WO2025035359A1 - 一种三元锂电池高压还原回收镍钴锰锂和负极石墨的方法 - Google Patents

一种三元锂电池高压还原回收镍钴锰锂和负极石墨的方法 Download PDF

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WO2025035359A1
WO2025035359A1 PCT/CN2023/112916 CN2023112916W WO2025035359A1 WO 2025035359 A1 WO2025035359 A1 WO 2025035359A1 CN 2023112916 W CN2023112916 W CN 2023112916W WO 2025035359 A1 WO2025035359 A1 WO 2025035359A1
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lithium
leaching
cobalt
manganese
negative electrode
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French (fr)
Inventor
安辉
阮丁山
李长东
陈若葵
付堂新
邓开伟
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to CN202380011474.3A priority Critical patent/CN117280053B/zh
Priority to PCT/CN2023/112916 priority patent/WO2025035359A1/zh
Publication of WO2025035359A1 publication Critical patent/WO2025035359A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00—Obtaining manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the present invention belongs to the technical field of valuable metal resource recycling, and specifically relates to a method for recovering nickel, cobalt, manganese, lithium and negative electrode graphite through high-voltage reduction of a ternary lithium battery.
  • Waste lithium-ion batteries usually contain a large amount of organic harmful pollutants and heavy metal inorganic compounds. Improper disposal will pose a serious threat to human health, the environment and biota.
  • the heavy metals and negative electrode graphite in waste batteries have recycling value because they can be reused in the manufacture of new energy materials, thereby reducing environmental pollution and generating good economic benefits.
  • Waste ternary lithium-ion batteries contain a large amount of valuable metals such as nickel, cobalt, manganese, and lithium. Recycling them is beneficial to environmental protection and improving economic benefits.
  • the main industrial process for recycling valuable metals in waste batteries is: under normal pressure, nickel, cobalt, manganese, and lithium in battery powder are recovered in the form of nickel sulfate, cobalt sulfate, manganese sulfate, and lithium sulfate by adding sulfuric acid and hydrogen peroxide.
  • This conventional method has low recovery efficiency, and bubbling occurs when hydrogen peroxide is added, which increases the safety risk of on-site operation.
  • Another method is to use a low-acid combined with high-pressure leaching process. However, this method does not take into account two safety hazards. On the one hand, there are inevitably fluorine-containing compounds in battery powder.
  • fluorine-containing compounds come from lithium hexafluorophosphate in the electrolyte or PVDF in the diaphragm. Fluorine will react with hydrogen ions to form hydrofluoric acid during high-pressure acid leaching. Hydrofluoric acid is a highly corrosive acid that will corrode the autoclave, causing safety hazards and increasing subsequent maintenance costs. On the other hand, battery powder also contains substances such as aluminum foil. If these elemental metals are not treated before high-pressure leaching, hydrogen will be generated by reacting with acid during high-pressure leaching, which poses an explosion risk. In addition, if the leached residue containing carbon powder is directly scrapped without recovering the negative electrode carbon powder, it will not only waste graphite resources, but also affect the environment and health. Therefore, it is urgent to develop a method for efficiently recovering valuable metals and negative electrode graphite in waste ternary lithium batteries.
  • the present disclosure aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present disclosure proposes a method for recovering nickel, cobalt, manganese, lithium and negative electrode graphite by high-voltage reduction of a ternary lithium battery.
  • a method for recovering nickel, cobalt, manganese, lithium and negative electrode graphite by high-voltage reduction of a ternary lithium battery comprising the following steps:
  • step S2 mixing the first acid leaching residue obtained in step S1 with alkali solution to prepare pulp, and roasting the pulp once to obtain roasted residue;
  • step S3 mixing the roasted slag obtained in step S2 with a second acid solution, leaching under pressure, obtaining a second acid leaching solution and a second acid leaching slag after solid-liquid separation, and performing secondary roasting on the second acid leaching slag to obtain battery-grade graphite powder;
  • step S1 the concentration of the first acid solution is 80-220 g/L, and the liquid-solid ratio of the first acid solution to the waste battery powder is (4-10): 1 mL/g;
  • step S2 the pulping temperature is 70-100°C;
  • step S3 the concentration of the second acid solution is 230-500 g/L, and the pressure of the pressurized leaching is 0.4-1.6 MPa.
  • the waste battery powder is obtained by discharging, disassembling and crushing waste ternary lithium batteries.
  • step S1 the liquid-to-solid ratio of the first acid solution to the waste battery powder is (5-8): 1 mL/g; and/or, the stirring speed during the leaching process is 300-500 rpm.
  • the first acid solution is a sulfuric acid solution
  • the concentration of the first acid solution is 100-200 g/L. Lithium in the battery powder is leached prior to nickel, cobalt, and manganese, and at the concentration of the first acid solution, lithium can be efficiently and completely leached to avoid affecting the subsequent defluorination process.
  • step S1 the amount of the first acid solution added is in excess of the lithium content in the waste battery powder.
  • step S1 the leaching is performed under normal pressure.
  • the leaching time is 3-7 hours; and/or the leaching time is During the process, the pH is controlled at 1.0-1.5; and/or, the leaching temperature is 60-90° C. After the first acid leaching liquid is subjected to conventional purification, extraction and other treatments, a metal liquid for preparing a ternary precursor is obtained.
  • the alkali solution is at least one of a sodium hydroxide solution or a potassium hydroxide solution.
  • the alkali solution is a potassium hydroxide solution.
  • potassium hydroxide is less corrosive to some equipment, and in the subsequent defluorination process, the solubility of potassium fluoride is much greater than that of sodium fluoride: potassium fluoride 142g/60°C, sodium fluoride 4.7g/60°C, and potassium hydroxide is used to form potassium fluoride that is easily soluble in water, which is conducive to removing fluorine.
  • the concentration of the alkali solution is 1-3 mol/L; and/or the liquid-to-solid ratio of the alkali solution to the first acid leaching residue is (1-4): 1 mL/g.
  • step S2 the stirring speed during the slurrying is 300-500 rpm; and/or the slurrying time is 2-4 hours.
  • the primary roasting environment is an air atmosphere; and/or the primary roasting temperature is 600-1000°C; and the primary roasting time is 0.5-2h.
  • the slurry contains potassium hydroxide solution, which can promote the carbon powder to reduce the high-valent cobalt and manganese in the first acid leaching residue that are difficult to leach into low-valent metal oxides that are easy to leach during roasting; and the potassium hydroxide solution can also react with the fluorine-containing compounds in the first acid leaching residue to remove them.
  • the slurry has been fully stirred before the first roasting.
  • the carbon powder will react with the metal oxide first.
  • the atmosphere of the first roasting is air
  • the carbon powder will not reduce the metal element to a single substance, avoiding the subsequent high-pressure leaching, the metal element reacts with the acid to generate hydrogen, forming an explosion risk.
  • the roasting time cannot be too long, otherwise the carbon powder will react with the oxygen in the air and cause more losses.
  • step S2 further comprises washing the calcined slag, washing the calcined slag with water, wherein the liquid-solid ratio of water to the calcined slag is (2-5): 1 mL/g; and/or the washing time is 1-3 h; and/or the washing temperature is 60-90° C.
  • the second acid solution is a sulfuric acid solution, and the concentration of the second acid solution is 250-450 g/L.
  • step S3 the liquid-to-solid ratio of the second acid solution to the calcined slag is (1-3): 1 mL/g.
  • the pressure leaching time is 3-8 hours; and/or the pressure leaching temperature is 110-200°C. Pressurization can increase the boiling point of water, thereby increasing the pressure leaching temperature. High temperature can effectively improve the leaching efficiency, and can also leach out the high-valent nickel and cobalt that may be contained in the roasted slag.
  • the secondary calcination environment is an inert atmosphere; and/or, the secondary calcination temperature is 2000-3000° C.; and/or, the secondary calcination time is 20-40 hours.
  • the secondary calcination converts the amorphous carbon material into a graphitized carbon material, thereby improving the recycling rate of graphite.
  • the stirring speed is independently 300-500 rpm.
  • a method for recycling lithium batteries comprising the steps of the method for recovering nickel, cobalt, manganese, lithium and negative electrode graphite by high-voltage reduction of ternary lithium batteries as described in the first aspect of the present disclosure.
  • the application of the method for recovering nickel, cobalt, manganese, lithium and negative electrode graphite by high-voltage reduction of ternary lithium batteries described in the first aspect of the present disclosure in lithium battery recovery is proposed.
  • the present disclosure provides a method for recovering nickel, cobalt, manganese, lithium and negative electrode graphite from waste ternary lithium batteries by high-pressure reduction.
  • the first step of the method is low-acid selective lithium extraction. By controlling the amount of acid, all the lithium in the raw material is leached out, as well as a small amount of nickel, cobalt and manganese. The leaching of part of the nickel, cobalt and manganese can reduce the burden of subsequent high-pressure leaching.
  • the aluminum surface in the waste battery powder is often coated with a layer of aluminum oxide, the aluminum oxide will not be dissolved under the conditions of low-acid leaching.
  • the boiling point of water can be increased by pressurization, thereby increasing the leaching temperature.
  • the complete leaching of nickel, cobalt and manganese can be ensured.
  • the use of a higher concentration of acid solution in high-pressure leaching is also beneficial to reduce the amount of new acid solution added when it is subsequently reused for low-acid leaching.
  • potassium hydroxide solution is added to prepare the slurry.
  • the fluorine-containing compound will react with potassium hydroxide to form potassium fluoride which is easily soluble in water. If lithium is present, lithium fluoride will be formed first. Lithium fluoride is insoluble in water, while potassium fluoride is easily soluble in water. The solubility of potassium fluoride is much greater than that of lithium fluoride. The presence of lithium in the fluorine removal process will make it difficult to completely remove fluorine. Therefore, the first step of low-acid selective lithium extraction is necessary to avoid the subsequent The formation of hydrogen fluoride during the high-pressure leaching process caused the autoclave to be corroded.
  • the present invention uses the first acid leaching residue and potassium hydroxide solution to make pulp and roast, which mainly has the following four functions:
  • the first acid leaching residue is stirred and reacted with potassium hydroxide solution at high temperature to remove aluminum/alumina from waste battery powder.
  • the elemental aluminum/alumina reacts with potassium hydroxide to form potassium aluminate soluble in water.
  • the first function is to avoid the elemental aluminum reacting with acid to generate hydrogen in high-pressure leaching, which may cause explosion risk.
  • the second function is to reduce the subsequent impurity removal load, such as the removal of impurities such as iron and aluminum.
  • the reaction equation is as follows: 2Al+2KOH+2H 2 O ⁇ 2KAlO 2 +3H 2 Al 2 O 3 +2KOH+2H 2 O ⁇ 2KAlO 2 +3H 2 O
  • the first acid leaching residue is stirred and reacted with potassium hydroxide solution at high temperature, and the fluorine-containing compounds can react with the potassium hydroxide solution to generate potassium fluoride that is easily soluble in water.
  • the potassium fluoride in the residue can be completely removed by water washing.
  • the fluorine-containing compounds include PVDF (chemical formula C 2 H 2 F 2 ) in the diaphragm, hydrogen fluoride residual from low-acid leaching, etc.
  • the reaction equation is as follows: C 2 H 2 F 2 (PVDF)+2KOH+O 2 ⁇ 2KF+CO 2 +2H 2 O HF+KOH ⁇ KF+ H2O
  • the Ni ions in the reactants are in a valence state of +2, the Co ions are in a valence state of +3, and the Mn ions are in a valence state of +4; the Ni, Co, and Mn ions in the products are all in a valence state of +2.
  • the metal residue in the second leaching residue of the present invention is extremely low.
  • the carbon material in graphite form can be obtained by high-temperature roasting under inert gas, which can be used as battery-grade graphite, solving the problem of difficulty in graphite recovery in battery powder leaching residue, and achieving effective recycling of graphite.
  • the present invention has the advantages of simple process, environmental friendliness, high safety, high economic benefit, high production efficiency and high recycling rate, which not only realizes the resource utilization of waste batteries, but also improves economic benefits.
  • FIG1 is a process flow chart of Example 1 of the present disclosure.
  • a method for recovering nickel, cobalt, manganese, lithium and negative electrode graphite from waste ternary lithium batteries by high-voltage reduction, as shown in FIG1 comprises the following steps:
  • the content of roasted washing slag F is 0.0001wt.%, and 1.5L water is added at a liquid-solid ratio of 3:1mL/g in a high-pressure reactor, and then 500g of 98% sulfuric acid is added.
  • the temperature is controlled at 160°C and the pressure is 0.8Mpa. After reacting for 3h, wait for the high pressure to react.
  • the autoclave temperature is cooled, and the high-pressure leaching liquid obtained by filtration is returned to the low-acid leaching as acid solution.
  • the obtained high-pressure leaching residue is washed and graphitized at 2000°C for 30 hours to obtain battery-grade graphite for sale.
  • the leaching results are as follows:
  • the recovery rates of Ni, CO, Mn and Li are obtained by the following steps: determining the mass of the battery powder raw material and the content of Ni, Co, Mn and Li therein, and the mass of the high-pressure leaching slag and the content of Ni, Co, Mn and Li therein, and calculating the masses of Ni, Co, Mn and Li in the battery powder raw material and the high-pressure leaching slag respectively.
  • the ratio of the difference between the two and the mass of the corresponding metal in the battery powder raw material is the recovery rate of the metal element.
  • the recovery rate of C is obtained by the following steps: using a carbon-sulfur meter to respectively determine the C content in the battery powder raw material and the high-pressure leaching slag after graphitization treatment, and calculating the mass of C therein based on the mass of the battery powder raw material and the high-pressure leaching slag after graphitization treatment.
  • the ratio of the mass of C in the high-pressure leaching slag after graphitization treatment to the mass of C in the battery powder raw material is the recovery rate of C.
  • a method for recycling lithium batteries comprising the steps of the method for recovering nickel, cobalt, manganese, lithium and negative electrode graphite through high-voltage reduction of the above-mentioned ternary lithium battery.
  • a method for recovering nickel, cobalt, manganese, lithium and negative electrode graphite from waste ternary lithium batteries by high-voltage reduction comprising the following steps:
  • the roasted washed slag F content is 0.0002wt.%, and 1L of water is added at a liquid-solid ratio of 2:1mL/g and placed in a high-pressure reactor. Then 400g of 98% sulfuric acid is added. The temperature is controlled at 180°C and the pressure is 1Mpa. After reacting for 4 hours, the autoclave temperature is cooled, and the high-pressure leaching liquid obtained by filtration is returned to the low-acid leaching as acid. The high-pressure leaching slag is washed and graphitized at 2500°C for 25 hours to obtain battery-grade graphite for sale.
  • the leaching results are as follows:
  • a method for recycling lithium batteries comprising the steps of the method for recovering nickel, cobalt, manganese, lithium and negative electrode graphite through high-voltage reduction of the above-mentioned ternary lithium battery.
  • a method for recovering nickel, cobalt, manganese, lithium and negative electrode graphite from waste ternary lithium batteries by high-voltage reduction comprising the following steps:
  • the roasting washing slag F content is 0.0001wt.% and 600mL of water is added at a liquid-solid ratio of 1:1mL/g and placed in a high pressure reactor.
  • 250g of 98% sulfuric acid was added to the autoclave, the temperature was controlled at 170°C, the pressure was 0.9Mpa, and the reaction was continued for 6 hours.
  • the high-pressure leaching liquid obtained by filtration was returned to the low-acid leaching as acid liquid.
  • the high-pressure leaching residue was washed and graphitized at 3000°C for 20 hours to obtain battery-grade graphite for sale.
  • the leaching results are as follows:
  • a method for recycling lithium batteries comprising the steps of the method for recovering nickel, cobalt, manganese, lithium and negative electrode graphite through high-voltage reduction of the above-mentioned ternary lithium battery.
  • a method for recovering nickel, cobalt, manganese, lithium and negative electrode graphite by high-voltage reduction of waste ternary lithium batteries which differs from Example 1 in that the low-acid leaching slag is not treated with a potassium hydroxide solution, comprises the following steps:
  • the low-acid slag has not been treated with potassium hydroxide solution to remove fluorine, and the fluorine content is relatively high, so it cannot enter the autoclave for the subsequent high-pressure leaching step.
  • a method for recovering nickel, cobalt, manganese, lithium and negative electrode graphite from waste ternary lithium batteries by high-voltage reduction which differs from Example 1 in that the acid solution concentration in step (1) is relatively low, and comprises the following steps:
  • step (1) the acid solution concentration is low and the lithium in the waste battery powder cannot be completely leached out.
  • lithium and fluorine-containing compounds generate lithium fluoride which is insoluble in water, resulting in a large amount of fluorine remaining in the roasting and washing residue.

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Abstract

一种三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，包括以下步骤：将废旧电池粉低酸浸出，固液分离后所得低酸渣与碱液混合制浆，浆料进行一次焙烧后得到的焙烧渣进行高压浸出，固液分离后所得高压浸出渣进行二次焙烧，得到电池级石墨粉。

Description

一种三元锂电池高压还原回收镍钴锰锂和负极石墨的方法 技术领域
本公开属于有价金属资源再生技术领域，具体涉及一种三元锂电池高压还原回收镍钴锰锂和负极石墨的方法。
背景技术
近年来，新能源汽车产业飞速发展的同时，也产生了大量的固体废物-废旧锂离子电池。废旧的锂离子电池中通常含有大量有机有害污染物和重金属无机化合物，处置不当会对人类健康、环境和生物群构成严重威胁。废旧电池中的重金属和负极石墨具有回收价值，因为它们在新能源材料制造中可以重复利用，从而减轻环境污染和产生良好的经济效益。废旧三元锂离子电池中含有大量的镍、钴、锰、锂等有价金属，对其进行回收有利于环境保护和提高经济效益。此外，天然石墨资源的不断减少以及人造石墨价格的快速增加，使得有效回收废旧电池中的负极石墨变得尤为重要。因此，高效率和高回收率的废旧电池回收技术将成为近年来发展的热点。
目前工业上回收废旧电池中的有价金属工艺主要是：常压下，通过硫酸加双氧水将电池粉中的镍、钴、锰、锂分别以硫酸镍、硫酸钴、硫酸锰和硫酸锂等形式回收。这种常规方法回收效率低，并且在加入双氧水的同时会出现冒槽现象，增加了现场操作的安全风险。另一种方法是采用低酸配合高压浸出的工艺流程。然而，这种方法没有考虑到两种安全隐患。一方面是电池粉中不可避免的会有含氟化合物，这些含氟化合物来自于电解液中的六氟磷酸锂或者隔膜中的PVDF，氟在高压酸浸的过程中会与氢离子形成氢氟酸。氢氟酸是一种腐蚀性很强的酸，会对高压釜造成腐蚀，造成安全隐患，同时也增加后续维护成本。另一方面电池粉中也含有铝箔等物质，若在高压浸出前没有处理这些单质金属，在高压浸出中与酸反应会生成氢气，存在爆炸风险。另外，若将最终含有碳粉的浸出渣直接报废处理，未回收其中的负极碳粉，不仅会造成石墨资源的浪费，还会影响环境和健康。因此，急需开发一种高效回收废旧三元锂电池中有价金属与负极石墨的方法。
发明内容
本公开旨在至少解决上述现有技术中存在的技术问题之一。为此，本公开提出一种三元锂电池高压还原回收镍钴锰锂和负极石墨的方法。
根据本公开的第一方面，提出了一种三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，包括以下步骤：
S1：将废旧电池粉与第一酸液混合浸出，固液分离后得到第一酸浸液与第一酸浸渣；
S2：将步骤S1制得的所述第一酸浸渣与碱液混合制浆，浆料进行一次焙烧后得到焙烧渣；
S3：将步骤S2制得的所述焙烧渣与第二酸液混合，加压浸出，固液分离后得到第二酸浸液与第二酸浸渣，所述第二酸浸渣进行二次焙烧后得到电池级石墨粉；
其中，步骤S1中，所述第一酸液的浓度为80-220g/L，所述第一酸液与所述废旧电池粉的液固比为(4-10)：1mL/g；
步骤S2中，所述制浆的温度为70-100℃；
步骤S3，中所述第二酸液的浓度为230-500g/L，所述加压浸出的压力为0.4-1.6MPa。
在一些实施方式中，步骤S1中，所述废旧电池粉由废旧三元锂电池进行放电、拆解及破碎处理后获得。
在一些实施方式中，步骤S1中，所述第一酸液与所述废旧电池粉的液固比为(5-8)：1mL/g；和/或，所述浸出的过程中搅拌速度为300-500rpm。
在一些实施方式中，步骤S1中，所述第一酸液为硫酸溶液，所述第一酸液的浓度为100-200g/L。电池粉中的锂优先于镍、钴、锰浸出，在所述第一酸液的浓度下能保证锂可以高效地全部浸出，避免对后续的除氟过程造成影响。
在一些实施方式中，步骤S1中，所述第一酸液的加入量过量于所述废旧电池粉中锂的含量。
在一些实施方式中，步骤S1中，所述浸出在常压下进行。
在一些实施方式中，步骤S1中，所述浸出的时间为3-7h；和/或，所述浸出的过 程中pH控制在1.0-1.5；和/或，所述浸出的温度为60-90℃。第一酸浸液经过常规净化、萃取等处理后，得到用于制备三元前驱体的金属液。
在一些实施方式中，步骤S2中，所述碱液为氢氧化钠溶液或氢氧化钾溶液中的至少一种。
在一些实施方式中，步骤S2中，所述碱液为氢氧化钾溶液。相较于氢氧化钠，氢氧化钾对一些设备的腐蚀性较弱，且后续除氟过程中，氟化钾的溶解度远大于氟化钠：氟化钾142g/60℃、氟化钠4.7g/60℃，用氢氧化钾形成易溶于水的氟化钾，有利于除去氟。
在一些实施方式中，步骤S2中，所述碱液的浓度为1-3mol/L；和/或，所述碱液与所述第一酸浸渣的液固比为(1-4)：1mL/g。
在一些实施方式中，步骤S2中，所述制浆时的搅拌速度为300-500rpm；和/或，所述制浆的时间为2-4h。
在一些实施方式中，步骤S2中，所述一次焙烧的环境为空气气氛；和/或，所述一次焙烧的温度为600-1000℃；所述一次焙烧的时间为0.5-2h。浆料中含有氢氧化钾溶液，能促进碳粉在焙烧时将第一酸浸渣中难浸出的高价态钴和锰还原为易浸出的低价态金属氧化物；同时氢氧化钾溶液还能与第一酸浸渣中的含氟化合物反应从而将其去除。
浆料在一次焙烧前已充分搅匀，在焙烧过程中碳粉将优先与金属氧化物反应；同时由于一次焙烧的气氛为空气气氛，碳粉不会把金属元素还原为单质，避免后续进行高压浸出时，金属单质与酸反应生成氢气，形成爆炸风险。焙烧的时间不能过长，否则碳粉会与空气中氧气发生反应而造成较多损失。
在一些实施方式中，步骤S2中，还包括对所述焙烧渣进行洗涤。用水洗涤所述焙烧渣，水与所述焙烧渣的液固比为(2-5)：1mL/g；和/或，所述洗涤的时间为1-3h；和/或，所述洗涤的温度为60-90℃。
在一些实施方式中，步骤S3中，所述第二酸液为硫酸溶液，所述第二酸液的浓度为250-450g/L。
在一些实施方式中，步骤S3中，所述第二酸液与所述焙烧渣的液固比为(1-3)：1mL/g。
在一些实施方式中，步骤S3中，所述加压浸出的时间为3-8h；和/或，所述加压浸出的温度为110-200℃。加压能提高水的沸点，从而提高加压浸出的温度。高温能有效提高浸出的效率，同时也能将焙烧渣中可能含有的高价态的镍和钴一同浸出。
在一些实施方式中，步骤S3中，所述二次焙烧的环境为惰性气氛；和/或，所述二次焙烧的温度为2000-3000℃；和/或，所述二次焙烧的时间为20-40h。二次焙烧将无定形碳材料转化为石墨化碳材料，提高了石墨的回收利用率。
在一些实施方式中，在步骤S1所述浸出的过程与步骤S3所述加压浸出的过程中，搅拌速度分别独立为300-500rpm。
根据本公开的第二方面，提出了一种锂电池回收的方法，包括本公开第一方面所述的三元锂电池高压还原回收镍钴锰锂和负极石墨的方法的步骤。
根据本公开的第三方面，提出了本公开第一方面所述的三元锂电池高压还原回收镍钴锰锂和负极石墨的方法在锂电池回收中的应用。
根据本公开的一种实施方式，至少具有以下有益效果：
1、本公开提供了一种废旧三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，该方法第一步为低酸选择性提锂，通过控制酸量将原料中的锂全部浸出以及少部分镍钴锰浸出，部分镍钴锰的浸出能为后续高压浸出减轻负担。另外，由于废旧电池粉中的铝表面往往包裹着一层氧化铝，所述氧化铝在低酸浸出的条件下不会被溶解。后续高压浸出的过程中，采用加压的方式可提高水的沸点，从而提高浸出温度，配合较高浓度的酸液，可确保镍、钴、锰完全浸出。高压浸出中采用较高浓度的酸液，还有利于后续回用于低酸浸出时减少新的酸液的加入量。
2、本公开的第二步加入氢氧化钾溶液制浆，浆料高温焙烧过程中，含氟化合物会与氢氧化钾反应生成易溶于水的氟化钾，若有锂存在则会优先形成氟化锂。氟化锂不溶于水，氟化钾易溶于水，并且氟化钾的溶解度远大于氟化锂，除氟工序中锂的存在会使得氟难以完全被去除，因此第一步低酸选择性提锂这一工序的设置是必要的，避免了后 续高压浸出过程中氟化氢的形成导致高压釜被腐蚀破坏。
3、本公开将第一酸浸渣与氢氧化钾溶液制浆焙烧，主要有以下四种作用：
(1)第一酸浸渣与氢氧化钾溶液在高温下搅拌反应，可以将废旧电池粉中的铝/氧化铝去除，单质铝/氧化铝与氢氧化钾反应生成溶于水的偏铝酸钾，作用一是避免高压浸出中单质铝与酸反应生成氢气，造成爆炸风险；作用二是减小后续除杂负荷，比如除铁铝等杂质；反应方程式如下：
2Al+2KOH+2H2O→2KAlO2+3H2
Al2O3+2KOH+2H2O→2KAlO2+3H2O
(2)第一酸浸渣与氢氧化钾溶液在高温下搅拌反应，可以将含氟化合物与氢氧化钾溶液反应生成易溶于水的氟化钾，经过水洗可将渣中的氟化钾去除完全，含氟化合物包括隔膜中的PVDF(化学式C2H2F2)、低酸浸出残留的氟化氢等，反应方程如下：
C2H2F2(PVDF)+2KOH+O2→2KF+CO2+2H2O
HF+KOH→KF+H2O
(3)将第一酸浸渣中的高价态金属在碳粉的还原作用下转化为易浸出的低价态金属氧化物，减少了还原剂辅料的投入成本。其中氢氧化钾起到催化作用，有利于还原反应的进行，催化机理如下：
2KOH+C→K2O+CO+H2


K2O+H2O→2KOH
其中，反应物中Ni离子为+2价态、Co离子为+3价态、Mn离子为+4价态；生成物中Ni、Co、Mn离子均为+2价态。
(4)焙烧将第一酸浸渣中未反应完全的金属单质氧化为金属氧化物，避免在高压反应釜中产生氢气，容易产生爆炸风险，相关反应方程如下：
2Al+3H2SO4→Al2(SO4)3+3H2↑
4Al+3O2→2Al2O3
Al2O3+3H2SO4→Al2(SO4)3+3H2O
4、本公开第二浸出渣中金属残留量极低，在惰性气体下高温焙烧可得到石墨化形态的碳材料，能作为电池级石墨，解决了电池粉浸出渣中石墨回收难度大问题，达到了石墨的有效回收利用
5、本公开具有流程简单、环境友好、安全性高、经济效益高、生产效率高、回收率高等优点，既实现了废旧电池的资源化利用，又提高了经济效益。
附图说明
下面结合附图和实施例对本公开做进一步的说明，其中：
图1为本公开实施例1的工艺流程图。
具体实施方式
以下将结合实施例对本公开的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本公开的目的、特征和效果。
实施例1
一种废旧三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，如图1所示，包括以下步骤：
1.取废旧电池粉1kg，其中镍、钴、锰、锂含量分别为26.2931％、4.0768％、3.5236％、4.0665％，按液固比5:1mL/g加入5L水，再加入600g 98％的硫酸，温度控制在70℃，搅拌速度为350rpm，反应过程中pH保持在1.1以下，反应6h后过滤得到低酸浸出液和低酸浸出渣，低酸浸出液经过除杂工序用于三元前驱体制备。
2.低酸浸出渣按液固比为1:3mL/g加入1mol/L氢氧化钾溶液，形成浆料85℃搅拌3h混匀，将混匀后的浆料放入焙烧炉中，温度为900℃，焙烧时间为1.5h，焙烧结束后，将焙烧渣用80℃纯水搅洗2h，过滤后再用纯水淋洗，得到焙烧洗涤渣。
3.焙烧洗涤渣F含量为0.0001wt.％，并按液固比3:1mL/g加入1.5L水置于高压反应釜内，再加入500g 98％的硫酸，温度控制在160℃，压力为0.8Mpa，反应3h后待高 压釜温度冷却，过滤得到的高压浸出液作为酸液返回低酸浸出，得到的高压浸出渣经洗涤后，经过2000℃、30h石墨化处理后，得到电池级石墨外售。
浸出结果如下：
其中，Ni、CO、Mn和Li的回收率通过以下步骤得到：测定电池粉原料的质量以及其中Ni、Co、Mn、Li的含量，和高压浸出渣的质量以及其中Ni、Co、Mn、Li的含量，分别算出电池粉原料、高压浸出渣中Ni、Co、Mn、Li质量，两者差值与电池粉原料中对应金属质量的比值即为该金属元素的回收率。
C的回收率通过以下步骤得到：利用碳硫仪分别测定电池粉原料及石墨化处理后的高压浸出渣中的C含量，并根据电池粉原料及石墨化处理后的高压浸出渣的质量算出其中的C的质量，石墨化处理后的高压浸出渣中C的质量与电池粉原料中C的质量的比值即为C的回收率。
一种锂电池回收的方法，包括上述三元锂电池高压还原回收镍钴锰锂和负极石墨的方法的步骤。
实施例2
一种废旧三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，包括以下步骤：
1.取废旧电池粉1kg，其中镍、钴、锰、锂含量分别为25.6394％、6.0311％、4.5143％、5.6091％，按液固比6:1mL/g加入6L水，再加入700g 98％的硫酸，温度控制在90℃，搅拌速度为300rpm，反应过程中pH保持在1.2以下，反应5h后过滤得到低酸浸出液和低酸浸出渣，低酸浸出液经过除杂工序用于三元前驱体制备。
2.低酸浸出渣按液固比为1:2mL/g加入3mol/L氢氧化钾溶液，形成浆料80℃搅拌 3h混匀，将混匀后的浆料放入焙烧炉中，温度为900℃，焙烧时间为1.5h，焙烧结束后，将焙烧渣用80℃纯水搅洗2h，过滤后再用纯水淋洗，得到焙烧洗涤渣。
3.焙烧洗涤渣F含量为0.0002wt.％并按液固比2:1mL/g加入1L水置于高压反应釜内，再加入400g 98％的硫酸，温度控制在180℃，压力为1Mpa，反应4h后待高压釜温度冷却，过滤得到的高压浸出液作为酸液返回低酸浸出，得到的高压浸出渣经洗涤后，经过2500℃、25h石墨化处理后，得到电池级石墨外售。
浸出结果如下：
一种锂电池回收的方法，包括上述三元锂电池高压还原回收镍钴锰锂和负极石墨的方法的步骤。
实施例3
一种废旧三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，包括以下步骤：
1.取废旧电池粉1kg，其中镍、钴、锰、锂含量分别为28.0455％、5.0033％、3.9018％、7.9602％，按液固比7:1mL/g加入7L水，再加入900g 98％的硫酸，温度控制在60℃，搅拌速度为400rpm，反应过程中pH保持在1.0，反应5.5h后过滤得到低酸浸出液和低酸浸出渣，低酸浸出液经过除杂工序用于三元前驱体制备。
2.低酸浸出渣按液固比为1:1mL/g加入2mol/L氢氧化钾溶液，形成浆料70℃搅拌2h混匀，将混匀后的浆料放入焙烧炉中，温度为1000℃，焙烧时间为1h，焙烧结束后，将焙烧渣用70℃纯水搅洗3h，过滤后再用纯水淋洗，得到焙烧洗涤渣。
3.焙烧洗涤渣F含量为0.0001wt.％并按液固比1:1mL/g加入600mL水置于高压反 应釜内，再加入250g 98％的硫酸，温度控制在170℃，压力为0.9Mpa，反应6h后待高压釜温度冷却，过滤得到的高压浸出液作为酸液返回低酸浸出，得到的高压浸出渣经洗涤后，经过3000℃、20h石墨化处理后，得到电池级石墨外售。
浸出结果如下：
一种锂电池回收的方法，包括上述三元锂电池高压还原回收镍钴锰锂和负极石墨的方法的步骤。
对比例1
一种废旧三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，与实施例1的区别在于，低酸浸出渣不经过氢氧化钾溶液处理，包括以下步骤：
取废旧电池粉1kg，其中镍、钴、锰、锂含量分别为26.2931％、4.0768％、3.5236％、4.0665％，按液固比5:1mL/g加入5L水，再加入600g 98％的硫酸，温度控制在70℃，搅拌速度为350rpm，反应过程中pH保持在1.1以下，反应6h后过滤得到低酸浸出液和低酸浸出渣，低酸浸出渣经检测氟含量为0.6％，氟残留含量较高，进入高压釜的原料氟含量不能高于0.1％，否则会腐蚀高压釜。
低酸渣未经氢氧化钾溶液处理除氟，氟含量较高，不能进入高压釜中进行后续高压浸出步骤。
对比例2
一种废旧三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，与实施例1的区别在于，步骤(1)中酸液浓度较低，包括以下步骤：
(1)取废旧电池粉1kg，其中镍、钴、锰、锂含量分别为26.2931％、4.0768％、3.5236％、 4.0665％，按液固比5:1mL/g加入5L水，再加入400g 98％的硫酸，温度控制在70℃，搅拌速度为350rpm，反应6h后过滤得到低酸浸出液和低酸浸出渣，低酸渣含量为下：Ni 16.69％、Co 3.77％、Mn 5.54％、Li 1.2％。
(2)低酸浸出渣按液固比为1:3mL/g加入1mol/L氢氧化钾溶液，形成浆料85℃搅拌3h混匀，将混匀后的浆料放入焙烧炉中，温度为900℃，焙烧时间为1.5h，焙烧结束后，将焙烧渣用80℃纯水搅洗2h，过滤后再用纯水淋洗，得到焙烧洗涤渣,渣中氟含量经检测为0.29％，氟残留含量较高，进入高压釜的原料氟含量不能高于0.1％，否则会腐蚀高压釜。
步骤(1)中酸液浓度较低，未能将废旧电池粉中的锂完全浸出，在焙烧过程中锂与含氟化合物生成难溶于水的氟化锂，导致焙烧洗涤渣中仍残留较多氟。
由实施例1-3、对比例1-2的实验结果可得，实施例1-3的Ni、Co、Mn和Li的回收率均达99.98％以上；同时高压浸出渣中金属含量极低，高温煅烧后可得到电池级的石墨；对比文件1缺少氢氧化钾处理步骤、对比文件2低酸浸出提锂不充分，两者的中间产物氟含量较高(分别为0.6％、0.29％)，不符合进入高压釜的标准(氟含量不高于0.1％)，因此无法进行后续高压浸出的步骤。

Claims (15)

  1. 一种三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，其特征在于，包括以下步骤：
    S1：将废旧电池粉与第一酸液混合浸出，固液分离后得到第一酸浸液与第一酸浸渣；
    S2：将步骤S1制得的所述第一酸浸渣与碱液混合制浆，浆料进行一次焙烧后得到焙烧渣；
    S3：将步骤S2制得的所述焙烧渣与第二酸液混合，加压浸出，固液分离后得到第二酸浸液与第二酸浸渣，所述第二酸浸渣进行二次焙烧后得到电池级石墨粉；
    其中，步骤S1中，所述第一酸液的浓度为80-220g/L，所述第一酸液与所述废旧电池粉的液固比为(4-10)：1mL/g；
    步骤S2中，所述制浆的温度为70-100℃；
    步骤S3中，所述第二酸液的浓度为230-500g/L，所述加压浸出的压力为0.4-1.6MPa。
  2. 根据权利要求1所述的三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，其特征在于，步骤S1中，所述第一酸液与所述废旧电池粉的液固比为(5-8)：1mL/g；和/或，所述浸出的过程中搅拌速度为300-500rpm。
  3. 根据权利要求1所述的三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，其特征在于，步骤S1中，所述第一酸液为硫酸溶液，所述第一酸液的浓度为100-200g/L。
  4. 根据权利要求1所述的三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，其特征在于，步骤S1中，所述浸出的时间为3-7h；和/或，所述浸出的过程中pH控制在1.0-1.5；和/或，所述浸出的温度为60-90℃。
  5. 根据权利要求1所述的三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，其特征在于，步骤S2中，所述碱液为氢氧化钠溶液或氢氧化钾溶液中的至少一种。
  6. 根据权利要求1所述的三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，其特征在于，步骤S2中，所述碱液的浓度为1-3mol/L；和/或，所述碱液与所述第一酸浸渣的液固比为(1-4)：1mL/g。
  7. 根据权利要求1所述的三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，其特征在于，步骤S2中，所述制浆时的搅拌速度为300-500rpm；和/或，所述制浆的时间为2-4h。
  8. 根据权利要求1所述的三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，其特征在于，步骤S2中，所述一次焙烧的环境为空气气氛；和/或，所述一次焙烧的温度为600-1000℃；所述一次焙烧的时间为0.5-2h。
  9. 根据权利要求1所述的三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，其特征在于，步骤S3中，所述第二酸液为硫酸溶液，所述第二酸液的浓度为250-450g/L。
  10. 根据权利要求1所述的三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，其特征在于，步骤S3中，所述第二酸液与所述焙烧渣的液固比为(1-3)：1mL/g。
  11. 根据权利要求1所述的三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，其特征在于，步骤S3中，所述加压浸出的时间为3-8h；和/或，所述加压浸出的温度为110-200℃。
  12. 根据权利要求1所述的三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，其特征在于，步骤S3中，所述第二酸浸液作为步骤S1中的第一酸液用于废旧电池粉的浸出。
  13. 根据权利要求1所述的三元锂电池高压还原回收镍钴锰锂和负极石墨的方法，其特征在于，步骤S3中，所述二次焙烧的环境为惰性气氛；和/或，所述二次焙烧的温度为2000-3000℃；和/或，所述二次焙烧的时间为20-40h。
  14. 一种锂电池回收的方法，包括权利要求1-13任一项所述的三元锂电池高压还原回收镍钴锰锂和负极石墨的方法的步骤。
  15. 权利要求1-13任一项所述的三元锂电池高压还原回收镍钴锰锂和负极石墨的方法在锂电池回收中的应用。
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