CN103633392A - Method for preparing the nickel-manganese hydroxide from waste power batteries through constant circulation - Google Patents
Method for preparing the nickel-manganese hydroxide from waste power batteries through constant circulation Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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- 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
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- 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
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- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention belongs to the technical field of nickel-manganese hydroxide preparation and discloses a method for preparing the nickel-manganese hydroxide from waste power batteries through constant circulation and application of the hydroxide. The method comprises the following concrete steps: dismantling a waste LiNi0.5Mn1.5O4 power battery to separate a positive plate from a negative plate; crushing the positive plate for heating and sieving, wherein the oversize is aluminium foil, and the undersize is LiNi0.5Mn1.5O4 cathode material powder and acetylene black; adding acid in the undersize to filter out the acetylene black so as to obtain a nickel-manganese containing mixed solution; sequentially adding a nickel source, a manganese source and a shape forming agent; adjusting the pH value, adding a nucleus formation additive for heating and dissolving, and performing microwave reaction; obtaining the nickel-manganese hydroxide through cooling, filtering, washing and drying. According to the method, the nucleus formation additive is adopted to form the nickel-manganese hydroxide crystal nucleuses which are connected to one another by the shape forming agent to obtain dandelion-shaped particles which are uniform in size and appearance structure and grow in order. The nickel-manganese hydroxide is used as the cathode material to prepare the battery with obviously improved specific capacity.
Description
Technical field
The invention belongs to nickel manganese hydroxide preparing technical field, particularly a kind of methods and applications of being prepared nickel manganese hydroxide by the directed circulation of waste and old electrokinetic cell.
Background technology
China < < is energy-conservation, and being totally sold to 2015 reaches 500,000 with new-energy automobile industrial development planning (2012-2020) > > electric automobile, and the year two thousand twenty reaches 5,000,000.Under the guidance of national policy, electrokinetic cell industry obtains develop rapidly.China's automobile industry standard regulation lithium-ion-power cell cycle life is no less than 500 times, current research finds that best lithium-ion-power cell cycle life is no more than 3000 times, according to the ruuning situation of domestic existing pure electric bus, the life-span of electrokinetic cell is 3～5 years.Dewulf scholar's analysis result finds to reclaim lithium ion battery can save 51.3% natural resources.
Universal its supporting lithium ion battery that impels of consumer electronics product and power vehicle develops to high-energy-density.Positive electrode directly determines the performance of lithium ion battery.Nickel manganate cathode material for lithium is because of considerable charge/discharge capacity and excellent cyclical stability, produces and uses increasingly extensively, demonstrates huge market prospects.Although raw material grind through long-time before roasting, lithium salts, nickel salt and manganese salt are all difficult to reach other even contact of molecular level, and the uniformity of material is poor.In order better to synthesize the nickel manganate cathode material for lithium with stoichiometric proportion, the solution of often taking is with nickel manganese hydroxide, by adding the roasting of lithium source to make nickel LiMn2O4.Size, pattern, the structure of nickel manganese hydroxide, have a direct impact size, pattern, the structure of the nickel LiMn2O4 of following process.Therefore, the performance quality of nickel manganese hydroxide has determined the performance quality of nickel LiMn2O4.
Directed circulating resourcesization is utilized, and refers to after a kind of product rejection, and this product, through reasonably decomposing and restructuring, is made to a kind of recycling process of the like product identical or close with original product performance.The directed circulating resourcesization of electrokinetic cell is utilized, and refers to after electrokinetic cell is scrapped, and power battery material is decomposed through element, by certain formula, is prepared into new power battery material.
Summary of the invention
In order to overcome the shortcoming and deficiency of above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of method of being prepared nickel manganese hydroxide by the directed circulation of waste and old electrokinetic cell, to obtain the presoma of the nickel lithium manganate battery material of high-quality.
The nickel manganese hydroxide that provides said method to prepare is provided another object of the present invention.
Still a further object of the present invention is to provide the application of above-mentioned nickel manganese hydroxide in synthesizing lithium ion positive electrode.The battery that utilizes this nickel manganese hydroxide to prepare as positive electrode has higher specific capacity, and the battery of making than common nickel manganese hydroxide improves can reach 8%.
Still a further object of the present invention is to provide the application of the above-mentioned method of preparing nickel manganese hydroxide by the directed circulation of waste and old electrokinetic cell in recycling waste and old electrokinetic cell.
Object of the present invention realizes by following proposal:
A method of being prepared nickel manganese hydroxide by the directed circulation of waste and old electrokinetic cell, comprises following concrete operations:
(1) disassemble waste and old nickel LiMn2O4 electrokinetic cell, separated positive plate and negative plate;
(2) positive plate is broken, heating, screening, oversize is aluminium foil, screenings is nickel manganate cathode material for lithium powder and acetylene black;
(3) acid adding in screenings, removes by filter acetylene black, obtains mixed solution nickeliferous, manganese;
(4) in step (3) mixed solution, add successively ,Meng source, nickel source and excipient;
(5) pH of regulating step (4) system, adds nucleation-accelerant, heating for dissolving, microwave reaction;
(6) cooling, filter, washing, dry, obtain nickel manganese hydroxide.
Nickel source described in step (4) refers at least one in nickel acetate, nickel chloride and nickelous sulfate.
Described manganese source refers at least one in manganese chloride, manganese sulfate and manganese acetate.
Described excipient refers at least one in glycerol, ethylene glycol, BT, 1,2-PD and 1,3-PD.
He Meng source, nickel used source amount so that after adding He Meng source, nickel source the nickel element in system and the mol ratio of manganese element be (3～5): 1 is as the criterion.
Preferably, add before ,Meng source, nickel source, utilize nickel, manganese element content in aas determination step (3) solution.
The quality of used excipient is (30～40) g:1mol with adding behind ,Meng source, nickel source the ratio of the total mole number of nickel element, manganese element in system.
Nucleation-accelerant described in step (5) refers at least one in softex kw, triethylenediamine, diethylenetriamines, hexamethylene imine and hexa.
Nucleation-accelerant used quality be (10～20) g:1mol with adding behind ,Meng source, nickel source the ratio of the total mole number of nickel element, manganese element in system.
Described heating for dissolving refers to be heated to 80～90 ℃ and stirs 10～20min.
Described microwave reaction refers to solution after dissolving to transfer in hydrothermal reaction kettle, with variable frequency microwave Hydrothermal Synthesis instrument, is heated to 120～200 ℃ of isothermal reaction 2～10h.
Described washing refers to pure water and alternately washing of ethanol.
Described dry finger is dry at 60 ℃.
The pH of described regulating step (4) system refers to add NaOH to regulate pH to 7, then adds ammoniacal liquor to regulate pH to 11～13.
The described acid of step (3) refers at least one in hydrochloric acid, sulfuric acid and nitric acid.
The concentration of described acid is 1～3mol/L.
The amount of acid used is that every 100～150g screenings is used 1L acid.
The nickel manganese hydroxide that the present invention also provides a kind of method of preparing nickel manganese hydroxide by the directed circulation of above-mentioned waste and old electrokinetic cell to prepare.
The application of above-mentioned nickel manganese hydroxide in synthesizing lithium ion positive electrode.The battery that utilizes this nickel manganese hydroxide to prepare as positive electrode has higher specific capacity, and the battery of making than common nickel manganese hydroxide improves can reach 8%.
The application of the above-mentioned method of preparing nickel manganese hydroxide by the directed circulation of waste and old electrokinetic cell in recycling waste and old electrokinetic cell.
Mechanism of the present invention is:
Building-up process of the present invention is first by nucleation-accelerant, to assemble nickel ion, manganese ion, hydroxide ion, form nickel manganese hydroxide nucleus, by excipient, connect the formed nucleus of nucleation-accelerant again, spiral dislocation by under hydrothermal condition and form unique hydrogen bond with water, makes to form on nucleus whisker.By the synergy of above nucleation-accelerant and excipient, obtain dandelion shape particle.Meanwhile, adopt variable frequency microwave heating, heated material obtains regular energy absorption frequency, effectively controls the speed of growth of crystal.
The present invention, with respect to prior art, has following advantage and beneficial effect:
(1) the present invention adopts glycerol etc. as excipient, utilizes excipient under hydrothermal condition, to cause spiral dislocation, forms unique hydrogen bond network with water, and the breeding of dislocation and hydrogen bond action cause nickel manganese hydroxide to form surperficial whisker.The nickel manganese hydroxide of this structure and lithium source are conducive to the melting Li that lithium source decomposes produces in sintering process
2o fully diffuses into nickel manganese hydroxide from dandelion shape space, material composition is distributed more even, obtains more preferably measuring comparing compound.
(2) the present invention adopts the control nickel manganese hydroxide nucleation such as softex kw.Softex kws etc. play the effect of transportation growing element, and growing element is assembled and formed dandelion shape particle.After reacting with lithium source, the nickel manganese hydroxide that makes to make there is larger tap density.
(3) the present invention adopts variable frequency microwave heating, and heated material obtains special energy absorption rhythm, effectively controls the speed of growth of crystal.
(4) the nickel manganese hydroxide that the present invention prepares has special structure and pattern.In the sintering process in nickel manganese hydroxide and lithium source, be conducive to the melting Li that lithium source decomposes produces
2o fully diffuses into nickel manganese hydroxide from dandelion shape space, material composition is distributed more even; Dandelion shape particle has larger tap density; Particle diameter is even, and appearance structure is consistent, grows more orderly.Utilize its battery preparing as positive electrode to have higher specific capacity, the battery of making than common nickel manganese hydroxide improves can reach 8%.
Accompanying drawing explanation
Fig. 1 is the nickel manganese hydroxide SEM figure of embodiment 1 preparation.
Fig. 2 is the charging and discharging curve of nickel manganese hydroxide.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1:
A method of being prepared nickel manganese hydroxide by the directed circulation of waste and old electrokinetic cell, comprises following concrete steps:
(1) by a quality, be that the waste and old nickel LiMn2O4 of 2170g electrokinetic cell is disassembled, take out 868.24g positive plate;
(2) positive plate is pulverized, at 400 ℃ of heating 1h, with 60 mesh standard sieve vibration screenings, oversize is 19.37g aluminium foil, and screenings is 803.73g nickel manganate cathode material for lithium powder and 45.14g acetylene black;
(3) in screenings, adding 8L molar concentration is the hydrochloric acid of 1mol/L, removes by filter acetylene black, obtains the mixed solution that filtrate is contained nickel, manganese;
(4) through aas determination, nickel ion concentration is 1.32mol/L, and manganese ion concentration is 0.31mol/L;
(5) in the mixed solution of step (3), add 1741.82g nickel chloride and 716.72g manganese chloride, then add 960g glycerol;
(6) in the mixed solution of step (5), add NaOH to regulate pH to 7, then add ammoniacal liquor to regulate pH to 11, add 320g softex kw, solution is heated to 80 ℃, stir 10min;
(7) above-mentioned solution is got to 80mL and be placed in 100mL hydrothermal reaction kettle, with variable frequency microwave Hydrothermal Synthesis instrument, be heated to 120 ℃, constant temperature 10h, then naturally cools to room temperature;
(8) upper step reaction solution is filtered, obtain filter residue, respectively with pure water and ethanol washing filter residue, in air, dry at 60 ℃; Crushed after being dried, it is 2915g nickel manganese hydroxide that shaking screen divides screenings.It is carried out to SEM scanning, as shown in Figure 1.As seen from Figure 1, the nickel manganese hydroxide obtaining is dandelion shape particle and has larger tap density; Particle diameter is even, and appearance structure is consistent, and growth in order.
Embodiment 2:
A method of being prepared nickel manganese hydroxide by the directed circulation of waste and old electrokinetic cell, comprises following concrete steps:
(1) by a quality, be that the waste and old nickel LiMn2O4 of 2225g electrokinetic cell is disassembled, take out 892.42g positive plate;
(2) positive plate is pulverized, at 400 ℃ of heating 1h, with 60 mesh standard sieve vibration screenings, oversize is 26.47g aluminium foil, and screenings is 825.73g nickel manganate cathode material for lithium powder and 40.22g acetylene black;
(3) in screenings, adding 6.5L molar concentration is the sulfuric acid of 2mol/L, removes by filter acetylene black, obtains the mixed solution that filtrate is contained nickel, manganese;
(4) through aas determination, nickel ion concentration is 1.53mol/L, and manganese ion concentration is 0.49mol/L;
(5) in the mixed solution of step (3), add 2490.93g nickelous sulfate and 514.32g manganese sulfate, then add 1137.5g ethylene glycol;
(6) in the mixed solution of step (5), add NaOH to regulate pH to 7, then add ammoniacal liquor to regulate pH to 12, add 487.5g triethylenediamine, solution is heated to 85 ℃, stir 15min;
(7) above-mentioned solution is got to 80mL and be placed in 100mL hydrothermal reaction kettle, with variable frequency microwave Hydrothermal Synthesis instrument, be heated to 160 ℃, constant temperature 5h, then naturally cools to room temperature;
(8) upper step reaction solution is filtered, obtain filter residue, respectively with pure water and ethanol washing filter residue, in air, dry at 60 ℃; Crushed after being dried, it is 2960g nickel manganese hydroxide that shaking screen divides screenings.
Embodiment 3:
A method of being prepared nickel manganese hydroxide by the directed circulation of waste and old electrokinetic cell, comprises following concrete steps:
(1) by a quality, be that the waste and old nickel LiMn2O4 of 2314g electrokinetic cell is disassembled, take out 900.13g positive plate;
(2) positive plate is pulverized, at 400 ℃ of heating 1h, with 60 mesh standard sieve vibration screenings, oversize is 29.51g aluminium foil, and screenings is 824.44g nickel manganate cathode material for lithium powder and 46.18g acetylene black;
(3) in screenings, adding 5.5L molar concentration is the nitric acid of 3mol/L, removes by filter acetylene black, obtains the mixed solution that filtrate is contained nickel, manganese;
(4) through aas determination, nickel ion concentration is 1.67mol/L, and manganese ion concentration is 0.62mol/L;
(5) in the mixed solution of step (3), add 3241.76g nickel acetate and 369.93g manganese acetate, then add 1320g1,2,4-butantriol;
(6) in the mixed solution of step (5), add NaOH to regulate pH to 7, then add ammoniacal liquor to regulate pH to 13, add 660g hexamethylene imine, solution is heated to 90 ℃, stir 20min;
(7) upper step solution is got to 80mL and be placed in 100mL hydrothermal reaction kettle, with variable frequency microwave Hydrothermal Synthesis instrument, be heated to 200 ℃, constant temperature 2h, then naturally cools to room temperature;
(8) upper step reaction solution is filtered, obtain filter residue, respectively with pure water and ethanol washing filter residue, in air, dry at 60 ℃; Crushed after being dried, it is 3026g nickel manganese hydroxide that shaking screen divides screenings.
Embodiment 4: comparative example
(1) compound concentration is the hydrochloric acid solution of 3mol/L nickel chloride, 1mol/L manganese chloride, adds sodium hydrate regulator solution pH=7, then adds ammoniacal liquor regulator solution pH=11, and solution is heated to 80 ℃, stirs 10min;
(2) upper step solution is got to 80mL and be placed in 100mL hydrothermal reaction kettle, with baking oven, be heated to 120 ℃, constant temperature 10h, then naturally cools to room temperature;
(3) upper step reaction solution is filtered, obtain filter residue, respectively with pure water and ethanol washing filter residue, in air, dry at 60 ℃; Crushed after being dried, shaking screen divides and obtains nickel manganese hydroxide comparative sample.
Embodiment 5: the Performance Detection of nickel manganese hydroxide
The nickel manganese hydroxide of getting 10g embodiment 1, embodiment 2, embodiment 3 and comparative example adds respectively 4g lithium carbonate to mix, and is placed in constant temperature 4h at 250 ℃, then is warming up to 800 ℃ of constant temperature 10h, and heating rate is 1 ℃/min, obtains respectively nickel LiMn2O4.
The nickel LiMn2O4 that above-described embodiment 1, embodiment 2, embodiment 3 and comparative example make of take is respectively anodal, take lithium metal as negative pole, be assembled into battery, with 1C multiplying power, carry out discharge test first, as shown in Figure 2, wherein curve A 1, B1, C1 and D1 are discharge curve, respectively corresponding embodiment 1, embodiment 2, embodiment 3 and comparative example; Curve A 2, B2, C2 and D2 are charging curve, respectively corresponding embodiment 1, embodiment 2, embodiment 3 and comparative example.Result shows, under 1C multiplying power, the first discharge specific capacity of the lithium ion battery of doing with nickel manganese hydroxides of the present invention is than the height of common hydro thermal method, the specific capacity of embodiment 1 is 151.5mAh/g, the specific capacity of embodiment 2 is 150.9mAh/g, the specific capacity of embodiment 3 is 149.6mAh/g, and the specific capacity of comparative example only has 139.0mAh/g.
Above-described embodiment is preferably execution mode of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. by the directed circulation of waste and old electrokinetic cell, prepared a method for nickel manganese hydroxide, it is characterized in that comprising following concrete operations:
(1) disassemble waste and old nickel LiMn2O4 electrokinetic cell, separated positive plate and negative plate;
(2) positive plate is broken, heating, screening, oversize is aluminium foil, screenings is nickel manganate cathode material for lithium powder and acetylene black;
(3) acid adding in screenings, removes by filter acetylene black, obtains mixed solution nickeliferous, manganese;
(4) in step (3) mixed solution, add successively ,Meng source, nickel source and excipient;
(5) pH of regulating step (4) system, adds nucleation-accelerant, heating for dissolving, microwave reaction;
(6) cooling, filter, washing, dry, obtain nickel manganese hydroxide.
2. the method for being prepared nickel manganese hydroxide by the directed circulation of waste and old electrokinetic cell according to claim 1, is characterized in that: the nickel source described in step (4) refers at least one in nickel acetate, nickel chloride and nickelous sulfate; Described manganese source refers at least one in manganese chloride, manganese sulfate and manganese acetate; Described excipient refers at least one in glycerol, ethylene glycol, BT, 1,2-PD and 1,3-PD.
3. the method for being prepared nickel manganese hydroxide by the directed circulation of waste and old electrokinetic cell according to claim 1, is characterized in that: the amount in He Meng source, nickel used source in step (4) so that after adding He Meng source, nickel source the nickel element in system be (3～5) with the mol ratio of manganese element: 1 is as the criterion.
4. the method for being prepared nickel manganese hydroxide by the directed circulation of waste and old electrokinetic cell according to claim 1, is characterized in that: in step (4), the quality of used excipient is (30～40) g:1mol with adding behind ,Meng source, nickel source the ratio of the total mole number of nickel element, manganese element in system.
5. the method for being prepared nickel manganese hydroxide by the directed circulation of waste and old electrokinetic cell according to claim 1, is characterized in that: the nucleation-accelerant described in step (5) refers at least one in softex kw, triethylenediamine, diethylenetriamines, hexamethylene imine and hexa; The quality of nucleation-accelerant used is (10～20) g:1mol with adding behind ,Meng source, nickel source the ratio of the total mole number of nickel element, manganese element in system.
6. the method for being prepared nickel manganese hydroxide by the directed circulation of waste and old electrokinetic cell according to claim 1, is characterized in that: the heating for dissolving described in step (5) refers to be heated to 80～90 ℃ and stirs 10～20min; Described microwave reaction refers to solution after dissolving to transfer in hydrothermal reaction kettle, with variable frequency microwave Hydrothermal Synthesis instrument, is heated to 120～200 ℃ of isothermal reaction 2～10h; Described washing refers to pure water and alternately washing of ethanol; Described dry finger is dry at 60 ℃.
7. the method for being prepared nickel manganese hydroxide by the directed circulation of waste and old electrokinetic cell according to claim 1, is characterized in that: the pH of described regulating step (4) system refers to add sodium hydrate regulator solution pH to 7, then adds ammoniacal liquor to regulate pH to 11～13; The described acid of step (3) refers at least one in hydrochloric acid, sulfuric acid and nitric acid; The concentration of described acid is 1～3mol/L; The amount of acid used is that every 100～150g screenings is used 1L acid.
8. a nickel manganese hydroxide, is characterized in that: according to the method for preparing nickel manganese hydroxide by the directed circulation of waste and old electrokinetic cell described in claim 1～7 any one, prepare.
9. the application of nickel manganese hydroxide according to claim 8 in synthesizing lithium ion positive electrode.
10. the application in recycling waste and old electrokinetic cell according to the method for preparing nickel manganese hydroxide by the directed circulation of waste and old electrokinetic cell described in claim 1～7 any one.
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| US20240039068A1 (en) * | 2021-07-22 | 2024-02-01 | Guangdong Brunp Recycling Technology Co., Ltd. | Method for selectively extracting lithium from retired battery and application of method |
| CN114843474A (en) * | 2022-05-17 | 2022-08-02 | 天能新能源(湖州)有限公司 | High-rate lithium ion battery positive electrode material and preparation method thereof |
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