WO2014154154A1 - Method of recycling lithium manganese battery anode material - Google Patents
Method of recycling lithium manganese battery anode material Download PDFInfo
- Publication number
- WO2014154154A1 WO2014154154A1 PCT/CN2014/074170 CN2014074170W WO2014154154A1 WO 2014154154 A1 WO2014154154 A1 WO 2014154154A1 CN 2014074170 W CN2014074170 W CN 2014074170W WO 2014154154 A1 WO2014154154 A1 WO 2014154154A1
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- WO
- WIPO (PCT)
- Prior art keywords
- lithium
- mixture
- positive electrode
- lithium manganate
- acid
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004064 recycling Methods 0.000 title claims abstract description 11
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 title abstract 5
- 239000010405 anode material Substances 0.000 title abstract 3
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 20
- 239000011888 foil Substances 0.000 claims abstract description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002386 leaching Methods 0.000 claims abstract description 11
- 239000002893 slag Substances 0.000 claims abstract description 11
- 229910000676 Si alloy Inorganic materials 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 9
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 7
- 239000006258 conductive agent Substances 0.000 claims abstract description 7
- 239000004571 lime Substances 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000007774 positive electrode material Substances 0.000 claims description 22
- 239000010406 cathode material Substances 0.000 claims description 14
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 9
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000000571 coke Substances 0.000 claims description 5
- 239000002006 petroleum coke Substances 0.000 claims description 5
- 239000002802 bituminous coal Substances 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 241001062472 Stokellia anisodon Species 0.000 claims 1
- 238000003723 Smelting Methods 0.000 abstract description 3
- 239000010926 waste battery Substances 0.000 abstract description 2
- 239000007767 bonding agent Substances 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 238000005453 pelletization Methods 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 239000002699 waste material Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- 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 positive electrode material of a lithium manganate battery, and belongs to the technical field of waste battery recycling.
- a lithium battery is a new generation of secondary batteries rapidly developed in the 1990s, and is widely used in small portable electronic communication products and electric vehicles.
- Traditional nickel-metal hydride batteries, nickel-cadmium batteries, and lead-acid batteries are affected by the sales of lithium batteries.
- the high-end market for lithium-ion batteries for mobile phones and notebook computers has been squeezed, and the demand for lithium batteries has increased significantly. Since the development of the first lithium battery by SONY in 1992, the lithium battery energy has also been greatly improved.
- the lithium battery cathode material has been developed from a single lithium cobalt oxide material to lithium cobaltate, lithium manganate, lithium nickel cobaltate, Lithium nickel cobalt manganate, lithium iron phosphate and other materials go hand in hand, of which lithium manganate is one of the more promising lithium ion cathode materials.
- the invention name is "A method for recovering Mn0 2 from the cathode material of lithium manganese oxide battery and its application", and the application number is CN200910116656.
- the invention discloses a method for recovering Mn0 2 from a cathode material of a lithium manganese oxide battery, which firstly pretreats the positive electrode sheet obtained by dissolving to obtain a positive electrode active material, and then uses a positive electrode active material as a raw material, and uses 0.
- the invention is entitled "A method for recovering valuable metals from a waste lithium manganese oxide battery", and the method disclosed in the patent application No.
- CN201010141128 uses an organic solvent to soak and peel the active material of the battery, and directly obtains a clean Aluminum, copper, nickel foil and separator; use acidic solution to react with LiMn 2 0 4 in the battery cell to form a soluble salt of lithium and manganese; adjust the p H value to 5 ⁇ 7 with NaOH solution or ammonia water to make the solution
- the iron ions, aluminum ions and copper ions are all precipitated and separated by filtration; then the pH is adjusted to 10 ⁇ 12 with Na OH solution or ammonia water, and the manganese hydroxide solid and the lithium-containing filtrate are obtained by precipitation and filtration;
- the solid is burned to obtain Mn0 2 , and the lithium-containing filtrate is reacted with sodium carbonate to form lithium carbonate, which is filtered, washed, and dried to obtain pure lithium carbonate.
- the above two methods can realize the recovery of the positive electrode material of the lithium manganate battery to a certain extent, but the above methods are all treated by the wet process, and the waste acid or waste alkali generated is easy to form secondary pollution.
- the treatment plant needs to be separately designed according to the process. Or the workshop, the investment is large, and the waste material used as the raw material of the recycling factory can not be guaranteed for a long time.
- the method for recovering a positive electrode material of a lithium manganate battery of the invention comprises the steps of separating an aluminum foil from a positive electrode sheet of a lithium manganate battery, wherein the positive electrode sheet of the lithium manganate battery is heated at 300 to 600 ° C for 1 to 4 hours, and then the aluminum foil is separated to obtain a manganese acid.
- the method for recovering the positive electrode material of the lithium manganate battery the separation method of the separated aluminum foil can be separated by mechanical separation or ultrasonic vibration.
- the method of the invention separates the aluminum foil from the positive electrode material by heat treatment of the pole piece by a specific temperature, and the separation effect is better than the direct pulverization screening, and the subsequent steps do not need to be chemically removed by aluminum, and the use is avoided.
- Organic solvents cause secondary pollution.
- the method for recovering the positive electrode material of the lithium manganate battery of the present invention preferably comprises the following steps: a. disassembling the lithium manganese oxide battery, and taking out the positive electrode sheet;
- the positive electrode sheet is heated at 300 ⁇ 600 ° C for l ⁇ 4h, and then the aluminum foil is separated to obtain a mixture of lithium manganate cathode material, a conductive agent and a binder;
- the mixture is calcined at 1000 ⁇ 1200 ° C for l ⁇ 3h, and then the ball is formed;
- the carbonaceous reducing agent described in the above step d may be at least one of a conventional carbonaceous reducing agent such as charcoal, petroleum coke, bituminous coal, blue carbon or coke.
- the acid used for acid leaching in the above e step may be hydrochloric acid or sulfuric acid.
- the concentration and amount of acid can be adjusted according to specific needs to achieve the purpose of leaching.
- the invention solves the problem of recycling and utilization of lithium manganate power battery resources, and relieves the worry of the development of electric vehicles, and does not generate secondary pollution of waste acid or waste alkali, and has broad application prospects.
- the method for recovering a positive electrode material of a lithium manganate battery of the present invention comprises the steps of separating an aluminum foil from a positive electrode sheet of a lithium manganate battery, which The positive electrode sheet of the lithium manganate battery is heated at 300 to 600 ° C for 1 to 4 hours, and then the aluminum foil is separated to obtain a mixture of a lithium manganate positive electrode material, a conductive agent and a binder.
- the method for recovering the positive electrode material of the lithium manganate battery the separation method of the separated aluminum foil can be separated by mechanical separation or ultrasonic vibration.
- the method of the invention separates the aluminum foil from the positive electrode material by heat treatment of the pole piece by a specific temperature, and the separation effect is better than the direct pulverization screening, and the subsequent steps do not need to be chemically removed by aluminum, and the use is avoided.
- Organic solvents cause secondary pollution.
- the method for recovering the positive electrode material of the lithium manganate battery of the present invention preferably comprises the following steps: a. disassembling the lithium manganese oxide battery, and taking out the positive electrode sheet;
- the positive electrode sheet is heated at 300 to 600 ° C for 1 to 4 hours, and then the aluminum foil is separated to obtain a mixture of a lithium manganate cathode material, a conductive agent and a binder;
- the mixture is calcined at 1000 ⁇ 1200 °C for l ⁇ 3h, and then the ball is formed;
- the carbonaceous reducing agent described in the above step d may be a conventional carbonaceous reducing agent such as at least one of charcoal petroleum coke, bituminous coal, blue carbon, and coke.
- the acid used for acid leaching in the above e step may be hydrochloric acid or sulfuric acid.
- the concentration and amount of acid can be adjusted according to specific needs to achieve the purpose of leaching.
- Example 1 Recovering a lithium manganese oxide battery cathode material by the method of the present invention
- the battery After the residual power of the waste lithium manganate power battery is discharged, the battery is disassembled, the positive electrode piece is taken out, and the battery case is recycled according to aluminum shell, steel shell, plastic, etc.; the positive electrode sheet is heat treated at 300 ° C, then ball milled, and the aluminum foil is separated and a mixture of positive electrode materials; the mixture was calcined at 1000 V and then pressed.
- the mixture was filled with 100 kg of coke, 20 kg of coke, 15 kg of lime, and 16 kg of silica.
- the mixture was smelted in an electric furnace for 2 hours, and 70 kg of manganese-silicon alloy was cast.
- the slag is acid leached to obtain a lithium-containing solution, which is then precipitated by adding a sodium carbonate solution, and filtered to obtain 11 kg of lithium carbonate.
- the obtained silicon alloy composition Mn 66%, Si0 2 23%, C 6.8%, P 0. 3%.
- Example 2 Recovering a lithium manganese oxide battery cathode material by the method of the present invention After the residual power of the waste lithium manganate power battery is discharged, the battery is disassembled, the positive electrode is taken out, and the battery casing is recycled according to aluminum shell, steel shell, plastic, etc.; the positive electrode sheet is heat treated at 400 ° C, then ball milled, and the aluminum foil is separated and a mixture of positive electrode materials; the mixture was calcined at 1200 ° C and then pressed.
- the mixture was filled with 100 kg of petroleum coke, 18 kg of petroleum coke, 14 kg of lime and 17 kg of silica. It was put into an electric furnace for lh and cast to obtain 68 kg of manganese-silicon alloy. The slag is acid leached to obtain a lithium-containing solution, which is then precipitated by adding a sodium carbonate solution, and filtered to obtain 10 kg of lithium carbonate.
- the obtained manganese silicon alloy composition Mn 65%, Si0 2 24%, C 6%, P 0.2%.
- Example 3 Recovering a lithium manganese oxide battery cathode material by the method of the present invention
- the battery After the residual power of the waste lithium manganate power battery is discharged, the battery is disassembled, the positive electrode is taken out, and the battery casing is recycled according to aluminum shell, steel shell, plastic, etc.; the positive electrode sheet is heat treated at 600 ° C, then ball milled, and the aluminum foil is separated and a mixture of positive electrode materials; the mixture was calcined at 1 ioo °c and then pressed.
Abstract
The present invention relates to the technical field of waste battery recycling. Disclosed is a method for recycling lithium manganese battery anode material, the method comprising the step of separating aluminum foil from a lithium manganese battery anode plate, in particular, heating the lithium manganese battery anode plate at 300-600℃ for 1-4 hrs; separating the aluminum foil therefrom to obtain a mixture of a lithium manganese anode material, a conductive agent, and a bonding agent; calcining the mixture at 1000-1200℃ for 1-3 hrs for pelletizing; mixing uniformly the pelletized mixture with carbonaceous reductant, silica, and lime according to a weight ratio of 100:18-22: 13-17: 14-18; smelting the mixture in an electric furnace for 1-3 hrs to obtain a manganese-silicon alloy and slag; conducting acid leaching on the slag to obtain a lithium-containing solution; and then adding a sodium carbonate solution, precipitating, and filtrating to obtain lithium carbonate.
Description
锰酸锂电池正极材料回收方法 技术领域 Method for recovering positive electrode material of lithium manganate battery
本发明涉及锰酸锂电池正极材料回收方法， 属于废旧电池回收技术领域。 The invention relates to a method for recovering a positive electrode material of a lithium manganate battery, and belongs to the technical field of waste battery recycling.
背景技术 锂电池是 20 世纪 90 年代迅速发展起来的新一代二次电池，广泛用于小型便携式电子通 讯产品和电动交通工具。 传统镍氢电池、 镍镉电池、 铅酸电池受锂电池销售配套化影响， 其 手机和笔记本电脑锂电池高端市场已被挤占， 锂电池需求量相应大幅增加。 从 1992年 SONY 公司开发出第一颗锂电池至今， 锂电池能量也已大幅提升， 锂电池正极材料已经从单一的钴 酸锂材料， 发展到钴酸锂、 锰酸锂、 镍钴酸锂、 镍钴锰酸锂、 磷酸铁锂等材料齐头并进的阶 段， 其中， 锰酸锂是较有前景的锂离子正极材料之一。 Background Art A lithium battery is a new generation of secondary batteries rapidly developed in the 1990s, and is widely used in small portable electronic communication products and electric vehicles. Traditional nickel-metal hydride batteries, nickel-cadmium batteries, and lead-acid batteries are affected by the sales of lithium batteries. The high-end market for lithium-ion batteries for mobile phones and notebook computers has been squeezed, and the demand for lithium batteries has increased significantly. Since the development of the first lithium battery by SONY in 1992, the lithium battery energy has also been greatly improved. The lithium battery cathode material has been developed from a single lithium cobalt oxide material to lithium cobaltate, lithium manganate, lithium nickel cobaltate, Lithium nickel cobalt manganate, lithium iron phosphate and other materials go hand in hand, of which lithium manganate is one of the more promising lithium ion cathode materials.
由于全世界经济和城市交通的发展， 引起了石油紧张和环境污染， 国际上许多发达国家 竞相开发绿色能源技术， 其中尤以电动车应用为代表的动力电源领域发展最为迅速。 电动汽 车要取代燃油汽车， 动力电池是关键。 由于传统化学电池存在着储存能量低、 重量大、 寿命 短和不安全等因素， 成为电动汽车产业化发展的瓶颈， 电动汽车中的锂电池的使用率正在明 显上升， 锂离子电池极可能将成为未来的主流技术路线， 未来锰酸锂行业还会有较大的发展 空间。 随着电动汽车锂离子电池的广泛应用， 将大量进入失效、 回收阶段。 如何回收废旧锂 离子电池和资源化循环利用已成为社会普遍关注的问题。 为了资源循环利用和行业可持续发 展的目的， 应对其中有价金属进行回收处理。 Due to the development of the world economy and urban transportation, oil shortages and environmental pollution have occurred. Many developed countries in the world are competing to develop green energy technologies. Among them, the power supply field represented by electric vehicle applications is the fastest growing. Electric vehicles are the key to replacing fuel vehicles. Due to the low storage energy, heavy weight, short life and unsafe factors of traditional chemical batteries, it has become a bottleneck in the industrialization of electric vehicles. The utilization rate of lithium batteries in electric vehicles is increasing significantly. Lithium-ion batteries are likely to become In the future mainstream technology route, there will be more room for development in the future lithium manganate industry. With the wide application of lithium-ion batteries for electric vehicles, a large number of failure and recovery stages will be entered. How to recycle used lithium-ion batteries and recycle resources has become a common concern in society. For the purpose of resource recycling and sustainable development of the industry, the valuable metals should be recycled.
目前， 已有关于锰酸锂电池正极材料回收方法的相关报道， 如： 发明名称为 "一种自废 旧锰酸锂电池正极材料中回收 Mn02的方法及其应用"， 申请号为 CN200910116656的专利申请 公开了一种自废旧锰酸锂电池正极材料中回收 Mn02的方法， 其首先将拆解得到的正极片经碱 溶等预处理得到正极活性材料，然后以正极活性材料为原料，用 0. 25〜10mol/L无机酸或常压 酸浸得到 λ -Mn02, 或水热酸浸得到 α— / β— / γ— Mn02。 又如： 发明名称为 "一种自废 旧锰酸锂电池中回收有价金属的方法"， 申请号为 CN201010141128的专利申请公开的方法采 用有机溶剂对电池的活性物质进行浸泡剥离， 直接得到洁净的铝、 铜、 镍箔与隔膜； 利用酸 性溶液与电池电芯中的 LiMn204反应， 生成锂与锰的可溶性盐类； 用 NaOH溶液或氨水调整 p H值至 5〜7， 使溶液中的铁离子、 铝离子、 铜离子全部沉淀、 过滤分离； 再用 N a O H溶液 或氨水调整 P H值至 10〜12， 经沉淀、 过滤得到氢氧化锰固体与含锂滤液； 最后将氢氧化锰
固体灼烧得到 Mn02， 将含锂滤液与碳酸钠反应生成碳酸锂， 再经过滤， 洗涤、 干燥即得到纯 净的碳酸锂。 上述两种方法在一定程度上能够实现锰酸锂电池正极材料的回收， 但是上述方 法均采用湿法处理， 产生的废酸或废碱易形成二次污染， 另外， 需根据工艺单独设计处理工 厂或车间， 投资大， 相当长时期内作为回收工厂原料的废料也无法得到保证。 发明内容 本发明所要解决的技术问题是提供一种锰酸锂电池正极材料回收方法。 At present, there have been reports on the recovery method of positive electrode materials for lithium manganate batteries, such as: The invention name is "A method for recovering Mn0 2 from the cathode material of lithium manganese oxide battery and its application", and the application number is CN200910116656. The invention discloses a method for recovering Mn0 2 from a cathode material of a lithium manganese oxide battery, which firstly pretreats the positive electrode sheet obtained by dissolving to obtain a positive electrode active material, and then uses a positive electrode active material as a raw material, and uses 0. 25~10mol/L inorganic acid or atmospheric pressure acid leaching to obtain λ-Mn0 2 , or hydrothermal acid leaching to obtain α - / β - / γ - Mn0 2 . For example, the invention is entitled "A method for recovering valuable metals from a waste lithium manganese oxide battery", and the method disclosed in the patent application No. CN201010141128 uses an organic solvent to soak and peel the active material of the battery, and directly obtains a clean Aluminum, copper, nickel foil and separator; use acidic solution to react with LiMn 2 0 4 in the battery cell to form a soluble salt of lithium and manganese; adjust the p H value to 5~7 with NaOH solution or ammonia water to make the solution The iron ions, aluminum ions and copper ions are all precipitated and separated by filtration; then the pH is adjusted to 10~12 with Na OH solution or ammonia water, and the manganese hydroxide solid and the lithium-containing filtrate are obtained by precipitation and filtration; The solid is burned to obtain Mn0 2 , and the lithium-containing filtrate is reacted with sodium carbonate to form lithium carbonate, which is filtered, washed, and dried to obtain pure lithium carbonate. The above two methods can realize the recovery of the positive electrode material of the lithium manganate battery to a certain extent, but the above methods are all treated by the wet process, and the waste acid or waste alkali generated is easy to form secondary pollution. In addition, the treatment plant needs to be separately designed according to the process. Or the workshop, the investment is large, and the waste material used as the raw material of the recycling factory can not be guaranteed for a long time. SUMMARY OF THE INVENTION The technical problem to be solved by the present invention is to provide a method for recovering a positive electrode material of a lithium manganate battery.
本发明锰酸锂电池正极材料回收方法， 包括从锰酸锂电池正极片中分离铝箔步骤， 其将 锰酸锂电池正极片于 300〜600°C加热 l〜4h， 然后分离铝箔， 得到锰酸锂正极材料、 导电剂 和粘结剂的混合物。 The method for recovering a positive electrode material of a lithium manganate battery of the invention comprises the steps of separating an aluminum foil from a positive electrode sheet of a lithium manganate battery, wherein the positive electrode sheet of the lithium manganate battery is heated at 300 to 600 ° C for 1 to 4 hours, and then the aluminum foil is separated to obtain a manganese acid. A mixture of a lithium positive electrode material, a conductive agent, and a binder.
其中， 上述锰酸锂电池正极材料回收方法， 其分离铝箔的分离方法可以采用机械分离或 超声波震荡方法分离。 Wherein, the method for recovering the positive electrode material of the lithium manganate battery, the separation method of the separated aluminum foil can be separated by mechanical separation or ultrasonic vibration.
本发明方法通过极片采用特定温度的热处理的方式使铝箔与正极材料分离， 分离效果相 较于直接粉碎筛分更佳， 且后续步骤不需要再需采用化学方法除铝， 同时又避免了采用有机 溶剂造成二次污染。 The method of the invention separates the aluminum foil from the positive electrode material by heat treatment of the pole piece by a specific temperature, and the separation effect is better than the direct pulverization screening, and the subsequent steps do not need to be chemically removed by aluminum, and the use is avoided. Organic solvents cause secondary pollution.
其中， 作为优选的技术方案， 本发明锰酸锂电池正极材料回收方法优选包括如下步骤： a、 拆解废旧锰酸锂电池， 取出正极片； As a preferred technical solution, the method for recovering the positive electrode material of the lithium manganate battery of the present invention preferably comprises the following steps: a. disassembling the lithium manganese oxide battery, and taking out the positive electrode sheet;
b、 正极片于 300〜600°C加热 l〜4h， 然后分离铝箔， 得到锰酸锂正极材料、 导电剂和粘 结剂的混合物； b, the positive electrode sheet is heated at 300~600 ° C for l~4h, and then the aluminum foil is separated to obtain a mixture of lithium manganate cathode material, a conductive agent and a binder;
c、 混合物于 1000〜1200°C煅烧 l〜3h， 然后造球； c, the mixture is calcined at 1000~1200 ° C for l~3h, and then the ball is formed;
d、 造球后的混合物与碳质还原剂、 硅石、 石灰按重量比 100 : 18〜22： 13〜17： 14〜18 混匀， 然后电炉冶炼 l〜3h， 得到锰硅合金和炉渣； d, the mixture after the ball and the carbonaceous reducing agent, silica, lime by weight ratio of 100: 18~22: 13~17: 14~18, and then electric furnace smelting l~3h, to obtain manganese silicon alloy and slag;
e、 炉渣酸浸得到含锂溶液， 再加入碳酸钠溶液沉淀， 过滤， 得到碳酸锂。 e, slag acid leaching to obtain a lithium-containing solution, and then precipitated by adding sodium carbonate solution, and filtered to obtain lithium carbonate.
其中， 上述 d步骤中所述的碳质还原剂可以为常规的碳质还原剂， 如： 木炭、 石油焦、 烟煤、 蓝炭、 焦炭中至少一种。 Wherein, the carbonaceous reducing agent described in the above step d may be at least one of a conventional carbonaceous reducing agent such as charcoal, petroleum coke, bituminous coal, blue carbon or coke.
进一步的， 上述 e步骤中酸浸所用酸可以为盐酸或硫酸。 酸的浓度和用量可以根据具体 需要进行调节， 达到浸出目的即可。 Further, the acid used for acid leaching in the above e step may be hydrochloric acid or sulfuric acid. The concentration and amount of acid can be adjusted according to specific needs to achieve the purpose of leaching.
本发明解决了锰酸锂动力电池资源回收利用问题， 为电动汽车的发展解除后顾之忧， 其 不会产生废酸或废碱的二次污染， 具有广阔的应用前景。 The invention solves the problem of recycling and utilization of lithium manganate power battery resources, and relieves the worry of the development of electric vehicles, and does not generate secondary pollution of waste acid or waste alkali, and has broad application prospects.
具体实施方式 detailed description
本发明锰酸锂电池正极材料回收方法， 包括从锰酸锂电池正极片中分离铝箔步骤， 其将
锰酸锂电池正极片于 300〜600 °C加热 l〜4h， 然后分离铝箔， 得到锰酸锂正极材料、 导电剂 和粘结剂的混合物。 The method for recovering a positive electrode material of a lithium manganate battery of the present invention comprises the steps of separating an aluminum foil from a positive electrode sheet of a lithium manganate battery, which The positive electrode sheet of the lithium manganate battery is heated at 300 to 600 ° C for 1 to 4 hours, and then the aluminum foil is separated to obtain a mixture of a lithium manganate positive electrode material, a conductive agent and a binder.
其中， 上述锰酸锂电池正极材料回收方法， 其分离铝箔的分离方法可以采用机械分离或 超声波震荡方法分离。 Wherein, the method for recovering the positive electrode material of the lithium manganate battery, the separation method of the separated aluminum foil can be separated by mechanical separation or ultrasonic vibration.
本发明方法通过极片采用特定温度的热处理的方式使铝箔与正极材料分离， 分离效果相 较于直接粉碎筛分更佳， 且后续步骤不需要再需采用化学方法除铝， 同时又避免了采用有机 溶剂造成二次污染。 The method of the invention separates the aluminum foil from the positive electrode material by heat treatment of the pole piece by a specific temperature, and the separation effect is better than the direct pulverization screening, and the subsequent steps do not need to be chemically removed by aluminum, and the use is avoided. Organic solvents cause secondary pollution.
其中， 作为优选的技术方案， 本发明锰酸锂电池正极材料回收方法优选包括如下步骤： a、 拆解废旧锰酸锂电池， 取出正极片； As a preferred technical solution, the method for recovering the positive electrode material of the lithium manganate battery of the present invention preferably comprises the following steps: a. disassembling the lithium manganese oxide battery, and taking out the positive electrode sheet;
b、 正极片于 300〜600 °C加热 l〜4h， 然后分离铝箔， 得到锰酸锂正极材料、 导电剂和粘 结剂的混合物； b. The positive electrode sheet is heated at 300 to 600 ° C for 1 to 4 hours, and then the aluminum foil is separated to obtain a mixture of a lithium manganate cathode material, a conductive agent and a binder;
c、 混合物于 1000〜1200 °C煅烧 l〜3h， 然后造球； c, the mixture is calcined at 1000~1200 °C for l~3h, and then the ball is formed;
d、 造球后的混合物与碳质还原剂、 硅石、 石灰按重量比 100 : 18〜22： 13〜17： 14〜18 混匀， 然后电炉冶炼 l〜3h， 得到锰硅合金和炉渣； d, the mixture after the ball and the carbonaceous reducing agent, silica, lime by weight ratio of 100: 18~22: 13~17: 14~18, and then electric furnace smelting l~3h, to obtain manganese silicon alloy and slag;
e、 炉渣酸浸得到含锂溶液， 再加入碳酸钠溶液沉淀， 过滤， 得到碳酸锂。 e, slag acid leaching to obtain a lithium-containing solution, and then precipitated by adding sodium carbonate solution, and filtered to obtain lithium carbonate.
其中， 上述 d步骤中所述的碳质还原剂可以为常规的碳质还原剂， 如： 木炭 石油焦、 烟 煤、 蓝炭、 焦炭中至少一种。 Wherein, the carbonaceous reducing agent described in the above step d may be a conventional carbonaceous reducing agent such as at least one of charcoal petroleum coke, bituminous coal, blue carbon, and coke.
进一步的， 上述 e步骤中酸浸所用酸可以为盐酸或硫酸。 酸的浓度和用量可以根据具体 需要进行调节， 达到浸出目的即可。 Further, the acid used for acid leaching in the above e step may be hydrochloric acid or sulfuric acid. The concentration and amount of acid can be adjusted according to specific needs to achieve the purpose of leaching.
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 specific embodiments of the present invention are further described below in conjunction with the embodiments, which are not intended to limit the scope of the embodiments.
实施例 1 采用本发明方法回收锰酸锂电池正极材料 Example 1 Recovering a lithium manganese oxide battery cathode material by the method of the present invention
将废旧锰酸锂动力电池残余电量放完， 拆解电池， 取出正极片， 电池外壳按铝壳、 钢壳、 塑料等分类回收； 正极片进行 300 °C热处理， 然后球磨筛分， 分离铝箔和正极材料混合物； 混合物经过 1000 V煅烧后压球。 After the residual power of the waste lithium manganate power battery is discharged, the battery is disassembled, the positive electrode piece is taken out, and the battery case is recycled according to aluminum shell, steel shell, plastic, etc.; the positive electrode sheet is heat treated at 300 ° C, then ball milled, and the aluminum foil is separated and a mixture of positive electrode materials; the mixture was calcined at 1000 V and then pressed.
取压球后混合物 100kg, 配入焦炭 20kg、 石灰 15kg、 硅石 16kg， 投入电炉中冶炼 2h， 浇铸得到 70kg锰硅合金。炉渣酸浸得到含锂溶液， 再加入碳酸钠溶液沉淀， 过滤， 得到 11kg 碳酸锂。 After the ball was taken, the mixture was filled with 100 kg of coke, 20 kg of coke, 15 kg of lime, and 16 kg of silica. The mixture was smelted in an electric furnace for 2 hours, and 70 kg of manganese-silicon alloy was cast. The slag is acid leached to obtain a lithium-containing solution, which is then precipitated by adding a sodium carbonate solution, and filtered to obtain 11 kg of lithium carbonate.
经检测， 所得猛硅合金成分： Mn 66%, Si02 23%, C 6. 8%, P 0. 3%。 After testing, the obtained silicon alloy composition: Mn 66%, Si0 2 23%, C 6.8%, P 0. 3%.
实施例 2 采用本发明方法回收锰酸锂电池正极材料
将废旧锰酸锂动力电池残余电量放完， 拆解电池， 取出正极片， 电池外壳按铝壳、 钢壳、 塑料等分类回收； 正极片进行 400°C热处理， 然后球磨筛分， 分离铝箔和正极材料混合物； 混合物经过 1200°C煅烧后压球。 Example 2 Recovering a lithium manganese oxide battery cathode material by the method of the present invention After the residual power of the waste lithium manganate power battery is discharged, the battery is disassembled, the positive electrode is taken out, and the battery casing is recycled according to aluminum shell, steel shell, plastic, etc.; the positive electrode sheet is heat treated at 400 ° C, then ball milled, and the aluminum foil is separated and a mixture of positive electrode materials; the mixture was calcined at 1200 ° C and then pressed.
取压球后混合物 100kg, 配入石油焦 18kg、 石灰 14kg、 硅石 17kg， 投入电炉中冶炼 lh， 浇铸得到 68kg锰硅合金。炉渣酸浸得到含锂溶液， 再加入碳酸钠溶液沉淀， 过滤， 得到 10kg 碳酸锂。 After the ball was taken, the mixture was filled with 100 kg of petroleum coke, 18 kg of petroleum coke, 14 kg of lime and 17 kg of silica. It was put into an electric furnace for lh and cast to obtain 68 kg of manganese-silicon alloy. The slag is acid leached to obtain a lithium-containing solution, which is then precipitated by adding a sodium carbonate solution, and filtered to obtain 10 kg of lithium carbonate.
经检测， 所得锰硅合金成分： Mn 65%, Si02 24%, C 6%, P 0. 2%。 After testing, the obtained manganese silicon alloy composition: Mn 65%, Si0 2 24%, C 6%, P 0.2%.
实施例 3 采用本发明方法回收锰酸锂电池正极材料 Example 3 Recovering a lithium manganese oxide battery cathode material by the method of the present invention
将废旧锰酸锂动力电池残余电量放完， 拆解电池， 取出正极片， 电池外壳按铝壳、 钢壳、 塑料等分类回收； 正极片进行 600°C热处理， 然后球磨筛分， 分离铝箔和正极材料混合物； 混合物经过 1 ioo°c煅烧后压球。 After the residual power of the waste lithium manganate power battery is discharged, the battery is disassembled, the positive electrode is taken out, and the battery casing is recycled according to aluminum shell, steel shell, plastic, etc.; the positive electrode sheet is heat treated at 600 ° C, then ball milled, and the aluminum foil is separated and a mixture of positive electrode materials; the mixture was calcined at 1 ioo °c and then pressed.
取压球后混合物 100kg, 配入烟煤 22kg、 石灰 18kg、 硅石 13kg， 投入电炉中冶炼 3h， 浇铸得到 71kg锰硅合金。炉渣酸浸得到含锂溶液， 再加入碳酸钠溶液沉淀， 过滤， 得到 10kg 碳酸锂。 After the ball was taken, 100 kg of the mixture was blended into 22 kg of bituminous coal, 18 kg of lime, and 13 kg of silica. The mixture was smelted in an electric furnace for 3 hours, and 71 kg of manganese-silicon alloy was cast. The slag is acid leached to obtain a lithium-containing solution, which is then precipitated by adding a sodium carbonate solution, and filtered to obtain 10 kg of lithium carbonate.
经检测， 所得锰硅合金成分： Mn 68%, Si02 21%, C 7%, P 0. 3%。
After testing, the composition of the obtained manganese silicon alloy: Mn 68%, Si0 2 21%, C 7%, P 0. 3%.
Claims
1、 锰酸锂电池正极材料回收方法， 包括从锰酸锂电池正极片中分离铝箔步骤， 其特征 在于： 将锰酸锂电池正极片于 300〜600°C加热 l〜4h， 然后分离铝箔， 得到锰酸锂正极材料、 导电剂和粘结剂的混合物。 1. The recycling method of lithium manganate battery cathode material includes the step of separating aluminum foil from the lithium manganate battery cathode sheet, which is characterized by: heating the lithium manganate battery cathode sheet at 300~600°C for 1~4 hours, and then separating the aluminum foil, A mixture of lithium manganate cathode material, conductive agent and binder is obtained.
2、根据权利要求 1所述的酸锂电池正极材料回收方法， 其特征在于： 分离铝箔的分离方 法采用机械分离或超声波震荡方法分离。 2. The method for recycling positive electrode materials of lithium-acid batteries according to claim 1, characterized in that: the separation method of separating aluminum foil adopts mechanical separation or ultrasonic vibration separation method.
3、 根据权利要求 1或 2所述的酸锂电池正极材料回收方法， 其特征在于包括如下步骤： a、 拆解废旧锰酸锂电池， 取出正极片； 3. The method for recycling cathode material of lithium acid battery according to claim 1 or 2, characterized by comprising the following steps: a. Disassemble the used lithium manganese oxide battery and take out the cathode sheet;
b、 正极片于 300〜600°C加热 l〜4h， 然后分离铝箔， 得到锰酸锂正极材料、 导电剂和粘 结剂的混合物； b. The positive electrode sheet is heated at 300~600°C for 1~4 hours, and then the aluminum foil is separated to obtain a mixture of lithium manganate positive electrode material, conductive agent and binder;
c、 混合物于 1000〜1200°C煅烧 l〜3h， 然后造球； c. The mixture is calcined at 1000~1200°C for 1~3h, and then pelletized;
d、 造球后的混合物与碳质还原剂、 硅石、 石灰按重量比 100 : 18〜22： 13〜17： 14〜18 混匀， 然后电炉冶炼 l〜3h， 得到锰硅合金和炉渣； d. Mix the pelletized mixture with carbonaceous reducing agent, silica, and lime in a weight ratio of 100: 18~22: 13~17: 14~18, and then smelt in an electric furnace for 1 to 3 hours to obtain manganese-silicon alloy and slag;
e、 炉渣酸浸得到含锂溶液， 再加入碳酸钠溶液沉淀， 过滤， 得到碳酸锂。 e. Acid leaching the slag to obtain a lithium-containing solution, then adding sodium carbonate solution to precipitate, and filtering to obtain lithium carbonate.
4、 根据权利要求 3所述的锰酸锂电池正极材料回收方法， 其特征在于： d步骤中所述的 碳质还原剂为木炭 石油焦、 烟煤、 蓝炭、 焦炭中至少一种。 4. The lithium manganate battery cathode material recovery method according to claim 3, characterized in that: the carbonaceous reducing agent in step d is at least one of charcoal, petroleum coke, bituminous coal, blue carbon, and coke.
5、 根据权利要求 3或 4所述的锰酸锂电池正极材料回收方法， 其特征在于： e步骤中酸 浸所用酸为盐酸或硫酸。
5. The method for recycling lithium manganate battery cathode materials according to claim 3 or 4, characterized in that: the acid used in the acid leaching in step e is hydrochloric acid or sulfuric acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310105266.8A CN103219561B (en) | 2013-03-28 | 2013-03-28 | Lithium manganate cell positive electrode material recovery method |
| CN201310105266.8 | 2013-03-28 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018184876A1 (en) * | 2017-04-07 | 2018-10-11 | Umicore | Process for the recovery of lithium |
| CN110311186A (en) * | 2019-03-06 | 2019-10-08 | 清华大学 | A method of recycling valuable element from waste and old lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103219561B (en) * | 2013-03-28 | 2015-08-19 | 四川天齐锂业股份有限公司 | Lithium manganate cell positive electrode material recovery method |
| CN103526035B (en) * | 2013-10-31 | 2015-08-05 | 长沙矿冶研究院有限责任公司 | The method of valuable metal is reclaimed from waste and old lithium ion battery and/or its material |
| CN105907983A (en) * | 2016-04-20 | 2016-08-31 | 天齐锂业股份有限公司 | Method of extracting lithium from furnace slag generated from pyrogenic process recovery of lithium battery |
| CN106450557B (en) * | 2016-11-30 | 2019-06-11 | 荆门市格林美新材料有限公司 | The method of the positive electrode and aluminium of separating waste, worn anode on piece |
| CN107910610B (en) * | 2017-11-16 | 2019-06-28 | 江苏智泰新能源科技有限公司 | A kind of anode and electrolyte mixing recovery method of lithium battery |
| CN109207725B (en) * | 2018-09-19 | 2020-06-30 | 中国科学院青海盐湖研究所 | Method and system for recovering lithium and manganese from waste lithium manganate battery |
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| CN112582601A (en) * | 2020-12-14 | 2021-03-30 | 中钢集团南京新材料研究院有限公司 | Method for preparing lithium nickel manganese oxide by utilizing waste lithium manganese oxide and lithium nickel manganese oxide |
| CN114015873A (en) * | 2021-09-18 | 2022-02-08 | 昆明理工大学 | Method for preparing manganese-silicon alloy from lithium ore and enriching lithium |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101707269A (en) * | 2009-10-14 | 2010-05-12 | 东莞新能源科技有限公司 | Method for recycling anode material of lithium ion battery |
| CN101942569A (en) * | 2010-10-28 | 2011-01-12 | 湖南邦普循环科技有限公司 | Method for recovering lithium from waste lithium ion battery and waste pole piece |
| WO2012140951A1 (en) * | 2011-04-15 | 2012-10-18 | 住友金属鉱山株式会社 | Method for recovering valuable metals |
| CN103219561A (en) * | 2013-03-28 | 2013-07-24 | 四川天齐锂业股份有限公司 | Method for recovering lithium manganate battery anode material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1262042C (en) * | 2004-06-09 | 2006-06-28 | 南开大学 | Method for regenerating anode materials of waste lithium ion secondary battery |
| JP5771031B2 (en) * | 2011-03-17 | 2015-08-26 | 株式会社シンコーフレックス | Method for recovering manganese-based alloys from manganese oxide-based waste |
| CN102367524B (en) * | 2011-09-29 | 2013-04-10 | 云南文山斗南锰业股份有限公司 | Smelting method of manganese alloy |
| CN102569838B (en) * | 2012-01-18 | 2015-08-26 | 广东邦普循环科技有限公司 | Method for recycling valuable metals in manganese series waste batteries |
-
2013
- 2013-03-28 CN CN201310105266.8A patent/CN103219561B/en active Active
-
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- 2014-03-27 WO PCT/CN2014/074170 patent/WO2014154154A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101707269A (en) * | 2009-10-14 | 2010-05-12 | 东莞新能源科技有限公司 | Method for recycling anode material of lithium ion battery |
| CN101942569A (en) * | 2010-10-28 | 2011-01-12 | 湖南邦普循环科技有限公司 | Method for recovering lithium from waste lithium ion battery and waste pole piece |
| WO2012140951A1 (en) * | 2011-04-15 | 2012-10-18 | 住友金属鉱山株式会社 | Method for recovering valuable metals |
| CN103219561A (en) * | 2013-03-28 | 2013-07-24 | 四川天齐锂业股份有限公司 | Method for recovering lithium manganate battery anode material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018184876A1 (en) * | 2017-04-07 | 2018-10-11 | Umicore | Process for the recovery of lithium |
| CN110494575A (en) * | 2017-04-07 | 2019-11-22 | 尤米科尔公司 | The method for recycling lithium |
| CN110494575B (en) * | 2017-04-07 | 2021-12-21 | 尤米科尔公司 | Method for recovering lithium |
| CN110311186A (en) * | 2019-03-06 | 2019-10-08 | 清华大学 | A method of recycling valuable element from waste and old lithium ion battery |
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| Publication number | Publication date |
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| CN103219561A (en) | 2013-07-24 |
| CN103219561B (en) | 2015-08-19 |
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