recycling method of waste zinc-manganese battery - Google Patents

Recycling method of waste zinc-manganese battery Download PDF

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CN110752384B
CN110752384B CN201910874497.2A CN201910874497A CN110752384B CN 110752384 B CN110752384 B CN 110752384B CN 201910874497 A CN201910874497 A CN 201910874497A CN 110752384 B CN110752384 B CN 110752384B
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zinc
manganese
batteries
battery
electrolyte
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CN110752384A (en
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雷立旭
冀帅
张天择
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Southeast 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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/21—Manganese oxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • 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 recycling method of waste zinc-manganese batteries, which comprises 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 to react 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.

Description

Recycling method of waste zinc-manganese battery
Technical Field
The invention relates to the recycling production of batteries, in particular to a recycling method of waste zinc-manganese batteries.
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 reserve 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. Enclosing electrochemically active MnO around a carbon rod 2 Forming a paste of mineral powder, graphite powder and aqueous ammonium chloride solution into the positive electrode of the battery, separating the positive electrode from a metallic zinc can as the negative electrode by a separator, and separating the positive and negative electrodes and sealing the batteryThe organic material forms an acidic (or carbon) zinc-manganese dry battery. Thus, the acid zinc-manganese battery contains carbon rods and MnO 2 The zinc-plated composite material comprises a zinc cylinder, an iron sheet shell, graphite powder, ammonium chloride and a paper diaphragm. The alkaline zinc-manganese dioxide battery is different from the alkaline zinc-manganese dioxide battery in structure, a negative electrode formed by zinc powder and a steel needle is arranged in the middle, electrolytic manganese dioxide and an iron bucket are used as positive electrodes and arranged outside, and KOH aqueous solution is used as electrolyte. Therefore, the alkaline zinc-manganese battery contains zinc, a steel needle, an iron shell and MnO 2 And an alkaline solution. In the waste battery, most of the metal zinc is changed into divalent zinc compound MnO 2 Most of them become trivalent manganese compounds.
The zinc-manganese battery has a disadvantage of being disposable, and thus, although the purchase cost is low, the use cost is higher than that of the secondary battery. At present, metals with higher toxicity such as mercury and cadmium are not used in the zinc-manganese battery, and the environmental friendliness is greatly improved. However, zinc-manganese batteries contain valuable elements such as zinc, manganese and iron, which cause certain environmental hazards when directly entering the environment, and more importantly, the valuable metal resources are wasted.
At present, some zinc-manganese battery recycling technical schemes exist. For example, chinese patent application No. 201210496512.2 discloses a method for treating waste zinc-manganese batteries, which comprises the technical route of crushing, dissolving and filtering the batteries to obtain a solution of zinc-manganese salt, then gradually electrodepositing metallic zinc and manganese dioxide, and then extracting heavy metals such as cadmium, copper, lead and the like through ion exchange. The existing zinc-manganese battery recovery treatment mainly aims at zinc oxide, and the resource utilization rate is generally low.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention aims to provide a method for recycling waste zinc-manganese batteries, which can obviously reduce energy consumption, material consumption and pollution risk and can realize the cyclic production of the zinc-manganese batteries.
The technical scheme is as follows: the invention relates to a method for recycling waste zinc-manganese batteries, which comprises the following steps:
(1) Putting the waste batteries into a sorting machine, and sorting according to the size, shape, weight and magnetism strength of the batteries to obtain zinc-manganese batteries, nickel-hydrogen batteries, nickel-cadmium batteries and lithium ion batteries with different specifications, wherein part of secondary batteries, such as the nickel-hydrogen batteries, the nickel-cadmium batteries and the lithium ion batteries, have the same shape and size and need to be separated according to the magnetism and the mass;
(2) And (3) placing zinc-manganese batteries with different specifications into a special shell breaking machine for shell breaking by using a mild physical disassembly technology. Because the iron sheet is easy to be attracted by a magnetic field, the iron sheet is separated by using a magnetic separation technology, and the zinc sheet, the carbon rod, the diaphragm, the steel nail and the battery powder are separated, so that organic matters for separating the positive electrode from the negative electrode and sealing the battery are classified by screening. Cleaning other parts except the battery powder, concentrating, selling or using for other purposes, and cleaning the obtained solid-liquid mixture for extracting electrolyte in the next step;
(3) And mixing the battery powder with the solid-liquid mixture obtained in the last step, adding water for several times to dissolve the electrolyte in the mixture, and performing solid-liquid separation to obtain a solution of the electrolyte and the battery powder without the electrolyte. Evaporating, concentrating and performing fractional crystallization on the electrolyte solution by adopting a low-energy-consumption MVR technology to obtain ammonia water, KCl and KOH;
(4) And (4) adding sulfuric acid and a reducing agent into the battery powder without the electrolyte obtained in the step (3), and stirring to convert all manganese compounds into manganese sulfate and all zinc compounds into zinc sulfate. The reducing agent is a substance capable of reacting with Mn (IV) or Mn (III) compound in sulfuric acid medium to obtain Mn (II) compound, and comprises H 2 O 2 Any one of formic acid, formaldehyde, methanol, oxalic acid, hydrazine and hydroxylamine; the temperature of the reduction reaction is between room temperature and 180 ℃; when the temperature is 100-180 ℃, the reaction is carried out in a pressure vessel. Filtering and separating to obtain a mixed solution of zinc sulfate and manganese sulfate and insoluble substances;
(5) Adding the zinc skin obtained in the step (2) into the mixed solution of zinc sulfate and manganese sulfate obtained in the step (4), stirring to ensure that impurity ions such as iron, lead, cadmium, copper and the like in the mixed solution are all reduced and precipitated to remove impurities, and filtering to obtain a solution only containing zinc sulfate and manganese sulfate;
(6) Electrolyzing the solution of zinc and manganese sulfate obtained in the step (5) to obtain electrolytic manganese dioxide at the anode and zinc at the cathode, wherein the electrolysis temperature is 15-80 ℃;
(7) The resulting zinc and electrolytic manganese dioxide are used to make new alkaline zinc-manganese batteries.
The waste zinc-manganese battery comprises an acid zinc-manganese battery and an alkaline zinc-manganese battery.
In the step (6), the pH value of the mixed solution is controlled to be 0-5, the cell voltage is controlled to be 2.0-2.5V, and the current density is controlled to be 40-200A/m 2 (ii) a When the pH value of the mixed solution is more than 5, adding dilute sulfuric acid to reduce the pH value to 5; and (4) when the pH value of the mixed solution is less than 0, stopping electrolysis, and replacing the sulfuric acid in the step (4) with the formed electrolyte solution for recycling.
The working principle is as follows: when the battery is broken, only the battery powder is chemically treated. First, ammonium chloride in an acid cell can react with KOH in an alkaline cell to produce ammonia gas. The reaction formula is as follows:
NH 4 Cl+KOH＝KCl+NH 3 +H 2 O
thus, ammonia is separated and absorbed by water to obtain ammonia water. Thereafter, water was added to the battery powder in several portions to wash out all the electrolyte. Evaporating, concentrating and performing fractional crystallization on the electrolyte solution to obtain solid such as KCl, KOH and the like. The obtained ZnO, mnOOH and MnO 2 Etc. and then reducing the high-valence manganese compound with a reducing agent. In principle, any organic or inorganic reducing agent which can be reacted with Mn (IV) or Mn (III) compounds in a sulphuric acid medium to give Mn (II) compounds can be used, in particular oxidation products which are harmless gases, such as N 2 、O 2 And CO 2 Substances of, e.g. H 2 O 2 Formic acid, formaldehyde, methanol, oxalic acid, hydrazine and hydroxylamine substances. With H 2 O 2 For example, the reaction formula is:
MnO 2 +H 2 O 2 +H 2 SO 4 ＝MnSO 4 +O 2 +2H 2 O
2MnOOH+H 2 O 2 +2H 2 SO 4 ＝2MnSO 4 +O 2 +4H 2 O
ZnO+H 2 SO 4 ＝ZnSO 4 +H 2 O
in this way, all the Zn and Mn compounds in the solid are dissolved to form a mixed salt solution of Zn and Mn. The solution can be purified by reducing and precipitating Fe, cu, etc. in the solution by adding the Zn flake separated previously to the solution:
Zn+Fe 2+ ＝Zn 2+ +Fe
Zn+Cu 2+ ＝Zn 2+ +Cu
……
under controlled conditions, the zinc sulphate and manganese sulphate solutions obtained as above are directly electrolysed to obtain electrolytic manganese dioxide on the anode and metallic zinc on the cathode, which can be used in the production of alkaline zinc-manganese batteries. Thus, the aim of manufacturing the high-performance alkaline zinc-manganese battery by using the waste zinc-manganese battery is fulfilled:
ZnSO 4 +MnSO 4 +2H 2 O＝Zn+MnO 2 +2H 2 SO 4
it can be seen that only some reducing agents are consumed in the process, only ammonia water, steel nails, carbon rods, iron sheets and the like are byproducts, and all sulfuric acid generated in the electrolysis process is used by the battery powder. Therefore, the process is very clean and has small pollution risk, and is a green process.
Has the advantages that: compared with the prior art, the invention has the following remarkable characteristics:
1. all battery components are recycled, the best use of the battery components is realized, the recycling rate is high, and the energy consumption, material consumption and pollution risks are greatly reduced;
2. the energy consumption, material consumption and pollution risk in the resource process are reduced to the minimum, and only CO is generated 2 、O 2 、N 2 The gas is discharged, and the byproduct is the mixture of ammonia water and solid saline alkali;
3. the production of low-quality acid zinc-manganese batteries can be eliminated step by step, and compounds for producing high-performance zinc-manganese batteries, such as zinc, electrolytic manganese dioxide and the like, can be directly obtained, so that the cyclic production of high-performance alkaline zinc-manganese batteries is realized;
4. the process is simple and easy to implement, redundant processes are avoided, the requirement of clean production is met, the production cost is reduced, and the resource and sustainable production of the waste zinc-manganese battery are facilitated.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
Example 1
The method for manufacturing the new alkaline zinc-manganese battery by using the waste acidic and alkaline zinc-manganese batteries as raw materials comprises the following steps:
(1) Waste zinc-manganese batteries are put into a sorting machine and sorted according to the size, shape and magnetic strength of the batteries, and particularly, because part of secondary batteries, such as nickel-hydrogen batteries, nickel-cadmium batteries and lithium ion batteries, have the same shape and size, the secondary batteries must be separated according to the magnetic property and mass;
(2) According to classification, the battery is placed in a special shell breaking machine for shell breaking, then iron components are separated by using a magnetic separation technology, other metals such as zinc sheets, steel nails, plastic parts and battery powder are classified by screening, except the battery powder is chemically treated in the following mode, other components are cleaned and then are sold in a centralized mode or used for other purposes, and liquid obtained in the cleaning process and solid powder contained in the liquid are used for extracting electrolyte in the next step;
(3) Mixing the battery powder with the solid-liquid mixture obtained in the step (2), adding water for several times, dissolving the electrolyte, filtering, heating and concentrating the electrolyte, and performing fractional crystallization to obtain ammonia water, KOH, KCl and other solids;
(4) Adding dilute sulfuric acid and H to the electrolyte-removed cell powder 2 O 2 Heating and stirring to react at room temperature to dissolve zinc and manganese compounds, and filtering to remove insoluble substances after the reaction is finished, wherein the solution is a zinc-manganese sulfate solution containing impurities;
(5) Adding the zinc skin obtained by the separation in the step (2) into the zinc-manganese sulfate solutionReducing and depositing impurity metal ions, filtering solids, introducing the electrolyte into an electrolytic cell for electrolysis, so as to obtain manganese dioxide on the anode and metal zinc on the cathode, wherein sulfuric acid is formed in the electrolyte, and the sulfuric acid is used in the step (4); when the pH value of the solution is between 0 and 5 during electrolysis, the cell voltage is controlled between 2.0 and 2.5V, and the current density is not more than 200A/m 2 When the pH value of the electrolyte is more than 5, dilute sulfuric acid needs to be added to reduce the pH value; when the pH value of the solution is less than 0 during electrolysis, stopping electrolysis;
(6) The metal zinc is made into powder and is used for manufacturing a new high-performance alkaline zinc-manganese battery together with manganese dioxide.
Example 2
The method for manufacturing the new alkaline zinc-manganese battery by using the waste acidic and alkaline zinc-manganese batteries as raw materials comprises the following steps:
(1) Waste zinc-manganese batteries are put into a sorting machine and sorted according to the size, shape and magnetic strength of the batteries, and particularly, because part of secondary batteries, such as nickel-hydrogen batteries, nickel-cadmium batteries and lithium ion batteries, have the same shape and size, the secondary batteries must be separated according to the magnetic property and mass;
(2) According to classification, the battery is placed in a special shell breaking machine for shell breaking, then iron components are separated by using a magnetic separation technology, other metals such as zinc sheets, steel nails, plastic parts and battery powder are classified by screening, except the battery powder is chemically treated in the following mode, other components are cleaned and then are sold in a centralized mode or used for other purposes, and liquid obtained in the cleaning process and solid powder contained in the liquid are used for extracting electrolyte in the next step;
(3) Adding water into the battery powder, dissolving the electrolyte, filtering, heating and concentrating the electrolyte, and performing fractional crystallization to obtain ammonia water, KOH, KCl and other solids;
(4) Adding dilute sulfuric acid and formic acid into the battery powder without the electrolyte, reacting at 180 ℃, heating and stirring to dissolve zinc and manganese compounds in the battery powder in a pressure container. After the reaction is finished, filtering to remove insoluble substances, wherein the solution is a mixed solution of zinc-manganese sulfate containing some impurities;
(5) To a mixed solution of zinc manganese sulfateAdding the zinc sheet obtained by the separation in the step (2) to reduce and deposit impurity metal ions, filtering solids, introducing the electrolyte into an electrolytic cell for electrolysis, and obtaining manganese dioxide on an anode and metal zinc on a cathode, wherein sulfuric acid is formed in the electrolyte and is reused in the step (4); when the pH value of the solution is between 0 and 5 during electrolysis, the cell voltage is controlled between 2.0 and 2.5V, and the current density is not more than 200A/m 2 When the pH value of the solution is more than 5 during electrolysis, dilute sulfuric acid needs to be added to reduce the pH value; when the pH value of the solution is less than 0 during electrolysis, the electrolysis is stopped;
(6) The metal zinc is made into powder and is used for manufacturing a new high-performance alkaline zinc-manganese battery together with manganese dioxide.
In the step (4), the reducing agent formic acid can be replaced by formaldehyde, methanol or oxalic acid.
Example 3
The method for manufacturing the new alkaline zinc-manganese battery by using the waste acidic and alkaline zinc-manganese batteries as raw materials comprises the following steps:
(1) Waste zinc-manganese batteries are put into a sorting machine and sorted according to the size, shape and magnetic strength of the batteries, and particularly, because part of secondary batteries, such as nickel-hydrogen batteries, nickel-cadmium batteries and lithium ion batteries, have the same shape and size, the secondary batteries must be separated according to the magnetic property and mass;
(2) According to classification, the battery is placed in a special shell breaking machine for shell breaking, then iron components are separated by using a magnetic separation technology, other metals such as zinc sheets and steel nails, plastic parts and battery powder are classified by screening, except the battery powder is chemically treated in the following mode, other parts are cleaned and then are sold in a centralized mode or used for other purposes, and liquid obtained in the cleaning process and solid powder contained in the liquid are used for extracting electrolyte in the next step;
(3) Mixing the battery powder with the solid-liquid mixture obtained in the step (2), adding water for several times, dissolving the electrolyte, filtering, heating and concentrating the electrolyte, and performing fractional crystallization to obtain ammonia water, KOH, KCl and other solids;
(4) Adding dilute sulfuric acid and hydrazine into the battery powder without the electrolyte, heating and stirring to react at the reaction temperature of 80 ℃, so as to dissolve the zinc and manganese compounds in the battery powder. Filtering to remove insoluble substances after the reaction is finished, wherein the solution is a mixed solution of zinc-manganese sulfate containing some impurities;
(5) Adding the zinc skin obtained by the separation in the step (2) into the mixed solution of zinc-manganese sulfate to reduce and deposit impurity metal ions, filtering out solids, introducing the electrolyte into an electrolytic cell for electrolysis, and obtaining manganese dioxide on an anode and metal zinc on a cathode, wherein sulfuric acid is formed in the electrolyte and is reused in the step (4); when the pH value of the solution is between 0 and 5 during electrolysis, the cell voltage is controlled between 2.0 and 2.5V, and the current density is not more than 200A/m 2 When the pH value of the electrolyte is more than 5, dilute sulfuric acid needs to be added to reduce the pH value; when the pH value of the solution is less than 0 during electrolysis, the electrolysis is stopped;
(6) The zinc metal is made into powder and is used for manufacturing a novel high-performance alkaline zinc-manganese battery together with manganese dioxide.
Wherein, the reducing agent hydrazine in the step (4) can be replaced by hydroxylamine.
Example 4
The method for manufacturing the new alkaline zinc-manganese battery by using the alkaline waste zinc-manganese battery as the raw material comprises the following steps:
(1) Waste zinc-manganese batteries are put into a sorting machine and sorted according to the size, shape and magnetic strength of the batteries, and particularly, because part of secondary batteries, such as nickel-hydrogen batteries, nickel-cadmium batteries and lithium ion batteries, have the same shape and size, the secondary batteries must be separated according to the magnetic property and mass;
(2) According to classification, the battery is placed in a special shell breaking machine for shell breaking, then iron components are separated by using a magnetic separation technology, other metals such as steel nails, plastic parts and battery powder are classified by screening, except the battery powder is chemically treated in the following mode, other parts are cleaned and then are intensively sold or used for other purposes, and liquid obtained in the cleaning process and solid powder contained in the liquid are used for extracting electrolyte in the next step;
(3) Mixing the battery powder and the solid-liquid mixture obtained in the step (2), adding water in times, dissolving the electrolyte in the mixture, filtering, heating the electrolyte for concentration, and performing fractional crystallization to obtain KOH and K 2 CO 3 Wait for solidationA body;
(4) Adding dilute sulfuric acid and hydroxylamine into the battery powder without the electrolyte to react in a pressure container at the reaction temperature of 140 ℃, heating and stirring to react so as to dissolve zinc and manganese compounds in the battery powder, and filtering to remove insoluble substances after the reaction is finished, wherein the solution is a mixed solution of zinc-manganese sulfate and a mixed solution of zinc-manganese sulfate containing impurities;
(5) Adding the zinc skin separated in the step (2) into a zinc-manganese sulfate mixed solution to reduce and deposit impurity metal ions, filtering solids, introducing an electrolyte into an electrolytic cell for electrolysis, and obtaining manganese dioxide on an anode and metal zinc on a cathode, wherein sulfuric acid is formed in the electrolyte and is reused in the step (4); when the pH value of the solution is between 0 and 5 during electrolysis, the cell voltage is controlled between 2.0 and 2.5V, and the current density is not more than 200A/m 2 When the pH value of the electrolyte is more than 5, dilute sulfuric acid needs to be added to reduce the pH value; when the pH value of the solution is less than 0 during electrolysis, stopping electrolysis;
(6) The zinc metal is made into powder and is used for manufacturing a novel high-performance alkaline zinc-manganese battery together with manganese dioxide.
Example 5
The method for manufacturing the new alkaline zinc-manganese battery by using the alkaline waste zinc-manganese battery as the raw material comprises the following steps:
(1) Waste zinc-manganese batteries are put into a sorting machine and sorted according to the size, shape and magnetic strength of the batteries, and particularly, because part of secondary batteries, such as nickel-hydrogen batteries, nickel-cadmium batteries and lithium ion batteries, have the same shape and size, the secondary batteries must be separated according to the magnetic property and mass;
(2) According to classification, the battery is placed in a special shell breaking machine for shell breaking, then iron components are separated by using a magnetic separation technology, other metals such as steel nails, plastic parts and battery powder are classified by screening, except the battery powder is chemically treated in the following mode, other parts are cleaned and then are intensively sold or used for other purposes, and liquid obtained in the cleaning process and solid powder contained in the liquid are used for extracting electrolyte in the next step;
(3) Mixing the battery powder and the solid-liquid mixture obtained in the step (2), adding water in portions, and allowing the mixture to standFiltering after dissolving the electrolyte, heating and concentrating the electrolyte, and performing fractional crystallization to obtain KOH and K 2 CO 3 And the like;
(4) Adding dilute sulfuric acid and formaldehyde into the battery powder without the electrolyte, heating and stirring to react at the reaction temperature of 80 ℃ to dissolve zinc and manganese compounds in the battery powder, and filtering to remove insoluble substances after the reaction is finished, wherein the solution is a mixed solution of zinc-manganese sulfate and a mixed solution of zinc-manganese sulfate containing impurities;
(5) Adding zinc powder into the mixed solution of zinc-manganese sulfate to reduce and deposit impurity metal ions, filtering solids, introducing the electrolyte into an electrolytic cell for electrolysis, so as to obtain manganese dioxide on the anode and metal zinc on the cathode, and reusing sulfuric acid formed in the electrolyte in the step (4); when the pH value of the solution is between 0 and 5 during electrolysis, the cell voltage is controlled between 2.0 and 2.5V, and the current density is not more than 200A/m 2 When the pH value of the electrolyte is more than 5, dilute sulfuric acid needs to be added to reduce the pH value; when the pH value of the solution is less than 0 during electrolysis, stopping electrolysis;
(6) The metal zinc is made into powder and is used for manufacturing a new high-performance alkaline zinc-manganese battery together with manganese dioxide.
Example 6
The method for manufacturing the new alkaline zinc-manganese battery by using the alkaline waste zinc-manganese battery as the raw material comprises the following steps:
(1) Waste zinc-manganese batteries are put into a sorting machine and sorted according to the size, shape and magnetic strength of the batteries, and particularly, because part of secondary batteries, such as nickel-hydrogen batteries, nickel-cadmium batteries and lithium ion batteries, have the same shape and size, the secondary batteries must be separated according to the magnetic property and mass;
(2) According to classification, the battery is placed in a special shell breaking machine for shell breaking, then iron components are separated by using a magnetic separation technology, other metals such as steel nails, plastic parts and battery powder are classified by screening, except the battery powder is chemically treated in the following mode, other parts are cleaned and then are intensively sold or used for other purposes, and liquid obtained in the cleaning process and solid powder contained in the liquid are used for extracting electrolyte in the next step;
(3) Mixing the battery powder with the step (2)Mixing the obtained solid-liquid mixture, adding water in several times, dissolving the electrolyte, filtering, heating the electrolyte for concentration, and fractional crystallization to obtain KOH and K 2 CO 3 And the like;
(4) Adding dilute sulfuric acid and H to the electrolyte-removed cell powder 2 O 2 Heating and stirring at the reaction temperature of 60 ℃ to react so as to dissolve zinc and manganese compounds in the solution, and filtering to remove insoluble substances after the reaction is finished, wherein the solution is a mixed solution of zinc-manganese sulfate and a mixed solution of zinc-manganese sulfate containing impurities;
(5) Adding zinc powder into the mixed solution of zinc-manganese sulfate to reduce and deposit impurity metal ions, filtering out solids, introducing the electrolyte into an electrolytic cell for electrolysis, so as to obtain manganese dioxide on an anode and metal zinc on a cathode, wherein sulfuric acid is formed in the electrolyte and is reused in the step (4); when the pH value of the solution is between 0 and 5 during electrolysis, the cell voltage is controlled between 2.0 and 2.5V, and the current density is not more than 200A/m 2 When the pH value of the electrolyte is more than 5, dilute sulfuric acid needs to be added to reduce the pH value; when the pH value of the solution is less than 0 during electrolysis, stopping electrolysis;
(6) The zinc metal is made into powder and is used for manufacturing a novel high-performance alkaline zinc-manganese battery together with manganese dioxide.

Claims (4)

1. A method for recycling waste zinc-manganese batteries is characterized by comprising the following steps:
(1) Putting the waste batteries into a sorting machine, and sorting according to the size, shape, weight and magnetism of the batteries to obtain zinc-manganese batteries, nickel-hydrogen batteries, nickel-cadmium batteries and lithium ion batteries with different specifications;
(2) Respectively crushing shells of zinc-manganese batteries with different specifications, separating iron sheets by using a magnetic separation technology, screening and classifying zinc skins, carbon rods, diaphragms, steel nails, battery powder and organic matters for insulating positive and negative electrodes and sealing the batteries, respectively cleaning other components except the battery powder, and using the obtained solid-liquid mixture containing the battery powder for next step of extracting electrolyte;
(3) Mixing the battery powder with the solid-liquid mixture obtained in the last step, adding water in several times to dissolve and elute the electrolyte in the mixture, and performing solid-liquid separation to obtain a solution of the electrolyte and the battery powder without the electrolyte; evaporating, concentrating and performing fractional crystallization on the electrolyte solution to obtain an electrolyte;
(4) Adding dilute sulfuric acid and a reducing agent into the battery powder without the electrolyte obtained in the step (3), wherein the reducing agent is a substance capable of reacting with a Mn (IV) or Mn (III) compound in a sulfuric acid medium to obtain a Mn (II) compound, and comprises any one of formic acid, formaldehyde, methanol, oxalic acid, hydrazine and hydroxylamine, the oxidation product of the reducing agent is a dischargeable harmless gas, stirring is carried out to convert all manganese compounds in the oxidizing product into manganese sulfate, all zinc compounds are converted into zinc sulfate, and filtering and separating are carried out to obtain a mixed solution of zinc sulfate and manganese sulfate and insoluble substances;
(5) Adding the zinc skin obtained in the step (2) into the mixed solution of zinc sulfate and manganese sulfate obtained in the step (4), stirring to remove impurity ions, and filtering to obtain a solution only containing zinc sulfate and manganese sulfate;
(6) Electrolyzing the solution of zinc and manganese sulfate obtained in the step (5), obtaining electrolytic manganese dioxide at the anode, obtaining zinc at the cathode, controlling the electrolysis temperature to be 15-80 ℃, controlling the pH value of the mixed solution to be 0-5, controlling the cell voltage to be 2.0-2.5V, and controlling the current density to be 40-200A/m 2 When the pH value of the mixed solution is more than 5, adding dilute sulfuric acid to reduce the pH value to 5, and when the pH value of the mixed solution is less than 0, stopping electrolysis, and using the formed electrolyte to replace sulfuric acid in the step (4) for recycling;
(7) The resulting zinc and electrolytic manganese dioxide are used to make new alkaline zinc-manganese batteries.
2. The recycling method of the waste zinc-manganese dioxide battery according to claim 1, characterized in that: the waste zinc-manganese battery comprises an acid zinc-manganese battery and an alkaline zinc-manganese battery.
3. The recycling method of the waste zinc-manganese dioxide battery according to claim 1, characterized in that: the temperature at which the reduction reaction in the step (4) occurs is room temperature to 180 ℃.
4. The recycling method of the waste zinc-manganese dioxide battery according to claim 3, characterized in that: and (4) carrying out the reduction reaction in the step (4) in a pressure container at the temperature of 100-180 ℃.
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