WO2018028167A1 - Recovery method for negative electrode piece of lithium metal battery - Google Patents

Recovery method for negative electrode piece of lithium metal battery Download PDF

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Publication number
WO2018028167A1
WO2018028167A1 PCT/CN2017/074130 CN2017074130W WO2018028167A1 WO 2018028167 A1 WO2018028167 A1 WO 2018028167A1 CN 2017074130 W CN2017074130 W CN 2017074130W WO 2018028167 A1 WO2018028167 A1 WO 2018028167A1
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Prior art keywords
lithium
negative electrode
metal
battery
electrode sheet
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PCT/CN2017/074130
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French (fr)
Chinese (zh)
Inventor
曹乃珍
徐川
陈欣
高洁
钟兆资
李仕红
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天齐锂业股份有限公司
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Publication of WO2018028167A1 publication Critical patent/WO2018028167A1/en

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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

Definitions

  • the invention relates to a method for recovering a negative electrode sheet of a metal lithium battery, and belongs to the technical field of batteries.
  • the composition of the lithium metal negative electrode sheet that a small amount of copper and a battery separator (generally PP or PE film) are mainly contained in the metal lithium or lithium alloy. If you can remove the copper and separator, you can regain high-purity, expensive battery-grade lithium metal or lithium alloy.
  • a battery separator generally PP or PE film
  • the first type is the recovery of metallic lithium for metallic lithium (such as lithium oxide, lithium nitride, etc.) having a surface which does not require a product, for example, metal lithium having a desired surface on the surface as mentioned in ZL201110296543.9
  • metallic lithium for metallic lithium (such as lithium oxide, lithium nitride, etc.) having a surface which does not require a product, for example, metal lithium having a desired surface on the surface as mentioned in ZL201110296543.9
  • the reaction with nitrogen forms lithium nitride and then reacts with carbon dioxide to form lithium carbonate, and then the formed lithium carbonate is reacted with hydrochloric acid to form lithium chloride, and the metal lithium is melted and electrolytically recovered.
  • This method is mainly for the recovery of surface products, and other large amounts of lithium metal are not recovered.
  • the process route is complicated, and the energy consumption, labor, and equipment cost are relatively high, which is equivalent to the whole process of re-preparing metal lithium, and the degree of application is low.
  • the second method is mainly for recovering metallic lithium from a waste lithium ion secondary battery, for example, as mentioned in ZL201010199758.4, all the reversible lithium ions on the negative electrode sheets of the used battery are transferred to the positive electrode, and formed on the positive electrode sheet.
  • a lithium salt a lithium salt
  • the battery after the discharge treatment is mechanically disassembled and the positive electrode sheet is completely taken out and dried
  • the lithium metal or lithium-clad material is used as a negative electrode sheet to match each positive electrode treated by the previous step.
  • the positive and negative sheet groups are respectively connected to the positive and negative bus bars of the DC power source, and subjected to externalization treatment to reversible lithium ions from the positive electrode sheets.
  • the invention mainly adopts the method of extracting lithium from the positive and negative electrodes respectively after pretreatment, but the method of subsequently extracting lithium is not described, and the key to extracting metallic lithium is the processing method on the pole piece.
  • the lithium extraction efficiency of the method is low, generally only reaches 70% to 90%, and the requirements for equipment, environment, operation and the like are high, and the recovery cost is also high.
  • the technical problem to be solved by the present invention is to provide a method for recovering a negative electrode sheet of a metal lithium battery, which extracts metal lithium or a lithium alloy from a negative electrode sheet of a metal lithium battery.
  • the method for recovering the negative electrode sheet of the metal lithium battery of the invention comprises the following steps:
  • the metal lithium battery negative electrode sheet is immersed in white oil
  • heating heating the white oil immersed in the negative electrode sheet of the metal lithium battery to 180-220 ° C, and stirring;
  • step b Insulation filtration: the white oil heated in step b is subjected to heat preservation filtration, and the filtrate is taken;
  • Degreasing Vacuum degreasing the solid metal lithium or lithium alloy to obtain a metallic lithium liquid or a lithium alloy liquid;
  • the soaking time is not less than 1 hour, preferably 1 hour.
  • the stirring rate is 100 to 150 rpm; the stirring time is 15 to 30 minutes.
  • the filter is subjected to thermal insulation filtration, and the filter has an accuracy of 15 to 30 ⁇ m, preferably a filter precision of 15 ⁇ m.
  • step d filtration is performed using a filter having an accuracy of 5 to 10 ⁇ m.
  • the vacuum deoiling temperature in the e step is 240 to 260 ° C
  • the degree of vacuum is 0.8 to 1.2 Pa, preferably the vacuum deoiling temperature is 250 ° C, and the degree of vacuum is 1 Pa.
  • the source of the negative electrode sheet of the metal lithium battery is a negative electrode sheet of a metal lithium battery negative electrode scrap, scrap or a metal lithium battery.
  • the metal lithium battery is a metal lithium primary battery, a metal lithium secondary battery, a lithium alloy primary battery, or a lithium alloy secondary battery.
  • the recycled material for the method of the present invention is the recovery of lithium metal or lithium alloy on the negative electrode sheet of the metal lithium battery, and the recovery process is to use white oil to purify and remove impurities, and recover high-purity metal lithium. Or lithium alloy, no need to re-electrolytic refining, the process is simple, low energy consumption, low comprehensive cost, easy to implement.
  • the recovered product has high purity and is easy to be added to the industrial process control.
  • the main reaction medium used is white oil. Recycle after treatment to reduce costs.
  • the method for recovering the negative electrode sheet of the metal lithium battery of the invention comprises the following steps:
  • the metal lithium battery negative electrode sheet is immersed in white oil
  • heating heating the white oil immersed in the negative electrode sheet of the metal lithium battery to 180-220 ° C, and stirring;
  • step b Insulation filtration: the white oil heated in step b is subjected to heat preservation filtration, and the filtrate is taken;
  • Degreasing Vacuum degreasing the solid metal lithium or lithium alloy to obtain a metallic lithium liquid or a lithium alloy liquid;
  • the white oil of the present invention is an industrial grade white oil obtained by petroleum refining, and the main component is a mixture of saturated cycloalkane and paraffin.
  • step a a certain amount of white oil is added to fully soak the negative electrode sheet of the metal lithium battery, and the separator attachment is gradually dissolved after contact with the white oil in the soaking process, and finally completely dissolved in the white oil.
  • the amount of white oil added is preferably a immersion metal lithium battery negative electrode sheet, and the immersion time is not less than 1 hour, preferably 1 hour.
  • step b as the temperature increases, the lithium metal or lithium alloy on the negative electrode sheet melts in the white oil, and the internal embedded impurities are released by stirring, wherein the stirring rate is 100 to 150 rpm, and the stirring reaction time is 15 to 30 minutes.
  • the reaction material is subjected to thermal filtration using a filter of a certain precision; copper and nitride and other deposits are deposited in the filter residue by filtration, and the filter has an accuracy of 15 to 30 ⁇ m.
  • step d the filtrate is cooled and filtered again to obtain a solid metal lithium or lithium alloy; the liquid metal lithium or lithium alloy is solidified in white oil and solidified, and the filtrate is white oil.
  • the filter accuracy is preferably 5 to 10 ⁇ m.
  • the vacuum degreasing temperature in the e step is 240 to 260 ° C, and the degree of vacuum is 0.8 to 1.2 Pa.
  • the vacuum deoiling temperature of the e step is 250 ° C and the degree of vacuum is 1 Pa.
  • the e step may be performed by placing lithium metal in a vacuum de-oiling tank to control the deoiling temperature at 250 ° C, and removing the volatile oil stain under the condition of a vacuum of 1 Pa.
  • the metal lithium liquid or the lithium alloy liquid obtained by de-oiling the e step is again filtered in a glove box under an argon atmosphere, and the filtrate is poured and cooled to obtain a battery-grade metal lithium ingot or a lithium alloy ingot.
  • the filter accuracy is preferably 5 to 10 ⁇ m.
  • Filtration of the f step of the invention is carried out under an inert atmosphere.
  • lithium nitride and lithium oxide are prevented from being formed, and on the other hand, lithium nitride, lithium oxide or the like contained in the raw material can be further removed by filtration.
  • the inert atmosphere is argon.
  • the invention mainly utilizes the scrap material of the negative electrode sheet of the metal lithium battery, the scrap or the negative electrode sheet disassembled by the metal lithium battery, and extracts the lithium metal or lithium alloy with higher purity.
  • the metal lithium battery is a metal lithium primary battery, a metal lithium secondary battery, a lithium alloy primary battery, or a lithium alloy secondary battery.
  • the metal lithium primary battery or the metal lithium secondary battery can be recovered by the method of the invention to obtain battery-grade metallic lithium
  • the lithium alloy primary battery or the lithium alloy secondary battery can be recovered by the method of the invention to obtain a relatively pure lithium alloy.
  • a lithium battery in which lithium metal or a lithium alloy is used as a negative electrode can be recovered without simply peeling off metallic lithium or a lithium alloy.
  • On the negative electrode sheet of the metal lithium battery there may be a deposit of the battery separator, a deposit of copper, and a surface deposit formed by the reaction of the metal lithium and the electrolytic solution.
  • the white oil is used for purification and impurity removal of the reaction medium, and the copper, the separator and other deposits therein can be removed to obtain a metal lithium or a lithium alloy with higher purity.
  • the lithium metal is recovered by the following method:
  • the reactor is heated so that the temperature of the white oil reaches 200 ° C and is fully stirred, and the stirring rate is 110 r / min; as the temperature increases, the metallic lithium on the pole piece melts in the white oil and is released by stirring.
  • reaction material is incubated with a 15 ⁇ m precision filter; the copper and nitride and other deposits are deposited in the filter residue by filtering;
  • the obtained metallic lithium is vacuum-depleted, and the metallic lithium is placed in a vacuum de-oiling tank to control the deoiling temperature to be 250 ° C, and the vacuum degree is 1 Pa to remove volatile oil, thereby obtaining a metallic lithium liquid.
  • the metal lithium liquid is again filtered in a glove box under an argon atmosphere, and the filtrate is poured and cooled to obtain a battery grade metal lithium ingot.
  • the filter has an accuracy of 5 to 10 ⁇ m.
  • the lithium metal is recovered by the following method:
  • the 100 g of the negative electrode sheet of the metal lithium secondary battery is placed in the reactor, and 100 ml of white oil is added to fully soak for 60 min. During the process, the separator deposit is gradually dissolved after contact with the white oil, and finally completely dissolved in the white oil;
  • the reactor is heated so that the temperature of the white oil reaches 180 ° C and is fully stirred, and the stirring rate is 100 r / min; as the temperature increases, the metallic lithium on the pole piece melts in the white oil and is released by stirring.
  • reaction material is incubated with a 15 ⁇ m precision filter; the copper and nitride and other deposits are deposited in the filter residue by filtering;
  • the obtained metallic lithium is vacuum-depleted, and the metallic lithium is placed in a vacuum de-oiling tank to control the deoiling temperature to be 240 ° C, and the vacuum degree is 0.8 Pa to remove the volatile oil stain to obtain a metallic lithium liquid.
  • the metal lithium liquid is again filtered in a glove box under an argon atmosphere, and the filtrate is poured and cooled to obtain a battery grade metal lithium ingot.
  • the filter has an accuracy of 5 to 10 ⁇ m.
  • the lithium metal is recovered by the following method:
  • the reactor is heated so that the temperature of the white oil reaches 180 ° C and is fully stirred, the stirring rate is 150 r / min; as the temperature increases, the metallic lithium on the pole piece melts in the white oil and is released by stirring. Internally embedded impurities;
  • reaction material is incubated with 30 ⁇ m precision filter; the copper and nitride and other deposits are deposited in the filter residue by filtering;
  • the obtained metallic lithium is vacuum-depleted, and the metallic lithium is placed in a vacuum de-oiling tank to control the deoiling temperature to be 240 ° C, and the vacuum degree is 0.8 Pa to remove the volatile oil stain to obtain a metallic lithium liquid.
  • the metal lithium liquid is again filtered in a glove box under an argon atmosphere, and the filtrate is poured and cooled to obtain a battery grade metal lithium ingot.
  • the filter has an accuracy of 5 to 10 ⁇ m.
  • the battery grade metallic lithium according to the present invention has the composition shown in Table 1.
  • the lithium alloy is recovered by the following method:
  • the lithium alloy primary battery negative electrode scrap 100g is placed in the reactor, and 800ml white oil is added and fully immersed for 60min. During the process, the separator attachment is gradually dissolved after contact with the white oil, and finally completely dissolved in the white oil;
  • the reactor is heated so that the temperature of the white oil reaches 180 ° C and is fully stirred, the stirring rate is 150 r / min; as the temperature increases, the lithium alloy on the pole piece melts in the white oil and is released by stirring.
  • reaction material is incubated with 30 ⁇ m precision filter; the copper and nitride and other deposits are deposited in the filter residue by filtering;
  • the filtrate is cooled and filtered again to obtain a solid lithium alloy; the liquid lithium alloy is cooled and solidified in white oil, and the filtrate is white oil;
  • the obtained lithium alloy is vacuum degreased, and the lithium alloy is placed in a vacuum degreaser to control the deoiling temperature to be 240 ° C, and the vacuum degree is 0.8 Pa to remove the volatile oil stain to obtain a lithium alloy liquid.
  • the metal lithium alloy liquid is again filtered in a glove box under an argon atmosphere, and the filtrate is poured and cooled to obtain a battery grade metal lithium ingot.
  • the filter has an accuracy of 5 to 10 ⁇ m.
  • the composition of the battery grade lithium alloy is shown in Table 2.

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  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
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Abstract

The present invention relates to a recovery method for a negative electrode piece of a lithium metal battery, relating to the technical field of batteries. The technical problem solved by the present invention is to provide a recovery method for a negative electrode piece of a lithium metal battery, so as to extract lithium metal or lithium alloy from the negative electrode piece of the lithium metal battery. The method comprises the following steps: a. immersing leftover materials of the negative electrode piece of the lithium metal battery into white oil; b. heating the white oil in which the negative electrode piece of the lithium metal battery is immersed to 180-220℃ and stirring the white oil; c. maintaining the temperature and filtering to obtain a filtrate; d. cooling the filtrate and filtering to obtain solid-state lithium metal or lithium alloy; e. performing vacuum deoiling on the solid-state lithium metal or lithium alloy to obtain a lithium metal liquid or lithium alloy liquid; and f. filtering and pouring: filtering the lithium metal liquid or lithium alloy liquid at an inert atmosphere, and then pouring the filtrate obtained after filtering to form a battery-grade lithium metal ingot or an lithium alloy ingot. Compared with the prior art, the product recovered by the method of the present invention has high purity; recovery process does not require re-electrolytic refining; and the invention is simple in process and low in energy consumption and comprehensive cost and is easy to implement.

Description

金属锂电池负极片的回收方法Method for recovering negative electrode sheet of metal lithium battery 技术领域Technical field
本发明涉及金属锂电池负极片的回收方法，属于电池技术领域。The invention relates to a method for recovering a negative electrode sheet of a metal lithium battery, and belongs to the technical field of batteries.
背景技术Background technique
近年来在玻璃、陶瓷、润滑剂、核工业、航空航天及合金材料领域，金属锂得到了广泛大量的应用。目前全球金属锂消费量为11250吨，其中用于金属锂一次电池二次电池的量为3937.5吨。金属锂在一次电池领域成熟应用的同时在二次电池领域得到了较大的突破，用于电池领域的金属锂正以迅猛的势头逐年增加。随着金属锂在高能二次电池负极方面的应用突破，当其与适当正极材料匹配构成电池时具有最高的电池电压和3860mAh/g的高理论容量，是未来锂电池发展的热门方向。而金属锂高额的消耗以及对环境和安全的考虑必须对其进行二次回收利用。全球的锂资源有限，为了锂资源的循环利用和可持续发展金属锂的回收迫在眉睫。In recent years, in the fields of glass, ceramics, lubricants, nuclear industry, aerospace and alloy materials, metallic lithium has been widely used. At present, the global consumption of lithium metal is 11,250 tons, of which the amount of secondary batteries for metal lithium primary batteries is 3937.5 tons. Metal lithium has made great breakthroughs in the field of secondary batteries while being matured in the field of primary batteries, and metal lithium used in the battery field is increasing rapidly with increasing momentum. With the breakthrough in the application of metallic lithium in the negative electrode of high-energy secondary batteries, it has the highest battery voltage and high theoretical capacity of 3860 mAh/g when it is matched with a suitable positive electrode material, which is a hot trend in the future development of lithium batteries. The high consumption of metallic lithium and environmental and safety considerations must be recycled. The global lithium resources are limited, and the recycling of lithium resources and the sustainable development of lithium metal are urgently needed.
从金属锂负极片的成分可以看出其中是以金属锂或锂合金为主体含有少量的铜和电池隔膜(一般为PP或PE膜)。如果能够把其中的铜和隔膜除去就能重新获取纯度极高，价格昂贵的电池级金属锂或者锂合金。It can be seen from the composition of the lithium metal negative electrode sheet that a small amount of copper and a battery separator (generally PP or PE film) are mainly contained in the metal lithium or lithium alloy. If you can remove the copper and separator, you can regain high-purity, expensive battery-grade lithium metal or lithium alloy.
当前金属锂负极片的回收技术主要有两种：At present, there are two main techniques for recycling lithium metal negative electrode sheets:
第一种是针对表面有不需要生成物的金属锂(如：氧化锂、氮化锂等)进行金属锂的回收，例如：ZL201110296543.9中提到的将表面有不需要生成物的金属锂与氮气反应形成氮化锂再与二氧化碳反应形成碳酸锂，然后将生成的碳酸锂与盐酸反应形成氯化锂，熔融、电解回收金属锂。该方法主要针对于表面生成物的回收，其它大量的金属锂并没有得到回收。并且该工艺路线繁杂，耗能、人工、设备成本较高，相当于比重新制备金属锂的全过程更加复杂，适用程度较低。The first type is the recovery of metallic lithium for metallic lithium (such as lithium oxide, lithium nitride, etc.) having a surface which does not require a product, for example, metal lithium having a desired surface on the surface as mentioned in ZL201110296543.9 The reaction with nitrogen forms lithium nitride and then reacts with carbon dioxide to form lithium carbonate, and then the formed lithium carbonate is reacted with hydrochloric acid to form lithium chloride, and the metal lithium is melted and electrolytically recovered. This method is mainly for the recovery of surface products, and other large amounts of lithium metal are not recovered. Moreover, the process route is complicated, and the energy consumption, labor, and equipment cost are relatively high, which is equivalent to the whole process of re-preparing metal lithium, and the degree of application is low.
第二种主要是针对从废旧锂离子二次电池中回收金属锂的方法，例如：ZL201010199758.4中提到的，使该废旧电池各负极片上的可逆锂离子全部转移至正极，在正极片上形成锂盐；将所述放电处理后的电池，用机械拆解的物理方式将正极片完整地取出，烘干；用金属锂或可覆锂的材料做负极片配合由前步骤处理后的各正极片，放入有电解液的专用化成槽中经电联接后，正负极片组分别接到直流电源的正、负极汇流排，进行外化成处理，使可逆的锂离子从所述各正极片转移至所述各负极片 上沉积；将所述经外化成处理后的各正、负极片取出，则负极片上析出的金属锂可直接回收利用。该发明主要是通过预处理后将正负极片分别提锂，但是后续提锂的方法并没有描述，而提取金属锂的关键正是在极片上的处理方法。该方法的提锂效率低，一般只能到达70％～90％，并且对设备、环境、操作等要求精度高，回收成本也较高。The second method is mainly for recovering metallic lithium from a waste lithium ion secondary battery, for example, as mentioned in ZL201010199758.4, all the reversible lithium ions on the negative electrode sheets of the used battery are transferred to the positive electrode, and formed on the positive electrode sheet. a lithium salt; the battery after the discharge treatment is mechanically disassembled and the positive electrode sheet is completely taken out and dried; and the lithium metal or lithium-clad material is used as a negative electrode sheet to match each positive electrode treated by the previous step. After being electrically connected in a specializing tank filled with an electrolyte, the positive and negative sheet groups are respectively connected to the positive and negative bus bars of the DC power source, and subjected to externalization treatment to reversible lithium ions from the positive electrode sheets. Transfer to the negative electrode sheets The upper and the negative electrode sheets which have been subjected to the externalization treatment are taken out, and the metal lithium deposited on the negative electrode sheet can be directly recycled. The invention mainly adopts the method of extracting lithium from the positive and negative electrodes respectively after pretreatment, but the method of subsequently extracting lithium is not described, and the key to extracting metallic lithium is the processing method on the pole piece. The lithium extraction efficiency of the method is low, generally only reaches 70% to 90%, and the requirements for equipment, environment, operation and the like are high, and the recovery cost is also high.
发明内容Summary of the invention
本发明解决的技术问题是提供金属锂电池负极片的回收方法，从金属锂电池负极片中提取金属锂或者锂合金。The technical problem to be solved by the present invention is to provide a method for recovering a negative electrode sheet of a metal lithium battery, which extracts metal lithium or a lithium alloy from a negative electrode sheet of a metal lithium battery.
本发明金属锂电池负极片的回收方法，包括如下步骤：The method for recovering the negative electrode sheet of the metal lithium battery of the invention comprises the following steps:
a、浸泡：将金属锂电池负极片浸泡于白油中；a, soaking: the metal lithium battery negative electrode sheet is immersed in white oil;
b、加热：将浸泡有金属锂电池负极片的白油加热至180～220℃，并进行搅拌；b. heating: heating the white oil immersed in the negative electrode sheet of the metal lithium battery to 180-220 ° C, and stirring;
c、保温过滤：将b步骤加热后的白油进行保温过滤，取滤液；c. Insulation filtration: the white oil heated in step b is subjected to heat preservation filtration, and the filtrate is taken;
d、二次过滤：将滤液冷却，过滤，得到固态的金属锂或锂合金；d, secondary filtration: the filtrate is cooled and filtered to obtain a solid metal lithium or lithium alloy;
e、除油：将固态的金属锂或锂合金进行真空除油，得到金属锂液或锂合金液；。e. Degreasing: Vacuum degreasing the solid metal lithium or lithium alloy to obtain a metallic lithium liquid or a lithium alloy liquid;
f、过滤浇注：在惰性气氛下将金属锂液或锂合金液过滤，过滤后将滤液浇注成电池级金属锂锭或锂合金锭。f. Filtration casting: The lithium metal liquid or the lithium alloy liquid is filtered under an inert atmosphere, and after filtration, the filtrate is poured into a battery-grade metal lithium ingot or a lithium alloy ingot.
其中，a步骤中，浸泡时间不低于1小时，优选为1小时。Among them, in the step a, the soaking time is not less than 1 hour, preferably 1 hour.
进一步的，b步骤中，搅拌速率为100～150转/分钟；搅拌时间为15～30分钟。Further, in the step b, the stirring rate is 100 to 150 rpm; the stirring time is 15 to 30 minutes.
进一步的，c步骤中，采用过滤器进行保温过滤，所述过滤器精度为15～30μm，优选过滤器精度为15μm。Further, in the step c, the filter is subjected to thermal insulation filtration, and the filter has an accuracy of 15 to 30 μm, preferably a filter precision of 15 μm.
进一步的，d步骤中，采用过滤器进行过滤，所述过滤器精度为5～10μm。Further, in the step d, filtration is performed using a filter having an accuracy of 5 to 10 μm.
进一步的，e步骤中的真空除油温度为240～260℃，真空度为0.8～1.2Pa，优选真空除油温度为250℃，真空度为1Pa。Further, the vacuum deoiling temperature in the e step is 240 to 260 ° C, the degree of vacuum is 0.8 to 1.2 Pa, preferably the vacuum deoiling temperature is 250 ° C, and the degree of vacuum is 1 Pa.
进一步的，所述金属锂电池负极片的来源为金属锂电池负极片边角料、废料或金属锂电池拆解后的负极片。Further, the source of the negative electrode sheet of the metal lithium battery is a negative electrode sheet of a metal lithium battery negative electrode scrap, scrap or a metal lithium battery.
所述金属锂电池为金属锂一次电池、金属锂二次电池、锂合金一次电池或锂合金二次电池。The metal lithium battery is a metal lithium primary battery, a metal lithium secondary battery, a lithium alloy primary battery, or a lithium alloy secondary battery.
与现有技术相比，本发明的方法所针对的回收物料为金属锂电池负极片上金属锂或锂合金的回收，其回收工艺是利用白油为反应介质提纯除杂，回收高纯度的金属锂或锂合金，无需重新电解提炼，其工艺简洁，能耗低，综合成本低，易于实现。回收得到的产品纯度高，更易于加入工业化过程控制当中，所用的主要反应介质白油可通 过处理后循环使用，降低成本。Compared with the prior art, the recycled material for the method of the present invention is the recovery of lithium metal or lithium alloy on the negative electrode sheet of the metal lithium battery, and the recovery process is to use white oil to purify and remove impurities, and recover high-purity metal lithium. Or lithium alloy, no need to re-electrolytic refining, the process is simple, low energy consumption, low comprehensive cost, easy to implement. The recovered product has high purity and is easy to be added to the industrial process control. The main reaction medium used is white oil. Recycle after treatment to reduce costs.
具体实施方式detailed description
本发明金属锂电池负极片的回收方法，包括如下步骤：The method for recovering the negative electrode sheet of the metal lithium battery of the invention comprises the following steps:
a、浸泡：将金属锂电池负极片浸泡于白油中；a, soaking: the metal lithium battery negative electrode sheet is immersed in white oil;
b、加热：将浸泡有金属锂电池负极片的白油加热至180～220℃，并进行搅拌；b. heating: heating the white oil immersed in the negative electrode sheet of the metal lithium battery to 180-220 ° C, and stirring;
c、保温过滤：将b步骤加热后的白油进行保温过滤，取滤液；c. Insulation filtration: the white oil heated in step b is subjected to heat preservation filtration, and the filtrate is taken;
d、二次过滤：将滤液冷却，过滤，得到固态的金属锂或锂合金；d, secondary filtration: the filtrate is cooled and filtered to obtain a solid metal lithium or lithium alloy;
e、除油：将固态的金属锂或锂合金进行真空除油，得到金属锂液或锂合金液；。e. Degreasing: Vacuum degreasing the solid metal lithium or lithium alloy to obtain a metallic lithium liquid or a lithium alloy liquid;
f、过滤浇注：在惰性气氛下将金属锂液或锂合金液过滤，过滤后将滤液浇注成电池级金属锂锭或锂合金锭。f. Filtration casting: The lithium metal liquid or the lithium alloy liquid is filtered under an inert atmosphere, and after filtration, the filtrate is poured into a battery-grade metal lithium ingot or a lithium alloy ingot.
本发明所述的白油为工业级白油，是由石油精炼所得的，主要成分为饱和的环烷烃与链烷烃的混合物。The white oil of the present invention is an industrial grade white oil obtained by petroleum refining, and the main component is a mixture of saturated cycloalkane and paraffin.
其中，a步骤中，加入一定量的白油充分浸泡金属锂电池负极片,浸泡过程中隔膜附着物与白油接触后逐渐溶解，最后完全溶于白油中。为了达到充分浸泡的目的，同时也为节约原料，白油的加入量优选为浸没金属锂电池负极片，浸泡时间不低于1小时，优选为1小时。Wherein, in step a, a certain amount of white oil is added to fully soak the negative electrode sheet of the metal lithium battery, and the separator attachment is gradually dissolved after contact with the white oil in the soaking process, and finally completely dissolved in the white oil. In order to achieve the purpose of sufficient immersion, and also to save raw materials, the amount of white oil added is preferably a immersion metal lithium battery negative electrode sheet, and the immersion time is not less than 1 hour, preferably 1 hour.
b步骤中，随着温度的升高，负极片上的金属锂或锂合金在白油中融化，通过搅拌释放出内部嵌入的杂质，其中，搅拌速率为100～150转/分钟，搅拌反应时间为15～30分钟。In step b, as the temperature increases, the lithium metal or lithium alloy on the negative electrode sheet melts in the white oil, and the internal embedded impurities are released by stirring, wherein the stirring rate is 100 to 150 rpm, and the stirring reaction time is 15 to 30 minutes.
c步骤中，利用一定精度的过滤器对反应物料进行保温过滤；通过过滤，铜和氮化物及其它附着物沉积在滤渣当中，所述过滤器精度为15～30μm。In the step c, the reaction material is subjected to thermal filtration using a filter of a certain precision; copper and nitride and other deposits are deposited in the filter residue by filtration, and the filter has an accuracy of 15 to 30 μm.
d步骤中，将滤液冷却后再次进行过滤，得到固态的金属锂或锂合金；液态金属锂或锂合金在白油当中冷却后凝固，滤液为白油。所述过滤器精度优选为5～10μm。In step d, the filtrate is cooled and filtered again to obtain a solid metal lithium or lithium alloy; the liquid metal lithium or lithium alloy is solidified in white oil and solidified, and the filtrate is white oil. The filter accuracy is preferably 5 to 10 μm.
进一步的，e步骤中的真空除油温度为240～260℃，真空度为0.8～1.2Pa。Further, the vacuum degreasing temperature in the e step is 240 to 260 ° C, and the degree of vacuum is 0.8 to 1.2 Pa.
作为优选方案，e步骤的真空除油温度为250℃，真空度为1Pa。具体的，e步骤可采用如下操作：将金属锂置于真空除油罐中控制脱油温度在250℃，真空度在1Pa的条件下脱除易挥发的油污。Preferably, the vacuum deoiling temperature of the e step is 250 ° C and the degree of vacuum is 1 Pa. Specifically, the e step may be performed by placing lithium metal in a vacuum de-oiling tank to control the deoiling temperature at 250 ° C, and removing the volatile oil stain under the condition of a vacuum of 1 Pa.
f步骤中，将e步骤除油后得到的金属锂液或锂合金液在氩气保护气氛的手套箱中再次过滤，滤液浇注冷却后得到电池级金属锂锭或锂合金锭。所述过滤器精度优选为5～10μm。 In the step f, the metal lithium liquid or the lithium alloy liquid obtained by de-oiling the e step is again filtered in a glove box under an argon atmosphere, and the filtrate is poured and cooled to obtain a battery-grade metal lithium ingot or a lithium alloy ingot. The filter accuracy is preferably 5 to 10 μm.
本发明f步骤的过滤在惰性气氛下进行。一方面避免生成氮化锂、氧化锂，另一方面可通过过滤进一步去除原料中含有的氮化锂、氧化锂等。Filtration of the f step of the invention is carried out under an inert atmosphere. On the one hand, lithium nitride and lithium oxide are prevented from being formed, and on the other hand, lithium nitride, lithium oxide or the like contained in the raw material can be further removed by filtration.
优选的，所述惰性气氛为氩气。Preferably, the inert atmosphere is argon.
本发明主要是利用金属锂电池负极片的边角料、废料或金属锂电池拆解后的负极片，从中提取纯度较高的金属锂或锂合金。所述金属锂电池为金属锂一次电池、金属锂二次电池、锂合金一次电池或锂合金二次电池。其中，金属锂一次电池或金属锂二次电池可通过本发明方法回收得到电池级金属锂，而锂合金一次电池或锂合金二次电池可通过本发明方法回收得到较纯的锂合金。The invention mainly utilizes the scrap material of the negative electrode sheet of the metal lithium battery, the scrap or the negative electrode sheet disassembled by the metal lithium battery, and extracts the lithium metal or lithium alloy with higher purity. The metal lithium battery is a metal lithium primary battery, a metal lithium secondary battery, a lithium alloy primary battery, or a lithium alloy secondary battery. Wherein, the metal lithium primary battery or the metal lithium secondary battery can be recovered by the method of the invention to obtain battery-grade metallic lithium, and the lithium alloy primary battery or the lithium alloy secondary battery can be recovered by the method of the invention to obtain a relatively pure lithium alloy.
以金属锂或锂合金为负极的锂电池并不是单纯的剥离金属锂或锂合金便可以实现回收。金属锂电池的负极片上可能存在电池隔膜的附着物、铜的附着物以及金属锂和电解液反应后形成的表面附着物。通过本发明的工艺，利用白油为反应介质提纯除杂，可除去其中的铜、隔膜及其它附着物，得到纯度较高的金属锂或锂合金。A lithium battery in which lithium metal or a lithium alloy is used as a negative electrode can be recovered without simply peeling off metallic lithium or a lithium alloy. On the negative electrode sheet of the metal lithium battery, there may be a deposit of the battery separator, a deposit of copper, and a surface deposit formed by the reaction of the metal lithium and the electrolytic solution. By the process of the invention, the white oil is used for purification and impurity removal of the reaction medium, and the copper, the separator and other deposits therein can be removed to obtain a metal lithium or a lithium alloy with higher purity.
下面结合实施例对本发明的具体实施方式做进一步的描述，并不因此将本发明限制在所述的实施例范围之中。The embodiments of the present invention are further described in conjunction with the embodiments, and are not intended to limit the invention.
实施例1Example 1
采用如下方法回收金属锂：The lithium metal is recovered by the following method:
1、将金属锂一次电池负极片边角料100g置于反应器当中，加入500ml的白油充分浸泡60min,过程中隔膜附着物与白油接触后逐渐溶解，最后完全溶于白油中；1. Place 100g of negative electrode scrap of metal lithium primary battery in the reactor, and add 500ml of white oil to fully soak for 60min. During the process, the separator deposit gradually dissolves after contact with white oil, and finally dissolves completely in white oil;
2、对反应器进行加热使白油的温度达到200℃并进行充分的搅拌，搅拌的速率为110r/min；随着温度的升高极片上的金属锂在白油中融化，通过搅拌释放出内部嵌入的杂质；2. The reactor is heated so that the temperature of the white oil reaches 200 ° C and is fully stirred, and the stirring rate is 110 r / min; as the temperature increases, the metallic lithium on the pole piece melts in the white oil and is released by stirring. Internally embedded impurities;
3、搅拌反应30min后,利用15μm精度的过滤器对反应物料进行保温过滤；通过过滤铜和氮化物及其它附着物沉积在滤渣中；3. After stirring for 30 minutes, the reaction material is incubated with a 15 μm precision filter; the copper and nitride and other deposits are deposited in the filter residue by filtering;
4、将滤液冷却后再次进行过滤，得到固态的金属锂；液态金属锂在白油中冷却凝固，滤液为白油；4. After cooling the filtrate, it is filtered again to obtain solid metal lithium; the liquid metal lithium is cooled and solidified in white oil, and the filtrate is white oil;
5、将得到的金属锂进行真空除油，将金属锂置于真空除油罐中控制脱油温度为250℃，真空度为1Pa的条件下脱除易挥发的油污，得到金属锂液。5. The obtained metallic lithium is vacuum-depleted, and the metallic lithium is placed in a vacuum de-oiling tank to control the deoiling temperature to be 250 ° C, and the vacuum degree is 1 Pa to remove volatile oil, thereby obtaining a metallic lithium liquid.
6、将金属锂液在氩气保护气氛的手套箱中再次过滤，滤液浇注冷却后得到电池级金属锂锭。所述过滤器精度为5～10μm。6. The metal lithium liquid is again filtered in a glove box under an argon atmosphere, and the filtrate is poured and cooled to obtain a battery grade metal lithium ingot. The filter has an accuracy of 5 to 10 μm.
实施例2 Example 2
采用如下方法回收金属锂：The lithium metal is recovered by the following method:
1、将金属锂二次电池负极片边角料100g置于反应器当中，加入100ml的白油充分浸泡60min,过程中隔膜附着物与白油接触后逐渐溶解，最后完全溶于白油中；1. The 100 g of the negative electrode sheet of the metal lithium secondary battery is placed in the reactor, and 100 ml of white oil is added to fully soak for 60 min. During the process, the separator deposit is gradually dissolved after contact with the white oil, and finally completely dissolved in the white oil;
2、对反应器进行加热使白油的温度达到180℃并进行充分的搅拌，搅拌的速率为100r/min；随着温度的升高极片上的金属锂在白油中融化，通过搅拌释放出内部嵌入的杂质；2. The reactor is heated so that the temperature of the white oil reaches 180 ° C and is fully stirred, and the stirring rate is 100 r / min; as the temperature increases, the metallic lithium on the pole piece melts in the white oil and is released by stirring. Internally embedded impurities;
3、搅拌反应20min后,利用15μm精度的过滤器对反应物料进行保温过滤；通过过滤铜和氮化物及其它附着物沉积在滤渣中；3. After stirring for 20 minutes, the reaction material is incubated with a 15 μm precision filter; the copper and nitride and other deposits are deposited in the filter residue by filtering;
4、将滤液冷却后再次进行过滤，得到固态的金属锂；液态金属锂在白油中冷却凝固，滤液为白油；4. After cooling the filtrate, it is filtered again to obtain solid metal lithium; the liquid metal lithium is cooled and solidified in white oil, and the filtrate is white oil;
5、将得到的金属锂进行真空除油，将金属锂置于真空除油罐中控制脱油温度为240℃，真空度为0.8Pa的条件下脱除易挥发的油污，得到金属锂液。5. The obtained metallic lithium is vacuum-depleted, and the metallic lithium is placed in a vacuum de-oiling tank to control the deoiling temperature to be 240 ° C, and the vacuum degree is 0.8 Pa to remove the volatile oil stain to obtain a metallic lithium liquid.
6、将金属锂液在氩气保护气氛的手套箱中再次过滤，滤液浇注冷却后得到电池级金属锂锭。所述过滤器精度为5～10μm。6. The metal lithium liquid is again filtered in a glove box under an argon atmosphere, and the filtrate is poured and cooled to obtain a battery grade metal lithium ingot. The filter has an accuracy of 5 to 10 μm.
实施例3Example 3
采用如下方法回收金属锂：The lithium metal is recovered by the following method:
1、将金属锂二次电池负极片边角料100g置于反应器当中，加入800ml的白油充分浸泡60min,过程中隔膜附着物与白油接触后逐渐溶解，最后完全溶于白油中；1. Place 100g of negative electrode scrap of metal lithium secondary battery in the reactor, and fully soak for 800min by adding 800ml of white oil. During the process, the separator deposit gradually dissolves after contact with white oil, and finally dissolves completely in white oil;
2、对反应器进行加热使白油的温度达到180℃并进行充分的搅拌，搅拌的速率为150r/min；随着温度的升高极片上的金属锂在白油中融化，通过搅拌释放出内部嵌入的杂质；2. The reactor is heated so that the temperature of the white oil reaches 180 ° C and is fully stirred, the stirring rate is 150 r / min; as the temperature increases, the metallic lithium on the pole piece melts in the white oil and is released by stirring. Internally embedded impurities;
3、搅拌反应30min后,利用30μm精度的过滤器对反应物料进行保温过滤；通过过滤铜和氮化物及其它附着物沉积在滤渣中；3. After stirring for 30 minutes, the reaction material is incubated with 30 μm precision filter; the copper and nitride and other deposits are deposited in the filter residue by filtering;
4、将滤液冷却后再次进行过滤，得到固态的金属锂；液态金属锂在白油中冷却凝固，滤液为白油；4. After cooling the filtrate, it is filtered again to obtain solid metal lithium; the liquid metal lithium is cooled and solidified in white oil, and the filtrate is white oil;
5、将得到的金属锂进行真空除油，将金属锂置于真空除油罐中控制脱油温度为240℃，真空度为0.8Pa的条件下脱除易挥发的油污，得到金属锂液。5. The obtained metallic lithium is vacuum-depleted, and the metallic lithium is placed in a vacuum de-oiling tank to control the deoiling temperature to be 240 ° C, and the vacuum degree is 0.8 Pa to remove the volatile oil stain to obtain a metallic lithium liquid.
6、将金属锂液在氩气保护气氛的手套箱中再次过滤，滤液浇注冷却后得到电池级金属锂锭。所述过滤器精度为5～10μm。6. The metal lithium liquid is again filtered in a glove box under an argon atmosphere, and the filtrate is poured and cooled to obtain a battery grade metal lithium ingot. The filter has an accuracy of 5 to 10 μm.
本发明所述的电池级金属锂，其成分如表1所示。 The battery grade metallic lithium according to the present invention has the composition shown in Table 1.
表1电池级金属锂中锂含量及杂质的含量Table 1 Lithium content and impurity content in battery grade lithium metal
含量(％)content(%) Li≥Li≥ Al＜Al< Si＜Si< Fe＜Fe< Mg＜Mg< Cu＜Cu< K＜K< Ca＜Ca< Na＜Na< Ni＜Ni<
金属锂Metal lithium 99.999.9 0.00170.0017 0.00320.0032 0.0010.001 0.00030.0003 0.00020.0002 0.00050.0005 0.00480.0048 0.00270.0027 0.00010.0001
实施例4Example 4
采用如下方法回收锂合金：The lithium alloy is recovered by the following method:
1、将锂合金一次电池负极片边角料100g置于反应器当中，加入800ml的白油充分浸泡60min,过程中隔膜附着物与白油接触后逐渐溶解，最后完全溶于白油中；1. The lithium alloy primary battery negative electrode scrap 100g is placed in the reactor, and 800ml white oil is added and fully immersed for 60min. During the process, the separator attachment is gradually dissolved after contact with the white oil, and finally completely dissolved in the white oil;
2、对反应器进行加热使白油的温度达到180℃并进行充分的搅拌，搅拌的速率为150r/min；随着温度的升高极片上的锂合金在白油中融化，通过搅拌释放出内部嵌入的杂质；2. The reactor is heated so that the temperature of the white oil reaches 180 ° C and is fully stirred, the stirring rate is 150 r / min; as the temperature increases, the lithium alloy on the pole piece melts in the white oil and is released by stirring. Internally embedded impurities;
3、搅拌反应30min后,利用30μm精度的过滤器对反应物料进行保温过滤；通过过滤铜和氮化物及其它附着物沉积在滤渣中；3. After stirring for 30 minutes, the reaction material is incubated with 30 μm precision filter; the copper and nitride and other deposits are deposited in the filter residue by filtering;
4、将滤液冷却后再次进行过滤，得到固态的锂合金；液态锂合金在白油中冷却凝固，滤液为白油；4. The filtrate is cooled and filtered again to obtain a solid lithium alloy; the liquid lithium alloy is cooled and solidified in white oil, and the filtrate is white oil;
5、将得到的锂合金进行真空除油，将锂合金置于真空除油罐中控制脱油温度为240℃，真空度为0.8Pa的条件下脱除易挥发的油污，得到锂合金液。5. The obtained lithium alloy is vacuum degreased, and the lithium alloy is placed in a vacuum degreaser to control the deoiling temperature to be 240 ° C, and the vacuum degree is 0.8 Pa to remove the volatile oil stain to obtain a lithium alloy liquid.
6、将金属锂合金液在氩气保护气氛的手套箱中再次过滤，滤液浇注冷却后得到电池级金属锂锭。所述过滤器精度为5～10μm。6. The metal lithium alloy liquid is again filtered in a glove box under an argon atmosphere, and the filtrate is poured and cooled to obtain a battery grade metal lithium ingot. The filter has an accuracy of 5 to 10 μm.
所述电池级锂合金的成分见表2。The composition of the battery grade lithium alloy is shown in Table 2.
表2电池级锂合金中锂含量及杂质的含量Table 2 Lithium content and impurity content in battery-grade lithium alloy
含量(％)content(%) Li≥Li≥ Al＜Al< Si＜Si< Fe＜Fe< Mg＜Mg< Cu＜Cu< K＜K< Ca＜Ca< Na＜Na< Ni＜Ni<
锂合金Lithium alloy 9999 0.90.9 0.00320.0032 0.0010.001 0.00030.0003 0.00020.0002 0.00050.0005 0.00480.0048 0.00270.0027 0.00010.0001

Claims (11)

  1. 金属锂电池负极片的回收方法，其特征在于，包括如下步骤：A method for recovering a negative electrode sheet of a metal lithium battery, comprising the steps of:
    a、浸泡：将金属锂电池负极片浸泡于白油中；a, soaking: the metal lithium battery negative electrode sheet is immersed in white oil;
    b、加热：将浸泡有金属锂电池负极片的白油加热至180～220℃，并进行搅拌；b. heating: heating the white oil immersed in the negative electrode sheet of the metal lithium battery to 180-220 ° C, and stirring;
    c、保温过滤：将b步骤加热后的白油进行保温过滤，取滤液；c. Insulation filtration: the white oil heated in step b is subjected to heat preservation filtration, and the filtrate is taken;
    d、二次过滤：将滤液冷却，过滤，得到固态的金属锂或锂合金；d, secondary filtration: the filtrate is cooled and filtered to obtain a solid metal lithium or lithium alloy;
    e、除油：将固态的金属锂或锂合金进行真空除油，得到金属锂液或锂合金液；e, degreasing: vacuum solid degreasing of lithium metal or lithium alloy to obtain lithium metal or lithium alloy liquid;
    f、过滤浇注：在惰性气氛下将金属锂液或锂合金液过滤，过滤后将滤液浇注成电池级金属锂锭或锂合金锭。f. Filtration casting: The lithium metal liquid or the lithium alloy liquid is filtered under an inert atmosphere, and after filtration, the filtrate is poured into a battery-grade metal lithium ingot or a lithium alloy ingot.
  2. 根据权利要求1所述的金属锂电池负极片的回收方法，其特征在于：a步骤中，浸泡时间为不低于1小时。The method for recovering a negative electrode sheet for a metal lithium battery according to claim 1, wherein in the step a, the soaking time is not less than 1 hour.
  3. 根据权利要求2所述的金属锂电池负极片的回收方法，其特征在于：a步骤中，浸泡时间为1小时。The method for recovering a negative electrode sheet for a metal lithium battery according to claim 2, wherein in the step a, the soaking time is 1 hour.
  4. 根据权利要求1所述的金属锂电池负极片的回收方法，其特征在于：b步骤中，搅拌速率为100～150转/分钟；搅拌时间为15～30分钟。The method for recovering a negative electrode sheet for a metal lithium battery according to claim 1, wherein in the step b, the stirring rate is 100 to 150 rpm, and the stirring time is 15 to 30 minutes.
  5. 根据权利要求1所述的金属锂电池负极片的回收方法，其特征在于：c步骤中，采用过滤器进行保温过滤，所述过滤器精度为15～30μm。The method for recovering a negative electrode sheet for a metal lithium battery according to claim 1, wherein in the step c, the filter is subjected to thermal insulation filtration, and the filter has an accuracy of 15 to 30 μm.
  6. 根据权利要求5所述的金属锂电池负极片的回收方法，其特征在于：过滤器精度为15μm。The method for recovering a negative electrode sheet for a metal lithium battery according to claim 5, wherein the filter has an accuracy of 15 μm.
  7. 根据权利要求1所述的金属锂电池负极片的回收方法，其特征在于：d步骤中，采用过滤器进行过滤，所述过滤器精度为5～10μm。The method for recovering a negative electrode sheet for a lithium metal battery according to claim 1, wherein in the step d, the filter is used for filtration, and the filter has an accuracy of 5 to 10 μm.
  8. 根据权利要求1所述的金属锂电池负极片的回收方法，其特征在于：e步骤中的真空除油温度为240～260℃，真空度为0.8～1.2Pa。The method for recovering a negative electrode sheet for a metal lithium battery according to claim 1, wherein the vacuum degreasing temperature in the step e is 240 to 260 ° C, and the degree of vacuum is 0.8 to 1.2 Pa.
  9. 根据权利要求8所述的金属锂电池负极片的回收方法，其特征在于：e步骤中的真空除油温度为250℃，真空度为1Pa。The method for recovering a negative electrode sheet for a metal lithium battery according to claim 8, wherein the vacuum deoiling temperature in the step e is 250 ° C and the degree of vacuum is 1 Pa.
  10. 根据权利要求1～9任一项所述的金属锂电池负极片的回收方法，其特征在于：所述金属锂电池负极片的来源为金属锂电池负极片边角料、废料或金属锂电池拆解后的负极。The method for recovering a negative electrode sheet for a metal lithium battery according to any one of claims 1 to 9, characterized in that the source of the negative electrode sheet of the lithium metal battery is a metal lithium battery negative electrode scrap, scrap or metal lithium battery after disassembling The negative pole.
  11. 根据权利要求1～10任一项所述的金属锂电池负极片的回收方法，其特征在 于：所述金属锂电池为金属锂一次电池、金属锂二次电池、锂合金一次电池或锂合金二次电池。 A method for recovering a negative electrode sheet for a metal lithium battery according to any one of claims 1 to 10, characterized in that The metal lithium battery is a metal lithium primary battery, a metal lithium secondary battery, a lithium alloy primary battery, or a lithium alloy secondary battery.
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