CN103151576B - Method for preparing lithium battery cathode material by using waste zinc-manganese battery - Google Patents
Method for preparing lithium battery cathode material by using waste zinc-manganese battery Download PDFInfo
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- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000002699 waste material Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 13
- 239000010406 cathode material Substances 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 239000011701 zinc Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 34
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 29
- 239000007773 negative electrode material Substances 0.000 claims abstract description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000011572 manganese Substances 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 238000011049 filling Methods 0.000 claims description 10
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229940010514 ammonium ferrous sulfate Drugs 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000010297 mechanical methods and process Methods 0.000 claims description 2
- 239000012086 standard solution Substances 0.000 claims description 2
- 238000004448 titration Methods 0.000 claims description 2
- SZKTYYIADWRVSA-UHFFFAOYSA-N zinc manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Zn++] SZKTYYIADWRVSA-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 238000007789 sealing Methods 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910001676 gahnite Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
Abstract
The invention discloses a method for preparing a lithium battery cathode material by using a waste zinc-manganese battery, belonging to the technical field of resource recovery treatment of solid wastes. The method comprises the following steps: (1) Mechanically disassembling the battery, and separating out a carbon rod, a metal cap, a zinc sheet, an iron sheet and a black mixture; (2) Cleaning zinc skins, crushing and drying for later use, and ball-milling and drying a black mixture for later use; (3) Measuring the content of zinc and manganese elements in the mixture by a chemical volumetric method; (4) Putting a certain proportion of zinc sheet and black mixture into a reaction kettle, adjusting the pH value to 5-9 with ammonia water, carrying out hydrothermal reaction at 180-220 ℃ for 1-3 days, taking out and cooling; and (5) washing, filtering and drying the product. The invention recycles the waste zinc-manganese batteries, reduces the environmental pollution and develops the negative electrode material ZnMn of the lithium battery with high added value 2 O 4 。
Description
Technical Field
The invention belongs to the technical field of recycling treatment of solid wastes, and particularly relates to a method for preparing a lithium battery cathode material by using a waste zinc-manganese battery. In particular to a method for preparing a negative electrode material ZnMn of a lithium battery by using a waste zinc-manganese battery as a raw material 2 O 4 The method of (1).
Background
China is a big country for producing and consuming dry batteries, the annual output reaches 150 hundred million, the world is the first, and accounts for about 1/3 of the total amount of the world, and 70 percent of the dry batteries are zinc-manganese dry batteries. Calculated by producing 100 million zinc-manganese dry batteries every year, the zinc and manganese consumed all year round is equivalent to the annual zinc and manganese production of three or four large smelting plants. The zinc-manganese dry battery is discarded at will, thereby not only wasting precious metal resources, but also polluting the environment and being harmful to human health. Due to the shortage of resources and the need of environmental governance, the recycling of waste batteries is highly valued in various countries, and is regarded as an important renewable resource of zinc and manganese.
At present, the recovery of waste zinc-manganese batteries is widely researched, but the recovery of resources is realized mainly by separating and extracting various metals or metal compounds in the modes of roasting, acid leaching and the like. In recent years, there has been research on the preparation of zinc-manganese ferrite directly using zinc-manganese batteries as raw materials, for example, patent [ 200410051920.2 ] method for preparing ferrite from waste zinc-manganese batteries; 200510017323.2 method for preparing manganese zinc ferrite from waste zinc-manganese batteries. Niyulong and other waste zinc-manganese dry cell containing zinc and MnO 2 The electrode material is used as a raw material, and a precipitation-calcination method is adopted to prepare uniformly dispersed tetragonal ZnMn with the grain diameter of about 10nm 2 O 4 Nano-catalyst, and researches on catalytic activity of nano-catalyst in catalytic synthesis of n-butyl acetate [ preparation of ZnMn based on waste zinc-manganese dry battery 2 O 4 Nano catalyst and research of synthesizing n-butyl acetate by catalysis thereof, anhui chemical industry, 2011,37 (5): 16-18). In recent years, composite metal oxides have been used as negative electrode materials for lithium ion secondary batteries, such as gahnite ZnM 2 O 4 (M = Mn, cr, fe, co, etc.) are attracting attention in succession, with Co, cr being expensive and environmentally unfriendly, and ZnMn 2 O 4 With ZnFe 2 O 4 Compared with the battery with the lower discharge platform, the battery with the positive electrode material has higher potential and higher energy density. Thus, the spinel type ZnMn 2 O 4 The negative electrode material is considered as a potential substitute material of graphite negative electrode of lithium ion battery (201010545470.8-ZnMn negative electrode material of lithium ion battery 2 O 4 The preparation method of (1), 201010573608.5 manganese spinel nano material and its preparation method and application.
However, the ZnMn serving as the negative electrode material of the lithium battery is directly hydrothermally synthesized by utilizing the zinc-manganese waste 2 O 4 It has not been reported. The invention utilizes the waste zinc-manganese battery to prepare the negative electrode material ZnMn of the lithium battery 2 O 4 Not only doRealizes the reutilization of wastes, reduces the environmental pollution, develops products with high added value and high growing industrial chain, and has good economic and social benefits.
Disclosure of Invention
The invention aims to provide a method for preparing a lithium battery cathode material by using a waste zinc-manganese battery, which is characterized by comprising the following steps of:
(1) Disassembling the waste zinc-manganese battery by a mechanical method, and recovering a carbon rod, a metal cap, an iron sheet, a zinc sheet and a black mixture;
(2) Cleaning, drying and crushing the zinc sheet obtained in the step (1) by using ultrasonic waves for later use; placing the black mixture into a ball milling tank, adding deionized water and a dispersing agent, grinding and drying for later use;
(3) Weighing 0.5g of the spare black mixture processed in the step (2), determining the content of Zn in the spare black mixture by using an EDTA titration method, and determining the content of Mn in 0.1g of the spare black mixture by using an ammonium ferrous sulfate standard solution;
(4) Putting the crushed zinc skin and the black mixture into a reaction kettle according to a certain zinc-manganese ratio, adding deionized water, adjusting the pH value to 5-9 by using ammonia water, carrying out hydrothermal reaction at the temperature of 180-220 ℃ for 1-3 days, taking out, and naturally cooling;
(5) Washing the product with deionized water, filtering the product to neutrality, and drying to obtain ZnMn 2 O 4 And (3) a negative electrode material.
The crushed zinc skin and the black mixture react according to a certain zinc-manganese ratio, and the molar ratio of zinc to manganese is Zn: mn = (1 +/-x): 2,x =0.01.
After water and ammonia water are added in the hydrothermal reaction, the filling degree of the treatment materials in the reaction kettle is 80vol%.
The invention provides a method for preparing a negative electrode material ZnMn of a lithium battery by using a waste zinc-manganese battery while recycling solid wastes 2 O 4 Other components in the battery such as carbon rods, metal caps and iron sheets are recycled, and sustainable utilization of waste is fully realized. The method is simple, low in cost and good in environmental protection benefit,and synthesized ZnMn 2 O 4 Has good application prospect. The method is simple and easy to implement and low in cost, and the carbon black doped in the raw materials enables the synthesized ZnMn 2 O 4 The electrochemical performance is more excellent.
Drawings
Fig. 1 is an XRD pattern of the negative electrode material in example 1.
Fig. 2 is an SEM image of the anode material in example 1.
Fig. 3 is an XRD pattern of the anode material in example 2.
Fig. 4 is an SEM image of the anode material in example 2.
Fig. 5 is an XRD pattern of the anode material in example 3.
Fig. 6 is an SEM image of the anode material in example 3.
Fig. 7 is an XRD pattern of the negative electrode material of example 4.
Fig. 8 is an SEM image of the anode material in example 4.
Fig. 9 is an XRD pattern of the negative electrode material in example 5.
Fig. 10 is an SEM image of the anode material in example 5.
Fig. 11 is an XRD pattern of the negative electrode material in example 6.
Fig. 12 is an SEM image of the anode material in example 6.
Fig. 13 is an XRD pattern of the negative electrode material in example 7.
Fig. 14 is an SEM image of the anode material in example 7.
Fig. 15 is an XRD pattern of the negative electrode material of example 8.
Fig. 16 is an SEM image of the anode material in example 8.
Fig. 17 is an XRD pattern of the negative electrode material in example 9.
Fig. 18 is an SEM image of the anode material in example 9.
Detailed Description
The invention provides a method for preparing a negative electrode material ZnMn of a lithium battery by using a waste zinc-manganese battery 2 O 4 The method of (1). The salient and salient features of the invention are further illustrated by the following examples, which are intended to illustrate the invention and are not to be construed as limiting it in any way.
Example 1
Weighing 5.1682g of the black mixture after ball milling in a stainless steel reaction kettle lined with polytetrafluoroethylene, and adding a certain amount of water, wherein the ratio of Zn to Mn = 0.95. After being sealed, the reaction kettle is placed into a homogeneous reactor, and the filling degree of treatment materials (black mixture, zinc skin and water) in the reaction kettle is 80vol%; the reaction was carried out at 180 ℃ for 1 day. And taking out the reaction kettle after the reaction is finished, and cooling to room temperature. Taking out the obtained product, washing with deionized water, filtering and drying to obtain ZnMn 2 O 4 The powder has the first discharge specific capacity of 551.5mAh/g under the charge-discharge multiplying power of 0.1C.
Example 2
Weighing 5.1682g and 0.0222g of the black mixture after ball milling in a stainless steel reaction kettle lined with polytetrafluoroethylene, adding a certain amount of water, and adjusting the pH to be =7 by using a certain amount of ammonia water, wherein the ratio of Zn to Mn is =1. After sealing, the reaction kettle is placed into a homogeneous reactor, and the filling degree of treatment materials (black mixture, zinc skin, water and ammonia water) in the reaction kettle is 80vol%; the reaction was carried out at 190 ℃ for 2 days. And taking out the reaction kettle after the reaction is finished, and cooling to room temperature. Taking out the obtained product, washing with deionized water, filtering and drying to obtain ZnMn 2 O 4 The powder has a first discharge specific capacity of 609.5mAh/g under the charge-discharge multiplying power of 0.1C.
Example 3
Weighing 5.1682g of black mixture after ball milling and 0.0444g of zinc sheet in a stainless steel reaction kettle lined with polytetrafluoroethylene, adding a certain amount of water, and adjusting the pH value to be =9 by using a certain amount of ammonia water, wherein the Zn: mn = 1.034. After sealing, the reaction kettle is placed into a homogeneous reactor, and the filling degree of treatment materials (black mixture, zinc sheet, water and ammonia water) in the reaction kettle is 80vol%; the reaction was carried out at 180 ℃ for 3 days. And taking out the reaction kettle after the reaction is finished, and cooling to room temperature. Taking out the obtained product, washing with deionized water, filtering and drying to obtain ZnMn 2 O 4 The powder has a first discharge specific capacity of 689.5mAh/g under the charge-discharge multiplying power of 0.1C.
Example 4
Weighing 5.1682g of black mixture after ball milling and 0.0438g of zinc sheet in a stainless steel reaction kettle lined with polytetrafluoroethylene, adding a certain amount of water, wherein (Mn = 1.02) 2 O 4 Powder, the first discharge specific capacity is 697.3mAh/g under the charge-discharge multiplying power of 0.1C.
Example 5
Weighing 5.1682g of the ball-milled black mixture in a stainless steel reaction kettle lined with polytetrafluoroethylene, adding a certain amount of water, and adjusting the pH to be =7 by using a certain amount of ammonia water, wherein n (Zn) = 0.98. After sealing, the reaction kettle is placed into a homogeneous reactor, and the filling degree of treatment materials (black mixture, zinc skin, water and ammonia water) in the reaction kettle is 80vol%; the reaction was carried out at 200 ℃ for 3 days. And taking out the reaction kettle after the reaction is finished, and cooling to room temperature. Taking out the obtained product, washing with deionized water, filtering and drying to obtain ZnMn 2 O 4 Powder, 0.1C charge-discharge rate, first timeThe specific discharge capacity is 741.9mAh/g.
Example 6
Weighing 5.1682g of the black mixture after ball milling and 0.0224g of zinc sheet in a stainless steel reaction kettle lined with polytetrafluoroethylene, adding a certain amount of water, and adjusting the pH to be =8 by using a certain amount of ammonia water, wherein the ratio of Zn to Mn is = 1.01. After sealing, the reaction kettle is placed into a homogeneous reactor, and the filling degree of treatment materials (black mixture, zinc skin, water and ammonia water) in the reaction kettle is 80vol%; the reaction was carried out at 195 ℃ for 1 day. And taking out the reaction kettle after the reaction is finished, and cooling to room temperature. Taking out the obtained product, washing with deionized water, filtering and drying to obtain ZnMn 2 O 4 The first discharge specific capacity of the powder is 762mAh/g under the charge-discharge multiplying power of 0.1C.
Example 7
Weighing 5.1682g of black mixture after ball milling and 0.022g of zinc skin in a stainless steel reaction kettle lined with polytetrafluoroethylene, adding a certain amount of water, wherein the ratio of Zn to Mn = 0.99. After being sealed, the reaction kettle is placed into a homogeneous reactor, and the filling degree of treatment materials (black mixture, zinc skin and water) in the reaction kettle is 80vol%; the reaction was carried out at 210 ℃ for 3 days. And taking out the reaction kettle after the reaction is finished, and cooling to room temperature. Taking out the obtained product, washing with deionized water, filtering and drying to obtain ZnMn 2 O 4 The powder has a first discharge specific capacity of 735.7mAh/g under the charge-discharge multiplying power of 0.1C.
Example 8
Weighing 5.1682g of the black mixture after ball milling and 0.0451g of zinc sheet in a stainless steel reaction kettle lined with polytetrafluoroethylene, adding a certain amount of water, and adjusting the pH to be =7 by using a certain amount of ammonia water, wherein the ratio of Zn to Mn is = 1.05. After sealing, the reaction kettle is placed into a homogeneous reactor, and the filling degree of treatment materials (black mixture, zinc sheet, water and ammonia water) in the reaction kettle is 80vol%; the reaction was carried out at 220 ℃ for 1 day. Reaction ofAnd taking out the reaction kettle after the reaction is finished, and cooling to room temperature. Taking out the obtained product, washing with deionized water, filtering and drying to obtain ZnMn 2 O 4 The powder has a first discharge specific capacity of 736.1mAh/g under the charge-discharge rate of 0.1C.
Example 9
Weighing 5.1682g of the black mixture after ball milling in a stainless steel reaction kettle lined with polytetrafluoroethylene, adding a certain amount of water, and adjusting the pH value to be =9 by using a certain amount of ammonia water, wherein the Zn: mn = 0.966. After sealing, the reaction kettle is placed into a homogeneous reactor, and the filling degree of treatment materials (black mixture, zinc skin, water and ammonia water) in the reaction kettle is 80vol%; the reaction was carried out at 215 ℃ for 2 days. And taking out the reaction kettle after the reaction is finished, and cooling to room temperature. Taking out the obtained product, washing with deionized water, filtering and drying to obtain ZnMn 2 O 4 The first discharge specific capacity of the powder is 742.6mAh/g under the charge-discharge multiplying power of 0.1C.
Claims (2)
1. A method for preparing a negative electrode material of a lithium battery by using a waste zinc-manganese battery is characterized by comprising the following steps:
(1) Disassembling the waste zinc-manganese battery by a mechanical method, and recovering a carbon rod, a metal cap, an iron sheet, a zinc sheet and a black mixture;
(2) Cleaning, drying and crushing the zinc sheet obtained in the step (1) by using ultrasonic waves for later use; placing the black mixture into a ball milling tank, adding deionized water and a dispersing agent, grinding and drying for later use;
(3) Weighing 0.5g of the spare black mixture processed in the step (2), determining the content of Zn in the spare black mixture by using an EDTA titration method, and determining the content of Mn in 0.1g of the spare black mixture by using an ammonium ferrous sulfate standard solution;
(4) Putting the crushed zinc skin and the black mixture into a reaction kettle according to the zinc-manganese ratio of Zn to Mn = (1 +/-x) = (2): 2,x =0.01, adding deionized water, adjusting the pH to 5-9 by using ammonia water, carrying out hydrothermal reaction at the temperature of 180-220 ℃ for 1-3 days, taking out, and naturally cooling;
(5) Washing the product with deionized water, filtering the product to neutrality, and drying to obtain ZnMn 2 O 4 And (3) a negative electrode material.
2. The method for preparing a negative electrode material for a lithium battery by using the waste zinc-manganese dioxide battery as claimed in claim 1, wherein the filling degree of the treatment material in the reaction kettle is 80vol% after water and ammonia water are added during the hydrothermal reaction.
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| CN201310115732.0A CN103151576B (en) | 2013-02-16 | 2013-04-03 | Method for preparing lithium battery cathode material by using waste zinc-manganese battery |
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| CN103441315B (en) * | 2013-09-05 | 2015-05-20 | 北京理工大学 | Method for preparing manganese-zinc ferrite soft magnet by taking biological leachate of waste zinc-manganese battery as raw material |
| CN103746127B (en) * | 2013-11-11 | 2016-01-13 | 甘肃大象能源科技有限公司 | Method for preparing lithium manganate cathode material by using waste zinc-manganese dry batteries |
| CN104749318A (en) * | 2013-12-30 | 2015-07-01 | 北京有色金属与稀土应用研究所 | Method for volumetric method determination of zinc content in silver copper zinc cadmium nickel solder |
| CN107134603B (en) * | 2017-04-18 | 2019-05-03 | 东北大学 | Recycling method of waste zinc-manganese battery |
| US10615412B2 (en) * | 2018-01-30 | 2020-04-07 | Octopus Technologies Inc. | Manganese oxide composition and method for preparing manganese oxide composition |
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| CN108808033B (en) * | 2018-06-01 | 2020-09-01 | 南京信息工程大学 | Method for preparing electrode material of supercapacitor by using waste zinc-manganese battery |
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| ZnMn2O4 nanoparticles synthesized by a hydrothermal method as an anode material for Li-ion batteries;Fabrice M.Courtel, et al;《Electrochimica Acta》;20120329;第71卷;123-127 * |
| 基于废旧锌锰干电池制备ZnMn_2O_4纳米催化剂及其催化合成乙酸正丁酯的研究;倪玉龙等;《安徽化工》;20111031(第05期);16-18 * |
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