WO2015192743A1

WO2015192743A1 - Resource reclamation and environmental protection method for recycling lithium ion battery wastes

Info

Publication number: WO2015192743A1
Application number: PCT/CN2015/081421
Authority: WO
Inventors: 王武生
Original assignee: 王武生
Priority date: 2014-06-16
Filing date: 2015-06-15
Publication date: 2015-12-23

Abstract

Disclosed is a resource reclamation and environmental protection method for recycling lithium ion battery wastes. The method comprises: placing a battery cell after being crushed and separated into a high-temperature liquid, so that a diaphragm in the battery cell is decomposed through heating of the high-temperature liquid into gas and/or oil to be discharged; and separating a positive pole material from a positive pole current collector and separating a negative pole material from a negative pole current collector through heating of the high-temperature liquid, to obtain a mixture containing the positive pole material, the negative pole material, the positive pole current collector having a positive pole tab, the negative pole current collector having a negative pole tab, and the high-temperature liquid, the temperature of the high-temperature liquid being not lower than the temperature of decomposition and/or separation of an adhesive. The present invention can not only achieve re-utilization of resources of the lithium ion battery wastes, but also achieve separation and recycling of various composing resources; the recycling process is environment-friendly; the method is applicable to the recycling of lithium ion battery wastes in any form and can be widely applied; the recycling operation is simple, the cost is low, and mass production can be easily realized.

Description

Method for recycling lithium ion battery waste by recycling resources

Technical field

The invention relates to a method for recycling environmentally-friendly lithium-ion battery waste, and belongs to the technical field of lithium ion battery recycling.

Background technique

With the rapid development of the national economy and the people's living standards have greatly improved, the mobile communication industry and the electric vehicle industry have shown rapid development in recent years, and the recycling and environmental pollution of used lithium-ion batteries and their accessories. It has received increasing attention from all walks of life and the public. At present, waste products produced in the production of waste lithium-ion batteries and lithium-ion batteries have become an important part of e-waste. If not handled properly, it will inevitably bring potential threats and pollution to human health and the ecological environment; if scientifically reasonable Recycling and recycling will turn waste into treasure and bring huge economic and social benefits to human society. Therefore, research on the recycling of lithium-ion battery waste has gradually attracted the attention of all countries in the world, especially developed countries, becoming a hot issue in the disposal of electronic waste and a major issue facing the sustainable development of the communication industry and the electric vehicle industry.

Since lithium-ion battery waste contains both toxic and harmful substances and valuable metal elements, effective and safe disposal and recovery of valuable metals in lithium-ion battery waste can not only solve the current environmental pollution caused by lithium-ion battery waste. It can also realize the recycling of resources, which is of great significance to the sustainable development of China's economy, society and environment and the recycling of renewable resources. However, at present, there is a lack of low-cost, environmentally friendly technology for recycling and recycling lithium-ion battery waste, which makes it difficult to obtain safe disposal and efficient resource utilization of lithium ion battery waste. For example, Chinese invention patent application CN01130735.8 discloses a method for recovering metal from a waste lithium ion battery. Although the method can achieve the purpose of recovering metal therein, high temperature furnace roasting is adopted in the recycling process, and also adopted. Adding acid etching and other means not only creates new environmental pollution problems in the recycling process, but also has high recycling cost and complicated process. Therefore, how to realize the pollution-free, low-cost and resource-recovery of lithium-ion battery waste based on the concept of circular economy and the principle of “reduction, reuse, and resource utilization” will have a long way to go and become a national demand An important issue to solve.

Summary of the invention

In view of the above problems and needs in the prior art, the object of the present invention is to provide a method for recycling lithium-ion battery waste by recycling resources, realizing the recycling of lithium ion battery waste, and achieving energy saving and emission reduction purposes.

To achieve the above object, the present invention adopts the following technical solutions:

The invention relates to a method for recycling lithium-ion battery waste in an environmentally-friendly manner, wherein the lithium ion battery waste is derived from waste products generated in a waste lithium ion battery or a lithium ion battery, including a battery core, and the battery core includes a positive electrode And a negative electrode comprising a positive electrode material, a positive electrode current collector and a positive electrode tab, the negative electrode comprising a negative electrode material, a negative electrode current collector and a negative electrode tab.

The method includes the following steps:

A) placing the crushed and separated battery core in a high temperature liquid, and decomposing the separator in the battery core into gas and/or oil discharge by heating the high temperature liquid;

B) The positive electrode material is separated from the positive electrode current collector, the negative electrode material and the negative electrode current collector by heating of the high temperature liquid to obtain a positive electrode material, a negative electrode material, a positive electrode current collector with a positive electrode tab, and a negative electrode with a negative electrode tab. a mixture of a current collector and a high temperature liquid; the temperature of the high temperature liquid is not lower than the decomposition or/and separation temperature of the binder.

Since the separator adheres to the positive electrode material and the negative electrode material during use of the lithium ion battery, the positive electrode material and the negative electrode material enter the high temperature liquid when the separator is decomposed by the heating of the high temperature liquid. In order to prevent the gas and/or oil generated by the decomposition from polluting the environment, and in order to fully recycle the resources, a gas and/or oil recovery device is disposed above the container for holding the high-temperature liquid to recover the gas generated by the decomposition of the separator. / or oil, to avoid secondary pollution to the environment, to achieve the use of this resource.

The separated mixture of the positive electrode material, the negative electrode material, the positive electrode current collector with the positive electrode tab, the negative electrode current collector with the negative electrode tab, and the high temperature liquid is subjected to water-soluble filtration to obtain a positive electrode material, a negative electrode material, and a A mixture of a positive electrode current collector of a positive electrode tab and a negative electrode current collector with a negative electrode tab, and a filtrate containing a high temperature liquid. Since the positive electrode material and the negative electrode material are in a powder form, and the positive electrode current collector having the positive electrode tab and the negative electrode current collector having the negative electrode tab are in the form of a sheet, the positive electrode material and the negative electrode can be obtained by sieving the filter cake. The material is separated from a positive current collector with a positive electrode tab and a negative current collector with a negative electrode tab.

The mixture of the separated positive electrode material and the positive electrode current collector with the positive electrode tab and the high temperature liquid or the mixture of the negative electrode material and the negative electrode current collector with the negative electrode tab and the high temperature liquid is subjected to water-soluble filtration. a filter cake comprising a mixture of a positive electrode material and a positive electrode current collector having a positive electrode tab or a mixture cake containing a negative electrode material and a negative electrode current collector having a negative electrode tab, and a filtrate containing a high temperature liquid, or filtered to obtain a positive electrode The filter cake of the positive electrode current collector of the ear and the filtrate containing the positive electrode material and the high temperature liquid or the filter cake obtained with the negative electrode current collector of the negative electrode tab and the filtrate containing the negative electrode material and the high temperature liquid.

A mixture of a positive electrode current collector having a positive electrode tab and a negative electrode current collector having a negative electrode tab separated by sieving is separated by a difference in melting point or specific gravity, and a positive electrode current collector having a positive electrode tab can be obtained. Separated from the negative current collector with the negative electrode tab.

The positive electrode current collector with the positive electrode tab or the negative electrode current collector with the negative electrode tab separated by sieving is crushed, and then the magnetic fluid is sorted or magnetically selected to make the tab and the current collector phase Separation.

The mixture of the positive electrode material and the negative electrode material obtained by the sieving treatment is subjected to a calcination treatment to separate the positive electrode material from the negative electrode material. Because graphite will volatilize when calcined, and lithium salts will be preserved.

By controlling the size of the filter hole, the positive electrode material and the negative electrode material can pass through the filter hole to obtain a mixture filter cake of the positive electrode current collector with the positive electrode tab and the negative electrode current collector with the negative electrode tab, and the positive electrode material and the negative electrode material. And the filtrate of the high temperature liquid. The separated filtrate containing the positive electrode material, the negative electrode material, and the high-temperature liquid is subjected to secondary filtration to obtain a mixture cake containing a positive electrode material and a negative electrode material, and a filtrate containing a high-temperature liquid.

The obtained filter cake containing the mixture of the positive electrode material and the negative electrode material is subjected to a calcination treatment to separate the positive electrode material from the negative electrode material. The filtrate containing the high temperature liquid is subjected to evaporation and concentration, and the high temperature liquid can be recovered for recycling.

If the positive current collector is aluminum foil and the negative current collector is copper foil, when the temperature of the high temperature liquid is between the melting point of aluminum and the melting point of copper, a separator mesh is disposed in the container for holding the high temperature liquid, so that the aluminum foil is melted. The copper foil is stopped by the isolation net and the copper foil is directly removed from the isolation net, thereby facilitating the separation between the positive current collector and the negative current collector.

In order to ensure that the copper foil does not leak from the isolation net, the fracture separation means that the battery core is torn into a sheet under a protective gas, and the electrolyte is pumped. The tearing method is to tear the cell into a sheet rather than a powder. A protective gas, such as argon, prevents the positive and negative phases from coming into contact during the crushing process to produce combustion. On the one hand, the pumping electrolyte can prevent contamination of the atmosphere, on the other hand, it can reduce the burning probability in the crushing process, and at the same time, the electrolyte can be recycled.

The invention relates to a method for recycling lithium-ion battery waste in an environmentally-friendly manner, wherein the lithium ion battery waste is derived from waste products generated in a waste lithium ion battery or a lithium ion battery, including a positive electrode and a negative electrode constituting a lithium ion battery core; Any one of the separators or a mixture formed arbitrarily between them, the positive electrode including a positive electrode material, a positive electrode current collector, and a positive electrode tab, the negative electrode including a negative electrode material, a negative electrode current collector, and a negative electrode tab. Due to the wide variety of lithium-ion batteries and complex specifications, a large number of battery and accessory waste products are also produced in the production process. Different pretreatment methods are adopted for these different types and different specifications of waste products. For example, if the mobile phone battery is small in size, it is generally recovered by mechanical crushing; while the automobile battery is bulky, the positive electrode, the negative electrode and the diaphragm can be separated by manual separation, and then recovered. For different waste products, the method comprises the following steps:

C) placing the membrane or the mixture containing the membrane in a high temperature liquid, and decomposing the membrane into gas and/or oil by heating of the high temperature liquid; the temperature of the high temperature liquid is not lower than the decomposition temperature of the membrane;

D) placing a positive electrode or a negative electrode or a mixture of a positive electrode and a negative electrode in a high-temperature liquid, and separating the positive electrode material from the positive electrode current collector or/and the negative electrode material and the negative electrode current collector by heating of the high-temperature liquid to obtain a positive electrode material and a Positive a mixture of a polar positive current collector or/and a negative electrode material and a negative electrode current collector having a negative electrode tab, and a high temperature liquid; the temperature of the high temperature liquid is not lower than a binder for bonding the positive electrode material and the negative electrode material Decomposition or separation temperature.

When the waste product is a diaphragm, it is added to the high temperature liquid, and the temperature of the high temperature liquid reaches a decomposition temperature of the membrane to between 450 degrees, and the diaphragm is decomposed into gas and/or oil by heating of the high temperature liquid; A gas and/or oil recovery device is disposed above the vessel to recover the gas and/or oil produced by the decomposition of the membrane to avoid secondary pollution to the environment and to utilize the resource. The high temperature liquid is then filtered to obtain a filter cake comprising a positive electrode material and/or a negative electrode material.

When the waste product is a positive electrode or a negative electrode, it is added to the high temperature liquid, and the temperature of the high temperature liquid is not lower than the decomposition or separation temperature of the binder for bonding the positive electrode material and the negative electrode material. Then, the high temperature liquid and the positive electrode material or the negative electrode material are filtered to obtain a filter cake of the positive electrode material or the negative electrode material and a filtrate containing the high temperature liquid; the filtrate is subjected to evaporation and concentration, and the high temperature liquid can be recovered for recycling.

When the obtained electrode material is a positive electrode material, the adhesive remaining therein can be decomposed and removed by heat oxidation. The positive electrode material obtained by the separation may leave some binder or a decomposition residue of the binder such as carbon, etc., and the carbon dioxide may be volatilized by high-temperature oxidation treatment, thereby improving the purity of the obtained positive electrode material such as lithium salt. Of course, oxygen can be added during the high temperature oxidation treatment to enhance the effect of the oxidation treatment.

When the waste product is a mixture of a positive electrode and a negative electrode, it is added to a high temperature liquid, and the temperature of the high temperature liquid is not lower than the decomposition or separation temperature of the binder for bonding the positive electrode material and the negative electrode material. The positive electrode material is separated from the positive electrode current collector, the negative electrode material and the negative electrode current collector by heating of the high temperature liquid to obtain a positive electrode current collector, a negative electrode material, a positive electrode current collector with a positive electrode tab, and a negative electrode current collector with a negative electrode tab. And a mixture of high temperature liquids.

The separated mixture of the positive electrode material, the negative electrode material, the positive electrode current collector with the positive electrode tab, the negative electrode current collector with the negative electrode tab, and the high temperature liquid is subjected to water-soluble filtration to obtain a positive electrode material, a negative electrode material, and a A mixture of a positive electrode current collector of a positive electrode tab and a negative electrode current collector with a negative electrode tab, and a filtrate containing a high temperature liquid. Since the positive electrode material and the negative electrode material are in a powder form, the positive electrode material and the negative electrode material can be separated from the positive electrode current collector of the positive electrode tab and the negative electrode current collector having the negative electrode tab by sieving the filter cake.

A positive current collector with a positive electrode tab or a negative current collector with a negative electrode tab obtained by separating the difference in melting point or specific gravity is used for crushing, and then magnetic fluid separation or magnetic separation is used to make the pole The ear is separated from the current collector.

If the positive current collector is aluminum foil and the negative current collector is copper foil, when the temperature of the high temperature liquid is between the melting point of aluminum and the melting point of copper, a separator mesh is disposed in the container for holding the high temperature liquid, so that the aluminum foil is melted. The copper foil is stopped by the isolation net and the copper foil is directly removed from the isolation net, thereby facilitating the separation between the positive current collector and the negative current collector. Since the thickness of the aluminum foil is very thin, it is recovered in the air by a conventional method, such as heat recovery, easy oxidation, low recovery rate, and waste of resources. When the temperature of the high-temperature liquid is higher than the melting point of aluminum, the aluminum foil is melted into aluminum particles, and when the aluminum particles are melted and recovered, the aluminum particles have the advantages of low loss and high yield, thereby improving the recovery value.

The high temperature liquid is a molten salt, and the molten salt is in a stable state at a high temperature and is not decomposed by heat. Such as: a mixed salt of chloride or chloride. Because the price of chlorinated salt is cheap, such as sodium chloride, magnesium chloride, etc., the raw materials are widely available. Chloride, such as salt, does not decompose at high temperatures, and the aluminum foil therein can be melted.

The high temperature liquid does not chemically react with the waste product added thereto to ensure the purity and reuse value of the recovered product. For example, the high temperature liquid used for recycling the positive electrode does not chemically react with the positive electrode and the positive electrode material; the high temperature liquid for recycling the negative electrode does not chemically react with the negative electrode and the negative electrode material; and the high temperature liquid for recovering the mixture of the positive electrode and the negative electrode does not react with the positive electrode and the positive electrode. The material reacts with the negative electrode and the negative electrode material.

Compared with the prior art, the present invention has the following beneficial effects:

The method for recycling and recycling lithium ion battery waste by the invention can not only realize the resource recycling of the lithium ion battery waste, but also complete the recycling and separation, and can realize the separation and resource utilization of various constituent resources; There is no waste water, waste gas and waste residue in the recycling process, which can avoid secondary pollution and achieve real energy saving and emission reduction. In addition, the method of the invention can be applied to any form of lithium ion battery waste, has wide application range, and recycling operation Simple, low cost, and easy to achieve scale.

DRAWINGS

1 is a flow chart of a process for recycling a positive electrode of a lithium ion battery according to the first embodiment.

2 is a flow chart of a process for recycling and recycling an anode of a lithium ion battery according to Embodiment 2.

3 is a flow chart showing another process for recycling and recycling a positive electrode of a lithium ion battery according to Embodiment 3.

4 is a flow chart showing another process for recycling a lithium ion battery negative electrode according to the fourth embodiment.

FIG. 5 is a flow chart showing a process for recycling and recycling a separator of a lithium ion battery according to Embodiment 5.

6 is a flow chart showing a process for recycling resources of a positive and negative electrode mixture of a lithium ion battery according to Embodiment 6.

7 is a flow chart showing another process for recycling resources of the positive and negative electrodes of the lithium ion battery according to the seventh embodiment.

8 is a process flow diagram of a negative electrode in a mixture of a positive electrode and a negative electrode of a waste lithium ion battery, which is provided in the eighth embodiment.

9 is a process flow diagram of a positive electrode in a mixture of a positive electrode and a negative electrode of a waste lithium ion battery, which is provided by the embodiment.

FIG. 10 is a process flow diagram of another negative electrode in a mixture of a positive electrode and a negative electrode of a waste lithium ion battery, which is provided by the embodiment 10.

11 is a process flow diagram of another positive electrode in a mixture of a positive electrode and a negative electrode of a waste lithium ion battery, which is provided by the embodiment 11.

12 is a process flow diagram of resource recycling and environmental protection recycling of a lithium ion battery cell according to Embodiment 12.

FIG. 13 is a flow chart showing another process for recycling and recycling a lithium ion battery cell according to Embodiment 13.

detailed description

The technical solutions of the present invention are further elaborated below in conjunction with the embodiments and the accompanying drawings:

Example 1

Referring to FIG. 1 , a process for recycling and recycling a positive electrode of a lithium ion battery provided by the embodiment is as follows: a positive electrode of a lithium ion battery is placed in a high temperature liquid, and the positive electrode may be a waste lithium ion battery. Separated, it can also be the positive waste produced in the production process. The temperature of the high temperature liquid is greater than the melting point of aluminum; the high temperature liquid described herein may be a molten salt such as sodium chloride, which is heated by a high temperature liquid, wherein the positive current collector-aluminum foil is melted and adhered to the positive electrode set. The positive electrode material on the fluid (such as lithium cobalt oxide) will be separated into the high temperature liquid; water is added to the high temperature liquid, and the water solution is dissolved to form an aqueous solution for one filtration. The so-called primary filtration is through the mesh of the control filter. The size of the pores enables the positive electrode material to be filtered and the aluminum particles cannot be filtered, thereby obtaining an aluminum filter cake and a mixed filtrate containing the positive electrode material and the high temperature liquid; the aluminum filter cake is washed and dried to obtain an aluminum block; Enter By secondary filtration, a filter cake containing a positive electrode material (such as a lithium salt) and a filtrate containing a high temperature liquid are obtained; the filter cake is washed and dried, and then heated and oxidized to obtain a high content of a positive electrode material (eg, cobalt). Lithium acid powder). The filtrate containing the high temperature liquid is subjected to evaporation concentration treatment, and a high temperature liquid can be recovered for recycling.

Example 2

Referring to FIG. 2, a process for recycling and recycling an anode of a lithium ion battery provided by the embodiment is as follows: a negative electrode of a lithium ion battery is added to a high temperature liquid, and the negative electrode may be separated from a waste lithium ion battery. The obtained waste can also be produced in the production process. The temperature of the high temperature liquid is generally controlled between 400 ° C and 500 ° C. At this temperature, the adhesive bonding the negative electrode material can be decomposed, so that the negative electrode material adhered to the negative electrode current collector is separated and enters the high temperature liquid. Water is added to the high-temperature liquid, and an aqueous solution is formed by the dissolution of water, and filtration is performed once to obtain a mixed cake containing the negative electrode current collector and a mixed filtrate containing the negative electrode material and the high-temperature liquid. The so-called primary filtration is to control the size of the filter mesh to filter the negative electrode material and the negative electrode current collector can not be filtered; after the filter cake containing the negative electrode current collector is cleaned and dried, the negative electrode current collector, such as copper foil; The mixed filtrate is subjected to secondary filtration to obtain a filter cake containing a negative electrode material and a filtrate containing a high temperature liquid; the filter cake is washed and dried to obtain a negative electrode material, such as graphite powder; the graphite powder can be washed and dried again. use. The filtrate containing the high temperature liquid is subjected to evaporation concentration treatment, and a high temperature liquid can be recovered for recycling.

Example 3

Referring to FIG. 3, another process for recycling and recycling the positive electrode of the lithium ion battery provided by the embodiment is as follows: the positive electrode of the lithium ion battery is put into the high temperature liquid, and the temperature of the high temperature liquid is higher than the melting point of the aluminum; The heating of the high-temperature liquid causes the positive current collector-aluminum foil to melt, so that the positive electrode material-lithium salt (such as lithium cobalt oxide) adhered to the positive current collector is separated into the high-temperature liquid; Water is added, an aqueous solution is formed by dissolution of water, and filtration is carried out to obtain a mixture cake containing a positive electrode material and a positive electrode current collector and a filtrate containing a high-temperature liquid; the obtained mixture cake is washed and dried, and then subjected to a sieving treatment. Since the positive electrode material is powdery, the size and specific gravity of the aluminum particles of the positive electrode current collector are different, so the two can be separated by sieving to obtain aluminum powder and fine powder of the positive electrode material; the fine powder of the positive electrode material is subjected to heat oxidation treatment, The residual adhesive is oxidized to carbon dioxide to volatilize, thereby obtaining a high content of a positive electrode material such as lithium cobalt oxide powder. The filtrate containing the high temperature liquid is subjected to evaporation concentration treatment, and a high temperature liquid can be recovered for recycling.

Example 4

Referring to FIG. 4, another process for recycling and recycling the lithium ion battery negative electrode provided by the embodiment is as follows: the negative electrode of the lithium ion battery is added to the high temperature liquid, and the temperature of the high temperature liquid is generally controlled at 400 ° C. Between 500 ° C, at this temperature, the adhesive bonding the negative electrode material can be decomposed, so that the negative electrode material adhered to the negative electrode is negative. The polar current collector is detached and enters into the high temperature liquid; water is added to the high temperature liquid, and the water solution is dissolved to form an aqueous solution, which is filtered to obtain a mixture cake containing the negative electrode material and the negative electrode current collector and a filtrate containing the high temperature liquid; The obtained mixture cake is washed and dried, and then subjected to sieving treatment; since the anode material is powdery, the size and specific gravity of the anode current collector-copper foil are different, so the two can be separated by sieving. Separate copper foil and anode material. The filtrate containing the high temperature liquid is subjected to evaporation concentration treatment, and a high temperature liquid can be recovered for recycling.

Example 5

Referring to FIG. 5, the process for resource recycling and environmental protection of the separator of the lithium ion battery provided by the embodiment is as follows: the waste lithium ion battery is split to obtain a diaphragm, and the positive and negative materials are adhered to the two sides of the diaphragm respectively. The separator is added to a high temperature liquid, and the temperature of the high temperature liquid is generally controlled between 400 ° C and 500 ° C. At this temperature, the oil obtained after decomposition of the separator has the highest recovery rate. By the heating of the high temperature liquid, the separator can be decomposed into gas and/or oil for recovery. Water is added to the high temperature liquid, and an aqueous solution is formed by the dissolution of water, and the filtrate and the filter cake are obtained by filtration. The filtrate is subjected to evaporation treatment to recover a high temperature liquid for recycling. After the filter cake is washed and dried, the obtained mixture of the positive and negative materials is subjected to heat oxidation treatment, and the graphite powder therein is oxidized to carbon dioxide volatilization to obtain lithium cobalt oxide powder.

Example 6

Referring to FIG. 6 , a process for recycling a positive and negative mixture of a lithium ion battery according to the present embodiment is as follows: the positive and negative mixture obtained by separating the used lithium ion battery into the mixture is put into In a high temperature liquid, the temperature of the high temperature liquid is greater than the melting point of aluminum lower than the melting point of copper. By the heating action of the high temperature liquid, the positive electrode current collector-aluminum foil is melted, and the positive electrode material (such as lithium cobalt oxide) adhered to the positive electrode current collector is separated from the positive electrode current collector aluminum foil into the high temperature liquid. The anode current collector—the graphite powder on the copper foil will detach from the high temperature liquid under the action of high temperature. Water is added to the high temperature liquid, an aqueous solution is formed by dissolution of water, and filtration is carried out to obtain a cake and a filtrate. The filtrate is subjected to evaporation treatment to recover a high temperature liquid for recycling. The filter cake is washed and dried, and then sieved. Since the positive and negative materials are fine powder, and the positive and negative current collectors are granular and flake, the two can be separated by sieving and sieved. After the separation, a mixture of fine powdery positive and negative materials and a mixture of particulate and flake positive and negative current collectors were obtained. The mixture of the positive and negative materials is subjected to heat oxidation treatment, and the graphite powder therein is oxidized to carbon dioxide volatilization to obtain lithium cobalt oxide powder. The mixture of the positive and negative current collectors is physically separated, for example, by utilizing the difference in specific gravity between the two or the difference in melting point between the two, for example, by magnetic fluid separation, the metal aluminum block and the metal copper foil can be separated.

Example 7

Referring to FIG. 7 , another embodiment of the present invention provides a resource ring for the positive and negative electrodes of a lithium ion battery. The recycling process is as follows: the positive and negative electrode mixture obtained by disassembling the waste lithium ion battery is put into a high temperature liquid, and the temperature of the high temperature liquid is higher than the melting point of aluminum lower than the melting point of copper. By the heating action of the high temperature liquid, the positive electrode current collector-aluminum foil is melted, and the positive electrode material (such as lithium cobaltate) adhered to the positive electrode current collector is separated from the positive electrode current collector-aluminum foil into the high temperature liquid. The anode current collector—the graphite powder on the copper foil will detach from the high temperature liquid under the action of high temperature. Water is added to the high temperature liquid, and an aqueous solution is formed by dissolution of water, and the filter cake and the filtrate are obtained by one filtration. The resulting filter cake was a mixture of particulate and flake positive and negative current collectors. Since the positive and negative materials are fine powder and the positive and negative current collectors are granular and flake-shaped, the size of the filter pores can be adjusted to allow the fine powdered positive and negative materials to pass through the filter screen. Fluid cannot pass. The filtrate is subjected to secondary filtration, and the positive and negative materials in the filtrate are filtered to obtain a filter cake containing a mixture of positive and negative materials and a filtrate containing a high temperature liquid, and the filtrate is subjected to evaporation treatment to recover a high temperature liquid for recycling. The filter cake containing the mixture of positive and negative materials is washed and dried to obtain a mixture of positive and negative materials, and the mixture of the positive and negative materials is heated and oxidized to oxidize the graphite powder to carbon dioxide to be separated. A lithium cobaltate powder is obtained. The filter cake containing the mixture of the positive and negative current collectors is washed and dried to obtain a mixture of positive and negative current collectors, and the mixture of the positive and negative current collectors is physically separated, for example, by utilizing the difference in specific gravity between the two or The difference in melting point between the two can be separated into a metal aluminum block and a metal copper foil.

Example 8

Referring to FIG. 8 , a process for recycling a negative electrode in a mixture of a positive electrode and a negative electrode of a waste lithium ion battery according to the present embodiment is as follows: a mixture of a positive electrode and a negative electrode obtained by crushing and separating a lithium ion battery The positive electrode and the negative electrode are separated by a jigging beneficiation method or a magnetic fluid separation method or a specific gravity separation method or an artificial separation method. The separated negative electrode is placed in a high temperature liquid having a temperature greater than a decomposition or separation temperature of the binder; and a negative electrode material (for example, graphite powder) adhered to the negative electrode current collector by heating of the high temperature liquid It will separate into the high temperature liquid; add water to the high temperature liquid, form an aqueous solution by dissolving the water, and filter to obtain a filter cake and a filtrate. The filter cake is washed and dried, and then sieved to obtain a negative electrode material (such as graphite powder) and a negative electrode current collector (such as copper foil). The filtrate containing the high temperature liquid is subjected to evaporation concentration treatment, and a high temperature liquid can be recovered for recycling.

Example 9

Referring to FIG. 9 , a process for recycling a positive electrode in a mixture of a positive electrode and a negative electrode of a waste lithium ion battery provided by the present embodiment is as follows: a mixture of a positive electrode and a negative electrode obtained by crushing and separating a lithium ion battery The positive electrode and the negative electrode are separated by a jigging beneficiation method or a magnetic fluid separation method or a specific gravity separation method or an artificial separation method. The separated positive electrode is placed in a high temperature liquid, and the temperature of the high temperature liquid is generally controlled between 450 ° C and 700 ° C at this temperature. The adhesive for bonding the positive electrode material is decomposed, so that the positive electrode material adhered to the positive electrode current collector is detached and enters the high temperature liquid; water is added to the high temperature liquid, and the water solution is dissolved to form an aqueous solution. Filtration can obtain a filter cake containing a positive electrode current collector and a mixed filtrate containing a positive electrode material and a high temperature liquid. The so-called primary filtration is to control the size of the filter mesh to filter the positive electrode material and the positive electrode current collector cannot be filtered; After the filter cake of the fluid is cleaned and dried, a positive current collector is obtained, such as an aluminum block; the mixed filtrate is subjected to secondary filtration to obtain a filter cake containing a positive electrode material and a filtrate containing a high temperature liquid; the filter cake is cleaned and baked. Dry, that is, to obtain a positive electrode material, such as: lithium cobalt oxide powder, the heating and oxidation treatment of the filter cake after washing and drying can increase the content thereof; the filtrate containing the high temperature liquid is subjected to evaporation concentration treatment, and the high temperature liquid can be recovered to recycle use.

Example 10

Referring to FIG. 10, another process for recycling the negative electrode in the mixture of the positive electrode and the negative electrode of the waste lithium ion battery provided by the present embodiment is as follows: the positive electrode and the negative electrode obtained by crushing and separating the lithium ion battery are obtained. The mixture is separated from the negative electrode by a jigging beneficiation method or a magnetic fluid separation method or a specific gravity separation method or an artificial separation method. The separated negative electrode is placed in a high temperature liquid, and the negative electrode material (such as graphite powder) adhered to the negative electrode current collector is separated into the high temperature liquid by the heating action of the high temperature liquid; water is added to the high temperature liquid, The aqueous solution is formed by dissolution of water, and once filtered, a filter cake containing a negative electrode current collector and a mixed filtrate containing a negative electrode material and a high temperature liquid can be obtained. The so-called primary filtration is to filter the negative electrode material by controlling the size of the filter mesh hole and the negative electrode. The current collector cannot be filtered; after the filter cake containing the negative current collector is cleaned and dried, a negative current collector, such as a copper foil, is obtained; and the mixed filtrate is subjected to secondary filtration to obtain a filter cake containing the negative electrode material and a high temperature. The liquid filtrate; the filtrate containing the high temperature liquid is subjected to evaporation concentration treatment, and the high temperature liquid can be recovered for recycling.

Example 11

Referring to FIG. 11 , another process for recycling the positive electrode in the mixture of the positive electrode and the negative electrode of the waste lithium ion battery provided by the present embodiment is as follows: the positive electrode and the negative electrode obtained by crushing and separating the lithium ion battery are obtained. The mixture is separated from the negative electrode by a jigging beneficiation method or a magnetic fluid separation method or a specific gravity separation method or an artificial separation method. The separated positive electrode is placed in a high temperature liquid, and the temperature of the high temperature liquid is generally controlled between 450 ° C and 700 ° C. At this temperature, the adhesive bonding the positive electrode material can be decomposed to adhere to the positive electrode. The positive electrode material is separated from the positive electrode current collector into the high temperature liquid; water is added to the high temperature liquid, and the water solution is dissolved to form an aqueous solution, which is filtered to obtain a mixture filter cake containing the positive electrode material and the positive electrode current collector and a high temperature liquid containing liquid. Filtrate; the obtained mixture cake is washed and dried before being subjected to sieving treatment; since the positive electrode material is powdery, the size and specific gravity of the positive electrode current collector aluminum particles are different, so the two can be separated by sieving. The separated aluminum particles and the fine powder of the positive electrode material are obtained; the content of the positive electrode material powder is heated and oxidized to increase the content thereof, and a positive electrode material such as lithium cobaltate powder is obtained. For high temperature liquids The filtrate is subjected to evaporation concentration treatment, and a high temperature liquid can be recovered for recycling.

Example 12

Referring to FIG. 12, a process for recycling and recycling a lithium ion battery core according to the embodiment is as follows: a lithium ion battery core obtained by disassembling a waste lithium ion battery is put into a high temperature liquid, and a high temperature liquid The temperature is generally controlled between 400 ° C ~ 500 ° C; because the two sides of the diaphragm are adhered to the positive and negative materials, when the diaphragm is added to the high temperature liquid, the diaphragm is decomposed into gas and / or by the heating of the high temperature liquid The oil is recovered. Continue to raise the temperature of the high temperature liquid so that the temperature is higher than the melting point of aluminum lower than the melting point of copper, and the positive electrode current collector aluminum foil is melted by the further heating of the high temperature liquid, and the positive electrode material adhered to the positive electrode current collector is lithium. The salt (such as lithium cobalt oxide) will leave the positive current collector - the aluminum foil enters the high temperature liquid, and the graphite powder adhered to the negative current collector - copper foil also escapes into the high temperature liquid under the action of high temperature. Water is added to the high-temperature liquid, and the aqueous solution is dissolved by water to perform primary filtration. Since the positive and negative electrode materials are fine powder, the positive and negative current collectors are granular and flake-shaped, and the size of the filter pores is adjusted by adjusting the size of the filter. The fine powdery positive and negative materials pass through the sieve, and the positive and negative current collectors cannot pass, and the filter cake and the filtrate are obtained. The obtained filter cake is a granular and flake-shaped positive and negative current collector. The filtrate is subjected to secondary filtration to obtain a filter cake and a filtrate containing the positive and negative materials, and the obtained filtrate is subjected to evaporation to recover a high-temperature liquid for recycling; the filter cake containing the positive and negative materials is washed and dried to obtain positive and a mixture of negative electrode materials; the obtained mixture of positive and negative materials is subjected to heat oxidation treatment, and the graphite powder therein is oxidized to carbon dioxide volatilization, that is, lithium cobaltate powder is separated. The filter cake containing the positive and negative current collectors is washed and dried to obtain a positive and negative current collector mixture, and the obtained positive and negative current collector mixtures are physically separated, for example, by utilizing the difference in specific gravity between the two or the melting point of the two. The difference is that a separated metal aluminum block and a metal copper foil can be obtained.

Example 13

Referring to FIG. 13 , another process for recycling and recycling the lithium ion battery core provided by the embodiment is as follows: the lithium ion battery core obtained by disassembling the waste lithium ion battery is put into the high temperature liquid, The two sides of the diaphragm are respectively adhered to the positive and negative materials. When the separator is added to the high temperature liquid, the temperature of the high temperature liquid is generally controlled between 400 ° C and 500 ° C. At this temperature, the oil obtained after the decomposition of the separator is recovered. The highest rate, by the heating of the high temperature liquid, the membrane is decomposed into gas and / or oil to be recovered. The temperature of the high temperature liquid is continuously increased so that the temperature of the high temperature liquid is higher than the melting point of aluminum lower than the melting point of copper. By further heating of the high temperature liquid, the positive electrode current collector-aluminum foil is melted, and the positive electrode material (such as lithium cobalt oxide) adhered to the positive electrode current collector is separated from the positive electrode current collector - the aluminum foil enters the high temperature liquid. In the same way, the graphite powder adhered to the negative current collector-copper foil also escapes into the high temperature liquid under the action of high temperature. Water is added to the high-temperature liquid, an aqueous solution is formed by dissolution of water, and filtration is carried out to obtain a cake and a filtrate, and the obtained filtrate is subjected to evaporation to recover a high-temperature liquid for recycling. The resulting filter cake is washed and dried, and then In the sieving, since the positive and negative materials are fine powder, and the positive and negative current collectors are in the form of granules and flakes, the two can be separated by sieving, and after sieving, respectively, a fine powder is obtained. A mixture of negative electrode materials and positive and negative current collectors in the form of granules and flakes. Then, the mixture of the positive and negative electrode materials is subjected to heat oxidation treatment, and the graphite powder therein is oxidized to carbon dioxide volatilization, and lithium cobaltate powder is separated. The positive and negative current collector mixtures are physically separated, for example, by using the difference in specific gravity between the two or the difference in melting point between the two, the two are separated to obtain a separated metal aluminum block and a metal copper foil.

Finally, it is necessary to note that the above embodiments are only used to further explain the technical solutions of the present invention, and are not to be construed as limiting the scope of the present invention. Some of the above-described contents of the present invention are made by those skilled in the art. Non-essential improvements and adjustments are within the scope of the invention.

Claims

The invention relates to a method for recycling lithium-ion battery waste in an environmentally-friendly manner, wherein the lithium ion battery waste is derived from waste products generated in a waste lithium ion battery or a lithium ion battery, including a battery core, and the battery core includes a positive electrode a positive electrode comprising a positive electrode material, a positive electrode current collector and a positive electrode tab, the negative electrode comprising a negative electrode material, a negative electrode current collector and a negative electrode tab; wherein the method comprises the following steps :

A) placing the crushed and separated battery core in a high temperature liquid, and decomposing the separator in the battery core into gas and/or oil discharge by heating the high temperature liquid;

B) The positive electrode material is separated from the positive electrode current collector, the negative electrode material and the negative electrode current collector by heating of the high temperature liquid to obtain a positive electrode material, a negative electrode material, a positive electrode current collector with a positive electrode tab, and a negative electrode with a negative electrode tab. a mixture of a current collector and a high temperature liquid; the temperature of the high temperature liquid is not lower than the decomposition or/and separation temperature of the binder.
The invention relates to a method for recycling lithium-ion battery waste in an environmentally-friendly manner, wherein the lithium ion battery waste is derived from waste products generated in a waste lithium ion battery or a lithium ion battery, including a positive electrode and a negative electrode constituting a lithium ion battery core; Any one of the separators or a mixture formed between them, the positive electrode comprising a positive electrode material, a positive electrode current collector and a positive electrode tab, the negative electrode comprising a negative electrode material, a negative electrode current collector and a negative electrode tab; The method comprises the steps of:

C) placing the membrane or the mixture containing the membrane in a high temperature liquid, and decomposing the membrane into gas and/or oil by heating of the high temperature liquid; the temperature of the high temperature liquid is not lower than the decomposition temperature of the membrane;

D) placing a positive electrode or a negative electrode or a mixture of a positive electrode and a negative electrode in a high-temperature liquid, and separating the positive electrode material from the positive electrode current collector or/and the negative electrode material and the negative electrode current collector by heating of the high-temperature liquid to obtain a positive electrode material and a a positive electrode current collector or/and a mixture of a negative electrode material and a negative electrode current collector having a negative electrode tab, and a high temperature liquid; the temperature of the high temperature liquid is not lower than a bond for bonding the positive electrode material and the negative electrode material The decomposition or separation temperature of the agent.
The method according to claim 1 or 2, wherein the method further comprises the steps of:

E) separating and separating the mixture containing the positive electrode material, the negative electrode material, the positive electrode current collector with the positive electrode tab, the negative electrode current collector with the negative electrode tab, and the high temperature liquid to obtain a positive electrode material, a negative electrode material, and a belt a mixture of a positive electrode current collector having a positive electrode tab and a negative electrode current collector with a negative electrode tab, and a filtrate containing a high temperature liquid, or a positive electrode current collector having a positive electrode tab and a negative electrode having a negative electrode tab A fluid mixture mixture filter cake and a filtrate containing a positive electrode material, a negative electrode material, and a high temperature liquid.
The method of claim 3, wherein the method further comprises the steps of:

F) sieving the separated mixture containing the positive electrode material, the negative electrode material, the positive electrode current collector with the positive electrode tab, and the negative electrode current collector with the negative electrode tab to obtain a mixture of the positive electrode material and the negative electrode material, and a belt a mixture of a positive current collector having a positive electrode tab and a negative current collector having a negative electrode tab;

G) The filtrate containing the positive electrode material, the negative electrode material, and the high temperature liquid is subjected to secondary filtration to obtain a mixture of the positive electrode material and the negative electrode material.
The method of claim 4, wherein the method further comprises the steps of:

H) calcining the separated mixture of the positive electrode material and the negative electrode material to separate the positive electrode material from the negative electrode material; separating the positive electrode current collector with the positive electrode tab and the negative electrode current collector with the negative electrode tab The mixture is separated by a difference in melting point or a difference in specific gravity, and the positive electrode current collector having the positive electrode tab is separated from the negative electrode current collector having the negative electrode tab.
The method of claim 2, wherein the method further comprises the steps of:

I) water-soluble filtration of the separated mixture containing the positive electrode material and the positive electrode current collector with the positive electrode tab and the high temperature liquid or the mixture of the negative electrode material and the negative electrode current collector with the negative electrode tab and the high temperature liquid. Obtaining a mixture filter cake containing a positive electrode material and a positive electrode current collector with a positive electrode tab or a mixture cake containing a negative electrode material and a negative electrode current collector with a negative electrode tab, and a filtrate containing a high temperature liquid, or filtered to obtain a positive electrode A filter cake of a positive electrode current collector of a polar ear, a filtrate containing a positive electrode material and a high temperature liquid, or a filter cake obtained with a negative electrode current collector of a negative electrode tab, and a filtrate containing a negative electrode material and a high temperature liquid.
The method of claim 6 wherein the method further comprises the steps of:

J) sieving the mixture of the separated positive electrode material and the positive electrode current collector with the positive electrode tab or the negative electrode material and the negative electrode current collector with the negative electrode tab to obtain a phase separated positive electrode material and a positive electrode a polar positive current collector or negative electrode material and a negative current collector with a negative electrode tab;

K) The separated filtrate or negative electrode material containing the positive electrode material and the high temperature liquid and the filtrate of the high temperature liquid are subjected to secondary filtration to obtain a separated positive electrode material or negative electrode material.
The method according to claim 5 or 7, wherein the method further comprises the steps of:

L) The separated positive electrode current collector with positive electrode tab or negative electrode current collector with negative electrode tab is crushed, and then the magnetic pole is separated from the current collector by magnetic fluid sorting or magnetic separation.
A method according to claim 1 or 2, characterized in that a gas and/or oil recovery means is arranged above the vessel containing the high temperature liquid.
The method according to claim 1 or 2, characterized in that a spacer is provided in the container for holding the high temperature liquid.
The method according to claim 1 or 2, wherein the high temperature liquid is a molten salt.
The method according to claim 1 or 2, wherein the high temperature liquid does not chemically react with the positive and negative electrode materials and the positive and negative current collectors.
The method according to claim 1, wherein the crushing separation in the step A) means that the battery core is torn into a sheet under a shielding gas, and the electrolyte is pumped.