CN115821045A - Method for separating and recovering valuable metal from lithium ion battery anode waste - Google Patents
Method for separating and recovering valuable metal from lithium ion battery anode waste Download PDFInfo
- Publication number
- CN115821045A CN115821045A CN202211569241.9A CN202211569241A CN115821045A CN 115821045 A CN115821045 A CN 115821045A CN 202211569241 A CN202211569241 A CN 202211569241A CN 115821045 A CN115821045 A CN 115821045A
- Authority
- CN
- China
- Prior art keywords
- lithium
- positive electrode
- ion battery
- waste
- electrode waste
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002699 waste material Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 30
- 150000002739 metals Chemical class 0.000 claims abstract description 27
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 22
- 238000009833 condensation Methods 0.000 claims abstract description 20
- 230000005494 condensation Effects 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 15
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 8
- 239000007859 condensation product Substances 0.000 claims description 8
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 238000002386 leaching Methods 0.000 abstract description 8
- 229910052748 manganese Inorganic materials 0.000 abstract description 8
- 239000011572 manganese Substances 0.000 abstract description 8
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 abstract description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 abstract description 3
- 230000001376 precipitating effect Effects 0.000 abstract description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 9
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000012320 chlorinating reagent Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- -1 mine tailings Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002906 medical waste Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明公开了一种从锂离子电池正极废料中分离回收有价金属的方法，包括以下步骤：将电池正极废料与CuCl2充分混合置于电阻炉中进行真空氯化焙烧，保温，控制多段冷凝温区，在对应区域收集冷凝产物，即锂、镍、钴、锰、铝的氯化物。本发明不仅充分回收了正极废料中的有价金属Ni、Co、Mn和Li，同时除去了废料中的杂质Al和Cu，使锂离子电池正极废物得到充分回收利用；与传统的浸出‑沉淀法相比，避免了浸出剂和沉淀剂的加入，简短了工艺流程，在未来工业化应用具有一定的潜力。
The invention discloses a method for separating and recovering valuable metals from lithium-ion battery positive electrode waste, comprising the following steps: fully mixing the battery positive electrode waste with CuCl2 and placing them in a resistance furnace for vacuum chlorination roasting, heat preservation, and multi-stage condensation control In the temperature zone, the condensed products are collected in the corresponding zone, namely the chlorides of lithium, nickel, cobalt, manganese and aluminum. The present invention not only fully recovers the valuable metals Ni, Co, Mn and Li in the positive electrode waste, but also removes the impurities Al and Cu in the waste, so that the positive electrode waste of the lithium ion battery is fully recycled; it is different from the traditional leaching-precipitation method Compared with that, the addition of leaching agent and precipitating agent is avoided, the process flow is shortened, and the industrial application has certain potential in the future.
Description
技术领域technical field
本发明属于锂离子电池固体废物的资源化利用技术领域，具体涉及一种从锂离子电池正极废料中分离回收有价金属的方法。The invention belongs to the technical field of resource utilization of lithium-ion battery solid waste, and in particular relates to a method for separating and recovering valuable metals from lithium-ion battery positive electrode waste.
背景技术Background technique
随着Ni、Co、Li等金属资源的短缺，这些有价金属的价格持续飞涨。为了满足生产锂离子电池所需的资源，废旧电池的回收显得愈发重要。目前，从废旧锂离子电池中提取有价金属的主流方法是用无机酸、有机酸或混合酸将有价金属转移到溶液体系中，再用草酸、碳酸盐等沉淀剂通过调节pH值逐步分离有价金属Ni、Co、Mn、Li，在此过程中可回收到接近纯的有价金属化合物。酸浸在提取废旧锂离子电池中有价金属的作用看上去无可替代，但是废酸和尾气的处理问题始终困扰着这一方法的进一步应用。With the shortage of metal resources such as Ni, Co, Li, etc., the prices of these valuable metals continue to soar. In order to meet the resources required for the production of lithium-ion batteries, the recycling of used batteries is becoming more and more important. At present, the mainstream method for extracting valuable metals from waste lithium-ion batteries is to use inorganic acids, organic acids or mixed acids to transfer valuable metals into the solution system, and then use oxalic acid, carbonate and other precipitants to gradually remove the valuable metals by adjusting the pH value. Separation of valuable metals Ni, Co, Mn, Li, during which nearly pure valuable metal compounds can be recovered. The role of acid leaching in extracting valuable metals from waste lithium-ion batteries seems irreplaceable, but the problem of waste acid and exhaust gas treatment has always plagued the further application of this method.
氯化工艺作为一种良好的固废处理方式，广泛应用于城市固废(MSW)、尾矿、医疗垃圾和核废物等领域中重金属的处理与回收。为了避免盐酸挥发造成的酸损失和空气污染，研究者们逐渐采用CaCl2、NaCl和MgCl2等不易挥发的氯化剂代替HCl。As a good solid waste treatment method, the chlorination process is widely used in the treatment and recovery of heavy metals in the fields of municipal solid waste (MSW), mine tailings, medical waste and nuclear waste. In order to avoid acid loss and air pollution caused by hydrochloric acid volatilization, researchers have gradually replaced HCl with non-volatile chlorinating agents such as CaCl 2 , NaCl and MgCl 2 .
根据相关文献报道，在锂离子电池回收领域采用酸浸工艺的研究中，有将近一半的方法仍然采用盐酸作为还原剂或浸出剂。为了改善这一状况，有研究提出了氯化焙烧的方法，用氯化剂CaCl2对废电池中的贵重金属Li进行氯化，然后浸入水中得到LiCl水溶液进行后续处理。该工艺通过严格控制工艺条件，可将锂离子电池废料中有价金属锂分离出来，具有良好的选择性。但是，所使用的氯化剂易溶于水，会引入额外的杂质元素；得到的副产物会与水发生反应，使溶液体系复杂化，对生态环境带来了不小的影响和挑战。采用氯化工艺的研究主要在常压条件下进行，目前没有Cl对真空、高温处理条件下重金属转化与挥发的相关研究。因此，研究真空-高温耦合条件下氯化物的转化与挥发热力学显得格外重要。According to relevant literature reports, in the research on the acid leaching process in the field of lithium ion battery recycling, nearly half of the methods still use hydrochloric acid as the reducing agent or leaching agent. In order to improve this situation, some studies have proposed a method of chlorination roasting, using the chlorination agent CaCl to chlorinate the precious metal Li in the waste battery, and then immersing it in water to obtain a LiCl aqueous solution for subsequent treatment. By strictly controlling the process conditions, the process can separate the valuable metal lithium from lithium-ion battery waste, and has good selectivity. However, the chlorinating agent used is easily soluble in water, which will introduce additional impurity elements; the obtained by-products will react with water, complicating the solution system and bringing considerable impact and challenges to the ecological environment. The research using the chlorination process is mainly carried out under normal pressure conditions. At present, there is no related research on the transformation and volatilization of heavy metals under the conditions of vacuum and high temperature treatment by Cl. Therefore, it is particularly important to study the conversion and volatilization thermodynamics of chlorides under coupled conditions of vacuum and high temperature.
因此，为了解决上述问题，本文提出一种从锂离子电池正极废料中分离回收有价金属的方法。Therefore, in order to solve the above problems, this paper proposes a method for separating and recovering valuable metals from lithium-ion battery cathode waste.
发明内容Contents of the invention
为了解决上述技术问题，本发明设计了一种从锂离子电池正极废料中分离回收有价金属的方法，不仅充分回收了正极废料中的有价金属Ni、Co、Mn和Li，同时除去了废料中的杂质Al和Cu，使锂离子电池正极废物得到充分回收利用。In order to solve the above technical problems, the present invention designs a method for separating and recovering valuable metals from the positive electrode waste of lithium ion batteries, which not only fully recycles the valuable metals Ni, Co, Mn and Li in the positive electrode waste, but also removes the The impurities Al and Cu in the lithium ion battery can fully recycle the positive electrode waste of lithium ion battery.
为了达到上述技术效果，本发明是通过以下技术方案实现的：一种从锂离子电池正极废料中分离回收有价金属的方法，其特征在于，包括以下步骤：In order to achieve the above technical effects, the present invention is achieved through the following technical solutions: a method for separating and recovering valuable metals from lithium-ion battery positive electrode waste, characterized in that it comprises the following steps:
Step1：将锂离子电池正极废料与CuCl2按摩尔比1：1.1～1.3充分混合，得到混合料；Step1: Fully mix the lithium-ion battery positive electrode waste with CuCl 2 in a molar ratio of 1:1.1-1.3 to obtain a mixture;
Step2：混合料置于电阻炉中进行真空氯化焙烧，真空氯化焙烧温度为730～850℃，气压为10～100Pa，保温时间为0.5～2h；Step2: The mixture is placed in a resistance furnace for vacuum chlorination roasting. The vacuum chlorination roasting temperature is 730-850°C, the air pressure is 10-100Pa, and the holding time is 0.5-2h;
Step3：控制冷凝温区为726～835℃、602～725℃、575～601℃、352～574℃、100～351℃，在对应区域收集冷凝产物，冷凝产物即为锂、镍、钴、锰、铝的氯化物。Step3: Control the condensation temperature zone to 726-835°C, 602-725°C, 575-601°C, 352-574°C, 100-351°C, collect condensation products in the corresponding areas, and the condensation products are lithium, nickel, cobalt, manganese , Aluminum chloride.
进一步的，包括以下步骤：Further, the following steps are included:
Step1：将锂离子电池正极废料与CuCl2按摩尔比1：1.2充分混合，得到混合料；Step1: Fully mix the lithium-ion battery positive electrode waste with CuCl 2 at a molar ratio of 1:1.2 to obtain a mixture;
Step2：混合料置于电阻炉中进行真空氯化焙烧，真空氯化焙烧温度为850℃，气压为100Pa，保温时间为0.5h；Step2: The mixture is placed in a resistance furnace for vacuum chlorination roasting. The vacuum chlorination roasting temperature is 850°C, the air pressure is 100Pa, and the holding time is 0.5h;
Step3：控制冷凝温区为726℃、602℃、575℃、352℃、100℃，在对应区域收集冷凝产物，冷凝产物即为锂、锰、镍、钴、铝的氯化物。Step3: Control the condensation temperature zone to 726°C, 602°C, 575°C, 352°C, and 100°C, and collect condensation products in the corresponding areas. The condensation products are chlorides of lithium, manganese, nickel, cobalt, and aluminum.
进一步的，所述锂离子电池正极废料包含三元镍钴锰酸锂(NCM)、三元镍钴铝酸锂(NCA)、镍酸锂(LNO)、钴酸锂(LCO)和锰酸锂(LMO)。Further, the positive electrode waste of the lithium ion battery comprises ternary nickel cobalt manganese oxide (NCM), ternary nickel cobalt lithium aluminate (NCA), lithium nickelate (LNO), lithium cobaltate (LCO) and lithium manganate (LMO).
本发明的有益效果是：The beneficial effects of the present invention are:
CuCl2作为氯化剂可以显著破坏锂离子电池正极废料的尖晶石结构，可以使氯化反应所需的温度接近理论值；CuCl2与正极废料中的杂质Al、Cu反应，生成易挥发的AlCl3，不易挥发的CuCl和CuO，可以除去这两种难以通过自动化生产分离的杂质；不仅充分回收了正极废料中的有价金属Ni、Co、Mn和Li，同时除去了废料中的杂质Al和Cu，使锂离子电池正极废物得到充分回收利用；与传统的浸出-沉淀法相比，避免了浸出剂和沉淀剂的加入，简短了工艺流程，在未来工业化应用具有一定的潜力。As a chlorinating agent , CuCl2 can significantly destroy the spinel structure of the positive electrode waste of lithium-ion batteries, and can make the temperature required for the chlorination reaction close to the theoretical value; CuCl2 reacts with impurities Al and Cu in the positive electrode waste to generate volatile AlCl 3 , non-volatile CuCl and CuO, can remove these two impurities that are difficult to separate through automated production; not only fully recover the valuable metals Ni, Co, Mn and Li in the positive electrode waste, but also remove the impurity Al in the waste and Cu, so that the positive electrode waste of lithium-ion batteries can be fully recycled; compared with the traditional leaching-precipitation method, it avoids the addition of leaching agents and precipitating agents, shortens the process, and has certain potential in future industrial applications.
附图说明Description of drawings
为了更清楚地说明本发明实施例的技术方案，下面将对实施例描述所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the accompanying drawings that are required for the description of the embodiments. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. Those of ordinary skill in the art can also obtain other drawings based on these drawings without any creative effort.
图1为本发明的工艺流程图。Fig. 1 is a process flow diagram of the present invention.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some, not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.
实施例1Example 1
一种从锂离子电池正极废料中分离回收有价金属的方法(见图1)，具体步骤如下：A method for separating and recovering valuable metals from lithium-ion battery positive electrode waste (see Figure 1), the specific steps are as follows:
(1)将10.2gNCM-523(Li、Ni、Co、Mn、Al和Cu的质量含量分别占比6.82％，28.85％，11.59％，16.20％，2.65％和1.25％)与24.7gCuCl2充分混合后在10Pa，730℃的条件下焙烧2h；(1) Mix 10.2g NCM-523 (the mass content of Li, Ni, Co, Mn, Al and Cu respectively accounted for 6.82%, 28.85%, 11.59%, 16.20%, 2.65% and 1.25%) with 24.7gCuCl2 Then bake at 10Pa, 730°C for 2h;
(2)控制冷凝区温度分别为726℃，575℃，352℃，602℃和100℃，在对应区域收集到LiCl，NiCl2，CoCl2，MnCl2和AlCl3的质量分别为4.2g，6.4g，2.6g，3.7g和1.3g，纯度分别为96.2％，98.3％，99.1％，99.2％和99.5％，综合回收率为99％；在坩埚中的焙烧渣质量为18.5g。(2) Control the temperature of the condensation zone to be 726°C, 575°C, 352°C, 602°C and 100°C respectively, and the masses of LiCl, NiCl 2 , CoCl 2 , MnCl 2 and AlCl 3 collected in the corresponding areas are 4.2g, 6.4 g, 2.6g, 3.7g and 1.3g, the purity is 96.2%, 98.3%, 99.1%, 99.2% and 99.5% respectively, and the comprehensive recovery rate is 99%; the roasted slag quality in the crucible is 18.5g.
降低体系中的气压，可以显著降低氯化焙烧的温度，并相应降低冷凝区的温度。但反应体系中温度整体偏低使得氯化焙烧受到化学反应速度的控制，需要相应延长焙烧时间。同时，适当降低冷凝区的温度更有利于氯化产物的冷凝，提高有价金属的回收率。冷凝温度偏低容易使较低沸点(升华点)的组分提前冷凝，使纯度降低。Reducing the air pressure in the system can significantly reduce the temperature of chlorination roasting, and correspondingly reduce the temperature of the condensation zone. However, the overall low temperature in the reaction system makes the chlorination roasting controlled by the chemical reaction speed, and the roasting time needs to be extended accordingly. At the same time, appropriately reducing the temperature in the condensation zone is more conducive to the condensation of chlorinated products and improves the recovery rate of valuable metals. A low condensation temperature tends to condense components with a lower boiling point (sublimation point) in advance, reducing the purity.
实施例2Example 2
一种从锂离子电池正极废料中分离回收有价金属的方法(见图1)，具体步骤如下：A method for separating and recovering valuable metals from lithium-ion battery positive electrode waste (see Figure 1), the specific steps are as follows:
(1)将10.1gNCM-622(Li、Ni、Co、Mn、Al和Cu的质量含量分别占比6.89％，34.95％，11.70％，10.91％，1.34％和1.26％)与27.9gCuCl2充分混合后在100Pa，850℃的条件下焙烧0.5h；(1) Mix 10.1g NCM-622 (the mass content of Li, Ni, Co, Mn, Al and Cu respectively accounted for 6.89%, 34.95%, 11.70%, 10.91%, 1.34% and 1.26%) with 27.9g CuCl 2 Then bake at 100Pa, 850°C for 0.5h;
(2)控制冷凝区温度分别为835℃，601℃，574℃，725℃和351℃，在对应区域收集到LiCl，NiCl2，CoCl2，MnCl2和AlCl3的质量分别为4.1g，7.5g，2.5g，2.4g和6.4g，纯度分别为99.3％，98.8％，98.6％，98.0％和98.5％，综合回收率为96％；在坩埚中的焙烧渣质量为22.2g。(2) Control the temperature of the condensation zone to be 835°C, 601°C, 574°C, 725°C and 351°C respectively, and the masses of LiCl, NiCl 2 , CoCl 2 , MnCl 2 and AlCl 3 collected in the corresponding areas are 4.1g, 7.5 g, 2.5g, 2.4g and 6.4g, the purity is 99.3%, 98.8%, 98.6%, 98.0% and 98.5% respectively, and the comprehensive recovery rate is 96%; the roasted slag quality in the crucible is 22.2g.
提高体系中的气压，氯化焙烧的温度需要适当增大，并相应提高冷凝区的温度。较高的焙烧温度有助于氯化反应的进行，也有助于氯化产物的挥发，可以缩短氯化反应所需的时间。但是，提高冷凝区的温度则会使沸点较高的氯化产物冷凝不完全，从而掺杂进入其他氯化产物，使有价金属的回收率偏低，同时使得低沸点组分纯度降低。To increase the air pressure in the system, the temperature of chlorination roasting needs to be increased appropriately, and the temperature of the condensation zone should be increased accordingly. A higher calcination temperature is conducive to the progress of the chlorination reaction and the volatilization of the chlorination products, which can shorten the time required for the chlorination reaction. However, increasing the temperature of the condensation zone will cause incomplete condensation of chlorinated products with higher boiling points, thereby doping into other chlorinated products, resulting in low recovery of valuable metals and lower purity of low boiling point components.
实施例3Example 3
一种从锂离子电池正极废料中分离回收有价金属的方法(见图1)，具体步骤如下：A method for separating and recovering valuable metals from lithium-ion battery positive electrode waste (see Figure 1), the specific steps are as follows:
(1)将10.2gNCM-811(Li、Ni、Co、Mn、Al和Cu的质量含量分别占比6.82％，46.13％，5.79％，5.40％，1.99％和1.25％)与26.3gCuCl2充分混合后在50Pa，780℃的条件下焙烧1h；(1) Mix 10.2g NCM-811 (the mass content of Li, Ni, Co, Mn, Al and Cu respectively accounted for 6.82%, 46.13%, 5.79%, 5.40%, 1.99% and 1.25%) with 26.3g CuCl 2 Then bake at 50Pa, 780°C for 1h;
(2)控制冷凝区温度分别为762℃，584℃，426℃，643℃和267℃，在对应区域收集到LiCl，NiCl2，CoCl2，MnCl2和AlCl3的质量分别为4.1g，10.1g，1.3g，1.2g和1.0g，纯度分别为99.3％，99.0％，99.2％，98.8％和99.5％，综合回收率为98％；在坩埚中的焙烧渣质量为20.5g。(2) Control the temperature of the condensation zone to be 762°C, 584°C, 426°C, 643°C and 267°C respectively, and the masses of LiCl, NiCl 2 , CoCl 2 , MnCl 2 and AlCl 3 collected in the corresponding areas were 4.1g, 10.1 g, 1.3g, 1.2g and 1.0g, the purity is respectively 99.3%, 99.0%, 99.2%, 98.8% and 99.5%, and the comprehensive recovery rate is 98%; the roasted slag quality in the crucible is 20.5g.
在适中的温度和压力条件下进行氯化焙烧，有利于降低反应能耗，减少氯化剂CuCl2的添加量，减少焙烧渣的产生量。综合3个实施例可以发现，冷凝温度的变化对NiCl2和CoCl2的影响较为显著：冷凝温度降低时，NiCl2和CoCl2的纯度提高；冷凝温度升高则相反。因此，综合考虑氯化反应效率、有价金属回收率和冷凝效率等因素后，应优选较高的反应温度和较低的冷凝温度。Chlorination roasting under moderate temperature and pressure conditions is beneficial to reduce reaction energy consumption, reduce the addition of chlorinating agent CuCl 2 , and reduce the production of roasted slag. Based on the three examples, it can be found that the change of condensation temperature has a more significant impact on NiCl2 and CoCl2 : when the condensation temperature decreases, the purity of NiCl2 and CoCl2 increases; the opposite is true when the condensation temperature increases. Therefore, after comprehensive consideration of factors such as chlorination reaction efficiency, recovery rate of valuable metals and condensation efficiency, a higher reaction temperature and a lower condensation temperature should be preferred.
传统的浸出-沉淀法回收锂离子电池正极废料中的有价金属，通常需要采用酸性浸出剂将金属以可溶性离子的形态转移到溶液中，再采用沉淀剂以调节pH的形式分别沉淀。传统方法的浸出率和沉淀率均约为99％，产物纯度约99.5％，由此可以计算得到有价金属的综合回收率约为97.5％。本发明的有价金属回收率与传统方法基本相同，但是避免了浸出剂和沉淀剂的加入，简短了工艺流程，在未来工业化应用具有一定的潜力。The traditional leaching-precipitation method to recover valuable metals in lithium-ion battery positive electrode waste usually requires the use of an acidic leaching agent to transfer the metals into the solution in the form of soluble ions, and then use a precipitant to adjust the pH for precipitation. The leaching rate and precipitation rate of the traditional method are both about 99%, and the product purity is about 99.5%, so it can be calculated that the comprehensive recovery rate of valuable metals is about 97.5%. The recovery rate of valuable metals in the present invention is basically the same as that of the traditional method, but avoids the addition of leaching agents and precipitating agents, shortens the process flow, and has certain potential for industrial application in the future.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211569241.9A CN115821045A (en) | 2022-12-08 | 2022-12-08 | Method for separating and recovering valuable metal from lithium ion battery anode waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211569241.9A CN115821045A (en) | 2022-12-08 | 2022-12-08 | Method for separating and recovering valuable metal from lithium ion battery anode waste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115821045A true CN115821045A (en) | 2023-03-21 |
Family
ID=85544553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211569241.9A Pending CN115821045A (en) | 2022-12-08 | 2022-12-08 | Method for separating and recovering valuable metal from lithium ion battery anode waste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115821045A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112342376A (en) * | 2020-10-30 | 2021-02-09 | 昆明理工大学 | Roasting device for sintering ash and application and use method thereof |
| CN114085999A (en) * | 2021-11-24 | 2022-02-25 | 昆明理工大学 | A method for recovering valuable metals from lithium battery cathode leaching waste liquid |
| CN114655969A (en) * | 2022-03-28 | 2022-06-24 | 北京科技大学 | Method for preparing lithium carbonate and iron phosphate by recycling high-impurity lithium iron phosphate positive electrode waste |
| CN114890441A (en) * | 2022-05-16 | 2022-08-12 | 昆明理工大学 | Method for recovering lithium chloride and cobalt oxide from waste lithium cobaltate battery positive plate |
-
2022
- 2022-12-08 CN CN202211569241.9A patent/CN115821045A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112342376A (en) * | 2020-10-30 | 2021-02-09 | 昆明理工大学 | Roasting device for sintering ash and application and use method thereof |
| CN114085999A (en) * | 2021-11-24 | 2022-02-25 | 昆明理工大学 | A method for recovering valuable metals from lithium battery cathode leaching waste liquid |
| CN114655969A (en) * | 2022-03-28 | 2022-06-24 | 北京科技大学 | Method for preparing lithium carbonate and iron phosphate by recycling high-impurity lithium iron phosphate positive electrode waste |
| CN114890441A (en) * | 2022-05-16 | 2022-08-12 | 昆明理工大学 | Method for recovering lithium chloride and cobalt oxide from waste lithium cobaltate battery positive plate |
Non-Patent Citations (1)
| Title |
|---|
| 胡国琛: "锂离子电池正极材料中有价金属回收研究进展", 《中国有色金属学报》, vol. 31, no. 11, 9 September 2021 (2021-09-09), pages 3320 - 3343 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108878866B (en) | Method for preparing ternary material precursor and recovering lithium by using ternary cathode material of waste lithium ion battery | |
| CN108550939B (en) | A method for selectively reclaiming lithium and preparing lithium carbonate from waste lithium batteries | |
| CN111825110A (en) | Recycling method of cathode material of waste lithium ion battery | |
| CN112079369B (en) | Method for preferentially extracting lithium and cooperatively recovering manganese from waste lithium ion battery | |
| CN106129511A (en) | A kind of method of comprehensively recovering valuable metal from waste and old lithium ion battery material | |
| CN111254294B (en) | Method for selectively extracting lithium from waste lithium-ion battery powder and electrolytically separating and recovering manganese dioxide | |
| CN113957255B (en) | Method for separating and recycling valuable metals in waste ternary lithium battery | |
| CN111254276A (en) | Method for selective extraction of valuable metals from waste lithium-ion battery powder based on phase inversion of reductive sodium roasting | |
| CN113921931B (en) | Method for recycling lithium carbonate from retired lithium ion battery black powder through carbothermic reduction | |
| CN115216630B (en) | Recycling treatment method of waste lithium-containing aluminum electrolyte | |
| CN117550628B (en) | Method for recycling valuable metal of waste lithium iron phosphate anode | |
| CN113793994A (en) | A kind of method of recycling waste lithium iron phosphate battery | |
| CN111118296A (en) | Method and system for recovering black powder of waste lithium ion battery | |
| CN115074540A (en) | Comprehensive recovery method for valuable components of waste power battery | |
| CN115747516A (en) | Method for recovering nickel, cobalt, magnesium and iron from high-magnesium-silicon laterite-nickel ore | |
| CN111455176A (en) | Method for recovering waste lithium cobaltate positive electrode material | |
| CN115821045A (en) | Method for separating and recovering valuable metal from lithium ion battery anode waste | |
| CN112481492A (en) | Method for recovering valuable metals from waste lithium battery lithium cobaltate positive electrode material | |
| CN116445736A (en) | Method for extracting lithium from lepidolite by utilizing composite salt roasting-water leaching process | |
| CN114956131A (en) | Method for recovering metal lithium and cobalt from waste lithium cobalt oxide battery positive electrode material | |
| CN114574705A (en) | Method for leaching and separating lithium and valuable metals from waste lithium ion battery | |
| CN114875240A (en) | Method for treating copper-cobalt alloy of waste lithium battery and application | |
| CN106498442B (en) | A kind of antimony electrolyte selectivity iron removaling and the method for preparing ferrous oxalate | |
| Cheng et al. | Classification and progress of extraction technologies for nonferrous metal resources | |
| CN105140504B (en) | A kind of method that electrode material of lithium battery is prepared using vanadium extraction waste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |