阅读说明：本技术 一种废旧动力锂电池全组分清洁回收方法 (Method for cleanly recovering all components of waste power lithium battery ) 是由 李兰兰 王甲琴 陈天翼 张明兰 保毓鹏 柴艮风 王杰伟 吴明敏 于 2019-09-12 设计创作，主要内容包括：本发明属于废旧电池回收技术领域,公开废旧动力锂电池全组分清洁回收方法。包括：(1)惰性气体保护、密闭状态下进行拆解、破碎得到电池碎料。(2)将废旧动力锂电池碎料采用强制萃取法分离回收电解液。(3)萃取回收粘结剂。(4)电池碎料烘干。(5)烘干的电池碎料通过分选、筛分,分离回收电极粉料及铜铝粒。有益效果：本发明通过萃取的方法,实现电极粉料与粘结剂及有机溶剂完全分离,高效回收废旧动力锂离子电池中的电解液、粘结剂、电极粉料。整个过程三废零排放,对环境友好。(The invention belongs to the technical field of waste battery recovery, and discloses a method for cleanly recovering all components of waste power lithium batteries. The method comprises the following steps: (1) and under the protection of inert gas, disassembling and crushing in a closed state to obtain the crushed battery. (2) And separating and recycling the electrolyte from the waste power lithium battery crushed aggregates by adopting a forced extraction method. (3) And extracting and recovering the binder. (4) And drying the crushed battery. (5) And separating and screening the dried battery crushed aggregates, and separating and recovering electrode powder and copper-aluminum particles. Has the advantages that: the invention realizes the complete separation of electrode powder from the binder and the organic solvent by an extraction method, and efficiently recovers the electrolyte, the binder and the electrode powder in the waste power lithium ion battery. The whole process has zero emission of three wastes and is environment-friendly.)

1. A method for cleaning and recovering all components of waste power lithium batteries is characterized by comprising the following steps: the method adopts the following technical processes:

a. carrying out charged crushing on the waste power lithium battery under the protection of inert gas and in a closed atmosphere to obtain waste battery crushed materials;

b. b, feeding the crushed battery materials obtained in the step a into a forced extraction device to extract and separate electrolyte, so as to realize the separation of the electrolyte, and recovering the electrolyte through evaporation and condensation;

c. c, carrying out novel extraction on the crushed battery materials obtained after the forced extraction in the step b again, and separating and recovering the binder in the crushed battery materials to separate electrode powder from the binder and the organic solvent;

d. c, drying the crushed battery materials obtained after the novel extraction in the step c at a certain temperature, and simultaneously evaporating the residual organic solvent and condensing and recovering the evaporated organic solvent;

e. and d, sorting and screening the crushed battery materials obtained in the step d to recover electrode powder.

2. The method for cleanly recovering all components of the waste power lithium battery as claimed in claim 1, is characterized in that: in the step a, the power lithium battery comprises: lithium batteries of various shapes, such as nickel-cobalt-manganese ternary lithium batteries, nickel-cobalt-aluminum lithium batteries, cobalt acid lithium batteries, manganese acid lithium batteries, iron phosphate lithium batteries, and the like.

3. The method for cleanly recovering all components of the waste power lithium battery as claimed in claim 1, is characterized in that: in the step a, the inert gas is nitrogen or argon or carbon dioxide, and the size of the battery crushed material obtained after crushing in a sealed atmosphere is 20mm multiplied by 20 mm.

4. The method for cleanly recovering all components of the waste power lithium battery as claimed in claim 1, is characterized in that: in the step b, the extraction agents adopted for forced extraction comprise a main extraction agent and an auxiliary extraction agent, wherein the main extraction agent is diethyl carbonate and ethylene carbonate, and the auxiliary extraction agent is N-methyl pyrrolidone.

5. The method for cleanly recovering all the components of the waste power lithium battery as claimed in claim 4, wherein in the step b, the extraction temperature of forced extraction is 18 ~ 25 ℃, the extraction time is 10 ~ 120min, and the extraction flow ratio is 1: 1-5.

6. The method for cleanly recovering all components of waste power lithium batteries as claimed in claim 1, is characterized in that in the step c, ethyl propionate and N-methyl pyrrolidone are adopted as novel extraction agents, 2-level extraction is carried out, the extraction temperature is 18 ~ 25 ℃, the extraction time is 10 ~ 120min, and the extraction flow ratio is 1: 1-5.

7. The method for cleanly recovering all components of the waste power lithium battery as claimed in claim 1, is characterized in that: in the step d, the drying temperature of the crushed battery materials is as follows: 50-70 ℃.

8. The method for cleanly recovering all components of the waste power lithium battery as claimed in claim 1, is characterized in that: and e, screening to obtain electrode powder, and directly entering a wet recovery system.

Technical Field

The invention relates to the field of waste lithium ion battery recovery, in particular to a clean recovery technology for all components of waste power lithium batteries.

Background

In recent years, China vigorously popularizes and applies new energy automobiles to drive the rapid growth of the market of power batteries. The output and sales of power storage batteries are rising year by year, and a large number of batteries face retirement and scrapping. According to the service life of the battery, calculated in 8-10 years, the power storage battery of the new energy automobile starts to be decommissioned in large scale after 2018 years, and is expected to exceed 20 ten thousand tons (24.6 GWh) by 2020, the scrappage in 2025 is 100GWh, and the scrappage in 2030 is 300 GWh. With the further popularization of new energy automobiles, the holding capacity of the electric automobiles is improved, and the market demand of power storage batteries is further released. In the future, the recycling market scale of the power battery is enlarged, and the industrial prospect is wide.

The recovery market scale created by recovering metals such as cobalt, nickel, manganese, lithium, iron, aluminum and the like from scrapped power lithium batteries is more than 100 million yuan in 2020, and the market scale of waste power lithium batteries reported in 2023 is 250 million yuan. At present, the recycling research of the scrapped lithium ion battery mainly focuses on the aspect of recycling of subsequent valuable metals of the waste lithium battery, but the research on recycling of electrolyte and organic matters in the pretreatment process of the waste lithium battery is less in the aspect of cleaning and recycling of the whole process, and the electrolyte can cause the problems of fluorine pollution and organic matter pollution during large-scale production. Therefore, how to efficiently recover nickel, cobalt, manganese and lithium metal elements in the waste lithium ion battery in an environment-friendly manner, and simultaneously realize green and clean recovery of electrolyte and organic substances in the pretreatment and crushing process of the waste lithium ion battery, the win-win situation of environmental protection and economic development is really realized, so that the lithium ion battery industry is well sustainable development, and becomes a key point and a difficulty of waste lithium ion battery recovery. Therefore, the technology for cleaning and recycling all components of the waste power lithium battery needs to be accelerated, and green and clean recycling of the waste lithium battery is comprehensively realized.

In the recovery technology of waste lithium ion batteries, there are several patent documents, such as chinese patents CN201210230857.3, CN201610872053.1, CN201410116605.7, and CN 201511029669.4.

Chinese patent CN201210230857.3 discloses a method, 1) using fluorine-containing organic acid aqueous solution to separate active substances and aluminum foil in the anode material of waste lithium ion batteries, and performing liquid-solid separation to obtain leachate, lithium-containing active substances and aluminum foil; 2) respectively carrying out high-temperature roasting and alkali liquor impurity removal treatment on the lithium-containing active substances; 3) respectively carrying out acid distillation on the leachate to recover fluorine-containing organic acid, alkali precipitation of impurity ions and ammonium carbonate coprecipitation to prepare a nickel-cobalt-manganese carbonate ternary precursor; 4) regulating and controlling the components of the treated active substance and the nickel-cobalt-manganese carbonate ternary precursor mixture, adding a certain proportion of lithium carbonate, and then carrying out high-temperature solid phase sintering to prepare the nickel-cobalt-manganese lithium manganate ternary composite positive electrode material. According to the method, fluorine-containing organic acid is adopted to separate active substances and aluminum foil in the waste lithium ion battery, the problem that the active substances and the aluminum foil are not completely separated exists, meanwhile, the active substances are placed in a high-temperature furnace to be roasted, a conductive agent and a binder in the active substances are removed, the dealuminized invalid positive electrode active substances are obtained, a large amount of fluorine-containing waste gas is generated through high-temperature roasting, and the waste lithium battery cannot be cleanly recovered.

Chinese patent CN201610872053.1 discloses a method, which comprises the following steps: the lower part is equipped with waste gas entry, the top is equipped with waste gas outlet's alkali lye spray column and the condenser that links to each other with waste gas outlet, and waste gas entry linkage is used for separating the cyclone of gas-solid phase in the organic gas, and the condenser passes through active carbon storage tank I and the active carbon storage tank II that the pipe connection is used for adsorbing waste gas, connects gradually filter, vacuum pump and gas-water separation tank through the pipeline after active carbon storage tank I and active carbon storage tank II are parallelly connected, the gas-water separation tank with the condenser links to each other, and the processing method of waste gas, including gas dust removal, alkali lye spray washing, gas condensation, pressure swing. The method carries out activated carbon absorption on the volatile fluorine-containing organic waste gas in the crushing process, and the method adopting activated carbon adsorption can not realize the efficient recycling of the electrolyte and the standard-reaching emission of the waste gas.

Chinese patent CN201410116605.7 discloses a method which comprises the following steps of a, discharging waste lithium ion batteries, b, crushing the waste lithium ion batteries into sheets with the diameter of 10 ~ 20mm in a closed shear type crusher, spraying when crushing, dissolving lithium hexafluorophosphate in the waste lithium ion batteries into spraying liquid, c, stripping carbon powder on the surface of a copper foil through stirring, dissolving electrolyte into the spraying liquid, then recovering the carbon powder, d, sending the sheet-shaped objects into a sodium hydroxide solution, stripping lithium cobaltate powder on the surface of an aluminum foil through stirring, then recovering the lithium cobaltate powder, e, cleaning the sheet-shaped objects, recovering the lithium cobaltate powder, f, separating and recovering plastic and copper-aluminum mixtures, and spraying and absorbing the lithium hexafluorophosphate in the pretreatment process of the recovered positive electrode powder to generate fluorine-containing waste water and cause secondary pollution to the environment.

Chinese patent CN201511029669.4 discloses a method, which comprises the following steps: and (4) fully discharging the waste lithium ion battery, then disassembling the waste lithium ion battery, and removing the shell, the positive and negative terminals, the sealing ring and the cover plate. Transferring the electrolyte, the current collectors with the positive and negative electrode materials and the diaphragm into a supercritical extraction device, adjusting the temperature, the pressure, the extraction time and the flow of the supercritical carbon dioxide fluid, then extracting the organic solvent and the additive, analyzing the components of the obtained solvent, supplementing electrolyte salt, the organic solvent and the additive according to the analysis result, and adjusting the mixture ratio to prepare the electrolytes with different functions. The method adopts a supercritical carbon dioxide method to extract and recover the electrolyte, has harsh process conditions and is difficult to realize large-scale industrial application.

Disclosure of Invention

Aiming at the defects of the method, the invention provides a method for effectively solving the problems, namely a method for cleanly recovering all components of waste power lithium batteries. The method has wide application range, the electrode powder, the electrolyte and the binder on the waste battery crushed aggregates are separated and recovered by adopting an extraction method, the recovery rate of the electrode powder is more than 98 percent, the clean recovery of all components of the waste power lithium ion battery in the crushing process is realized, the zero discharge of three wastes in the whole process is realized, and the green development concept of the waste power battery recovery industry is met.

The concrete contents are as follows: (1) adopting inert gas protection and closed atmosphere charged crushing: and disassembling and crushing the waste power lithium battery under the protection of inert gas in a closed state to obtain the crushed waste battery. (2) The method comprises the following steps of: and (3) feeding the crushed waste power lithium batteries into extraction equipment, extracting the electrolyte in the crushed waste batteries into an extracting agent, and separating and recovering the electrolyte. (3) The method comprises the following steps of extracting and recovering the binder by a novel extraction method: and the crushed battery materials after the electrolyte is extracted enter extraction equipment to extract and separate the binder, so that the electrode powder is thoroughly separated from the binder and the organic solvent. (4) Drying the crushed battery materials: drying the extracted battery crushed aggregates at a certain temperature, and simultaneously evaporating and condensing the residual organic extracting agent on the crushed aggregates for recovery. (5) And (3) recovering electrode powder: and separating and recovering the electrode powder and the copper-aluminum particles from the dried battery crushed aggregates by a sorting and screening method.

The power lithium battery includes: lithium ion batteries of various shapes such as nickel-cobalt-manganese ternary lithium batteries, nickel-cobalt-aluminum lithium batteries, cobalt acid lithium batteries, lithium manganate batteries, lithium iron phosphate batteries, and the like.

The inert gas is nitrogen, argon, carbon dioxide, etc., and the size of the crushed battery material obtained after crushing in a sealed atmosphere is 20mm multiplied by 20 mm.

The extraction agent adopted by the forced extraction comprises a main extraction agent and an auxiliary extraction agent, wherein the main extraction agent comprises diethyl carbonate and ethylene carbonate, and the auxiliary extraction agent comprises N-methyl pyrrolidone, the extraction temperature is 18 ~ 25 ℃, and the extraction time is 10 ~ 120min, and the extraction flow ratio is 1: 1-5.

The novel extraction adopts ethyl propionate and N-methyl pyrrolidone as extraction agents, the extraction temperature is 18 ~ 25 ℃, the extraction time is 10 ~ 120min, and the extraction flow ratio is 1:1-5, and the extraction is 2-grade extraction.

Drying temperature of the crushed battery: sieving at 50-70 deg.C to obtain electrode powder, which can be directly fed into wet recovery system. The recovered electrode powder does not contain fluorine-containing organic matters, and the recovery rate of the electrode powder can reach more than 98 percent.

Compared with the prior art, the invention has the beneficial effects that:

1. the method has a wide application range, realizes efficient separation and recovery of electrolyte, binder and electrode powder in the waste power lithium ion battery in the crushing process by an extraction method, avoids the generation of fluorine-containing waste gas by conventional high-temperature calcination, realizes green clean recovery of all components of the waste power battery, and accords with the green development concept of waste power battery recovery industry. The recovery rate of the electrode powder in the whole treatment process is more than 98 percent, and continuous, stable and large-scale industrial production can be realized.

2. The extraction method is used for extracting, recycling and reusing the electrolyte and the binder in the waste power lithium battery, and meanwhile, the organic solvents such as the binder and the like are thoroughly separated from the electrode powder, and no waste water, waste gas and waste residues are generated in the whole treatment process. The method fundamentally solves the problem of environmental pollution caused by volatilization of the electrolyte in the pretreatment process of the waste power lithium battery, really realizes zero emission of three wastes, is environment-friendly, and has great economic benefit and social benefit.

Drawings

FIG. 1 is a process flow diagram of the present invention.

Detailed Description