CN110061319A - A kind of reclaiming method of waste and old power lithium-ion battery tertiary cathode material - Google Patents
A kind of reclaiming method of waste and old power lithium-ion battery tertiary cathode material Download PDFInfo
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Abstract
The present invention relates to a kind of reclaiming methods of waste and old power lithium-ion battery tertiary cathode material.This method is using waste and old ternary power lithium ion battery as raw material, waste and old tertiary cathode material after the recovery is added into lithium, transition metal element and a certain amount of fluxing agent by sol-gel method, and high temperature sintering is combined, repair tertiary cathode material structure and performance in waste and old power lithium-ion battery.The addition of fluxing agent can reduce the fusing point of reactant, solid-phase reactant can be made preferably to melt and react, while it is uniform to obtain particle size；In addition, the fluxing agent chosen is the fluxing agent for being conducive to improve ternary material performance, avoids ternary material and further adulterate and coat, shorten processing technology, prepare with dominance energy and tertiary cathode material.With the advantages that high production efficiency, operation is simple, save the cost in terms of industrialization, while environment is protected, obtain reconstituted product, realize waste and old power battery material resource utilization, there is biggish economic benefit and social benefit.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries recovery technology fields, and in particular to a kind of waste and old lithium ion power
The recycling and regeneration method of battery tertiary cathode material.
Background technique
The power battery used on China's new-energy automobile at present is broadly divided into two classes: ternary material lithium ion battery and
Ferric phosphate lithium ion battery, wherein the energy density of ternary material lithium ion battery is higher, has occupied the mainstream in market.It is useless
It abandons in ternary material lithium ion battery containing a variety of valuable metals such as Li, Ni, Co, Mn, Cu, Al, the heavy metal contained, electricity
Solution liquid can all cause natural environment greatly to destroy, and a variety of valuable metals and nonmetallic materials that it contains have greatly
Recovery value and space.In face of the recycling market of huge waste lithium ion tertiary cathode material, it is discarded to be badly in need of exploitation
The high efficiency, low cost recovery technology of power lithium-ion battery ternary material, so that having in discarded ternary material lithium ion battery
Valence metal and nonmetallic materials are utilized effectively, and have not only avoided the wasting of resources but also have protected environment.
The ternary cathode material of lithium ion battery recovery method of mainstream at present, it is main using using soda acid dissolution, extraction or
Precipitating recycling valuable metal method, as Shenzhen City GeLinMei high New Technology Co., Ltd application protection application No. is
" a kind of waste and old power battery ternary system anode material processing method " of 201110243034.X and Sichuan day neat lithium industry share
Co., Ltd application protection application No. is 201610095291.6 " using recycling lithium ion battery material preparation ternary just
Method of pole material precursor " etc., these types of recovery process is although valuable metal in positive electrode can effectively be recycled such as
Lithium, nickel, cobalt, manganese etc., but entire removal process needs the techniques such as soda acid dissolution-removal of impurities-extraction and back extraction-precipitating, recycles
Process flow is long, and cost recovery is high；The a large amount of acid for the treatment of process, alkali and toxic solvent, to environment and operative employee
People's health forms biggish pressure.
Therefore, the efficient recycling method for developing a kind of waste and old power battery tertiary cathode material, can combine valuable
The clean and environmental protection of the high yield of metal, the high quality of product and high added value and treatment process is waste and old lithium ion power
Battery recycling technical field critical issue urgently to be resolved.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of waste and old lithium ion powers efficiently, inexpensive, environmentally friendly
The reclaiming method of battery tertiary cathode material.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of reclaiming method of waste and old power lithium-ion battery tertiary cathode material, Bao Kuo as lower Walk is rapid:
(1) extraction of power lithium-ion battery anode pole piece is discarded: by electric discharge completely discarded ternary power battery dismantling
After decladding, anode pole piece, cathode pole piece, diaphragm separation are separated from battery core.The anode pole piece is crushed, sieve
After point, the mixture A of tertiary cathode material, binder, conductive agent and a small amount of aluminium powder is obtained.
(2) purification of tertiary cathode material waste material: the mixture A that step (1) is obtained is placed in high-temperature incinerator,
Burning disposal is carried out under oxidizing atmosphere, after natural cooling, screening, obtains the mixed of tertiary cathode material and minute quantity aluminium
Close object B.The mixture B is placed in the sodium hydroxide solution that concentration is 4-10mol/L, a small amount of aluminium powder is removed, by clear
After washing, be centrifuged, drying, closing batch, the tertiary cathode material waste material C that is purified.
(3) tertiary cathode material waste material C main element analysis: the tertiary cathode material waste material that analysis testing procedure (3) obtains
The constituent content of lithium, nickel, cobalt, manganese in C.
(4) prepared by desiccant gel:
Tertiary cathode material waste material C and fluxing agent after 4a) weighing a certain amount of step (2) purification；According to tertiary cathode
The 0.5-5wt% of material waste C mass, weighs the fluxing agent of corresponding amount；
4b) according to the test result of step (3), according to nickel, cobalt, manganese in ternary material waste material C weighed in step (4a)
The 5-20% of content weighs the nickel acetate, manganese acetate, cobalt acetate of corresponding amount；
4c) the ratio for being 1:1.03 according to the molar ratio of nickel cobalt manganese total mole number and lithium in step (4a), step (4b)
, after the lithium in deduction step (4a) member positive material waste C, it is supplemented weighing the lithium acetate of corresponding amount；
4d) weigh the total moles of the step (4b), the nickel acetate in step (4c), manganese acetate, cobalt acetate, lithium acetate
The citric acid that several 1.5-2 times is measured；
4e) by step (4b), step (4c), the weighed nickel acetate of step (4d), manganese acetate, cobalt acetate, lithium acetate and
It is citric acid, soluble in water and be sufficiently mixed, blackish green solution is formed, being configured to metal ion total concentration is the molten of 2-4mol/l
Liquid；
4f) under conditions of mechanical stirring, step (4a) weighed ternary is added to step (4e) the blackish green solution
Material waste C and fluxing agent, and be vigorously stirred, it is adjusted to uniform suspension, then with the pH value of ammonium hydroxide adjusting solution to 7-
8, it is heated to 60-100 DEG C and continuous evaporation water, obtains gelinite D；
4g) by step (4f) the gelinite D, vacuum rotating is 6-10 hours dry at 80~150 DEG C, obtains xerogel
Body E；
(5) tertiary cathode material materials recycling: the xerogel body E that step (4g) obtains is distributed into crucible or saggar,
Then it is transferred to high temperature sintering furnace, is warming up between 750-1000 DEG C with the rate of 2-5 DEG C/min, under oxidizing atmosphere, sintering
10-20 hours.Then to get the tertiary cathode material finished product arrived after regeneration after supercooling, broken, screening.
Further, in the method for purification of step (2) the tertiary cathode material waste material, the oxidizing atmosphere be can be
The mixed atmosphere of air, oxygen or air and oxygen；The temperature of the high temperature incineration processing is between 200-600 DEG C, preferably
Ground, the temperature of burning disposal are between 300-500 DEG C.
Further, the main element analysis method of tertiary cathode material waste material described in step (3) can be chemistry drop
Determine one of method, ICP-AES, AAS or a variety of.
Further, in desiccant gel the preparation method described in step (4), the fluxing agent is selected from zirconium tetrafluoride, bifluoride
One of magnesium, aluminum trifluoride, boron oxide, boric acid, lithium metaborate, lithium borate are a variety of, and the fluxing agent dosage is described three
The 0.1-5% of first positive material waste C mass；Preferably, the dosage of the fluxing agent is the tertiary cathode material waste material C
The 0.5-2% of quality.
Further, in desiccant gel the preparation method described in step (4), the soluble nickel salt, cobalt salt, manganese salt difference
For one of nitrate, acetate, chlorate and sulfate corresponding to three kinds of nickel, cobalt, manganese metals or a variety of；It is described can
Insoluble nickel salt, cobalt salt, manganese salt total metal ion be nickel cobalt manganese total mole number in the tertiary cathode material waste material
Between 5%-20%.
Further, in desiccant gel the preparation method described in step (4), the soluble lithium salt is lithium acetate, lithium nitrate
One or both of.
Further, in desiccant gel the preparation method described in step (4), lithium and (Ni+Mn+Co) in the desiccant gel E
Molar ratio be 1.01-1.05.
Further, tertiary cathode material materials recycling described in step (5) is realized by high temperature sintering；It is described
The oxidizing atmosphere of high temperature sintering can be the mixed atmosphere of air, oxygen or air and oxygen；The sintering temperature is 750-
1000 DEG C, sintering time 10-20 hours.
A kind of reclaiming method of waste and old power lithium-ion battery tertiary cathode material of the present invention, with prior art phase
Than having the following beneficial effects:
(1) present invention adds lithium and transition metal element by sol-gel method, and combines high temperature sintering, makes waste and old dynamic
Tertiary cathode material structure and performance in power lithium ion battery are repaired, and the tertiary cathode material of high quality is obtained.
(2) a certain amount of fluxing agent is added during regenerating tertiary cathode material waste material in the present invention.Fluxing agent adds
Enter, can reduce the fusing point of reactant, solid-phase reactant can be made preferably to melt and react, while it is equal to obtain particle size
It is even；In addition, the fluxing agent chosen is the fluxing agent for being conducive to improve ternary material performance, it is further to avoid ternary material
Doping and cladding, shorten processing technology, prepare the tertiary cathode material with excellent cycling performance and high rate performance.
Detailed description of the invention
Fig. 1: the XRD diagram of 1 sample of embodiment.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer with reference to specific embodiments into
One step illustrates the present invention.It should be appreciated that described herein, specific examples are only used to explain the present invention, is not used to limit
The present invention.Any modification, equivalent substitution, improvement and etc. done within the spirit and principles of the present invention should be included in this
Within the protection scope of invention.
Embodiment 1:
After the waste and old ternary power lithium ion battery of new-energy automobile is thoroughly discharged, the recycling of tertiary cathode material is carried out
Regeneration, includes the following steps:
(1) extraction of power lithium-ion battery anode pole piece is discarded: by electric discharge completely discarded ternary power battery dismantling
After decladding, anode pole piece, cathode pole piece, diaphragm separation are separated from battery core.The anode pole piece is crushed, sieve
After point, the mixture A of tertiary cathode material, binder, conductive agent and a small amount of aluminium powder is obtained.
(2) purification of tertiary cathode material waste material: the mixture A that step (1) is obtained is placed in high-temperature incinerator,
Burning disposal is carried out under oxidizing atmosphere, after natural cooling, screening, obtains the mixed of tertiary cathode material and minute quantity aluminium
Close object B.By the mixture B be placed in concentration be 4mol/L sodium hydroxide solution in, remove a small amount of aluminium powder, through over cleaning,
It is centrifuged, is dry, after conjunction batch, the tertiary cathode material waste material C purified.
(3) lithium, the nickel, cobalt, manganese in ICP-AES method test waste material tertiary cathode material waste material C main element analysis: are utilized
Content, and calculate corresponding molar ratio.
(4) prepared by desiccant gel:
The zirconium tetrafluoride of 1 kilogram of ternary material waste material C, 20g 4a) are weighed, for use；
4b) according to the test result of step (3), according to nickel, cobalt, manganese in ternary material waste material C weighed in step (4a)
The 10% of content weighs the nickel acetate, manganese acetate, cobalt acetate of corresponding amount；
4c) the ratio for being 1:1.03 according to the molar ratio of nickel cobalt manganese total mole number and lithium in step (4a), step (4b)
Example, weighs the lithium acetate of corresponding amount；
4d) according to the total moles of weighed nickel acetate, manganese acetate, cobalt acetate, lithium acetate in step (4b), step (4c)
Number, weighs the citric acid of above-mentioned 2 times of total mole numbers；
4e) by step (4b), step (4c), the weighed nickel acetate of step (4d), manganese acetate, cobalt acetate, lithium acetate and
It is citric acid, soluble in water and be sufficiently mixed, blackish green solution is formed, the solution that metal ion total concentration is 4mol/l is configured to；
4f) under conditions of mechanical stirring, step (4a) weighed ternary is added to step (4e) the blackish green solution
Material waste C and zirconium tetrafluoride, and be vigorously stirred, are adjusted to uniform suspension, then adjusted with ammonium hydroxide the pH value of solution to
8, and it is heated to 80 DEG C and continuous evaporation water, obtain gelinite D；
4g) by the gelinite D, vacuum rotating is 8 hours dry at 110 DEG C, obtains xerogel body E.
(5) tertiary cathode material materials recycling: the xerogel body E that step (4) obtains is distributed into crucible, is then turned
Enter high temperature sintering furnace, be warming up to 920 DEG C with the rate of 2 DEG C/min, under oxidizing atmosphere, is sintered 20 hours.Then through being subcooled
But, to get the tertiary cathode material finished product to after regenerating after being crushed, sieving.
Structural characterization is carried out to tertiary cathode material prepared by embodiment 1 using x-ray powder diffraction instrument, as a result such as Fig. 1
It is shown.It can be seen that diffraction maximum and α-NaFeO2Kissing is right higher, and without dephasign peak, peak shape is more sharp, illustrates have very
Good layer structure.
Embodiment 2:
Embodiment 2 and step (1) in embodiment 1, step (2) and step (3) it is identical, difference is only that step (4) and step
Suddenly (5):
(4) prepared by desiccant gel:
1 ton of ternary material waste material C, 10 kilograms of lithium borates 4a) are weighed, for use；
4b) according to the test result of step (3), according to nickel, cobalt, manganese in ternary material waste material C weighed in step (4a)
The 15% of content weighs the nickel acetate, manganese acetate, cobalt acetate of corresponding amount；
4c) the ratio for being 1:1.02 according to the molar ratio of nickel cobalt manganese total mole number and lithium in step (4a), step (4b)
Example, weighs the lithium acetate of corresponding amount；
4d) according to the total moles of weighed nickel acetate, manganese acetate, cobalt acetate, lithium acetate in step (4b), step (4c)
Number, weighs the citric acid of above-mentioned 1.5 times of total mole numbers；
4e) by step (4b), step (4c), the weighed nickel acetate of step (4d), manganese acetate, cobalt acetate, lithium acetate and
It is citric acid, soluble in water and be sufficiently mixed, blackish green solution is formed, the solution that metal ion total concentration is 3mol/l is configured to；
4f) under conditions of mechanical stirring, step (4a) weighed ternary is added to step (4e) the blackish green solution
Material waste C and lithium borate, and be vigorously stirred, are adjusted to uniform suspension, the pH value of solution are then adjusted with ammonium hydroxide to 7,
And it is heated to 80 DEG C and continuous evaporation water, obtain gelinite D；
4g) by the gelinite D, vacuum rotating is 10 hours dry at 110 DEG C, obtains xerogel body E.
(5) tertiary cathode material materials recycling: the xerogel body E that step (4) obtains is distributed into saggar, is then turned
Enter high temperature sintering furnace, be warming up to 900 DEG C with the rate of 5 DEG C/min, under oxidizing atmosphere, is sintered 20 hours.Then through being subcooled
But, to get the tertiary cathode material finished product to after regenerating after being crushed, sieving.
Embodiment 3:
Embodiment 3 and step (1) in embodiment 1, step (2) and step (3) it is identical, difference is only that step (4) and step
Suddenly (5):
(4) prepared by desiccant gel:
5 tons of ternary material waste material C, 50 kilograms of aluminum trifluorides 4a) are weighed, for use；
4b) according to the test result of step (3), according to nickel, cobalt, manganese in ternary material waste material C weighed in step (4a)
The 20% of content weighs the nickel acetate, manganese acetate, cobalt acetate of corresponding amount；
4c) the ratio for being 1:1.05 according to the molar ratio of nickel cobalt manganese total mole number and lithium in step (4a), step (4b)
Example, weighs the lithium acetate of corresponding amount；
4d) according to the total moles of weighed nickel acetate, manganese acetate, cobalt acetate, lithium acetate in step (4b), step (4c)
Number, weighs the citric acid of above-mentioned 1.8 times of total mole numbers；
4e) by step (4b), step (4c), the weighed nickel acetate of step (4d), manganese acetate, cobalt acetate, lithium acetate and
It is citric acid, soluble in water and be sufficiently mixed, blackish green solution is formed, the solution that metal ion total concentration is 2mol/l is configured to；
4f) under conditions of mechanical stirring, step (4a) weighed ternary is added to step (4e) the blackish green solution
Material waste C and lithium borate, and be vigorously stirred, are adjusted to uniform suspension, then adjusted with ammonium hydroxide the pH value of solution to
7.5, it is heated to 80 DEG C and continuous evaporation water, obtains gelinite D；
4g) by the gelinite D, vacuum rotating is 10 hours dry at 110 DEG C, obtains xerogel body E.
(5) tertiary cathode material materials recycling: the xerogel body E that step (4) obtains is distributed into saggar, is then turned
Enter high temperature sintering furnace, be warming up to 880 DEG C with the rate of 3 DEG C/min, under oxidizing atmosphere, is sintered 20 hours.Then through being subcooled
But, to get the tertiary cathode material finished product to after regenerating after being crushed, sieving.
Claims (8)
1. a kind of reclaiming method of waste and old power lithium-ion battery tertiary cathode material, it is characterised in that, Bao Kuo such as lower Walk
It is rapid:
(1) discard the extraction of power lithium-ion battery anode pole piece: by electric discharge, completely discarded ternary power battery disassembles decladding
Afterwards, anode pole piece, cathode pole piece, diaphragm separation are separated from battery core.The anode pole piece is crushed, after screening,
Obtain the mixture A of tertiary cathode material, binder, conductive agent and a small amount of aluminium powder.
(2) purification of tertiary cathode material waste material: the mixture A that step (1) is obtained is placed in high-temperature incinerator, in oxygen
Change and carry out burning disposal under atmosphere, after natural cooling, screening, obtains the mixture B of tertiary cathode material Yu minute quantity aluminium.
By the mixture B be placed in concentration be 4-10mol/L sodium hydroxide solution in, remove a small amount of aluminium powder, through over cleaning, from
The heart, drying, after closing batch, the tertiary cathode material waste material C that is purified.
(3) tertiary cathode material waste material C main element analysis: in the tertiary cathode material waste material C that analysis testing procedure (3) obtains
Lithium, nickel, cobalt, manganese constituent content.
(4) prepared by desiccant gel:
Tertiary cathode material waste material C and fluxing agent after 4a) weighing a certain amount of step (2) purification；According to tertiary cathode material
The 0.5-5wt% of waste material C mass, weighs the fluxing agent of corresponding amount；
4b) according to the test result of step (3), according to nickel, cobalt, manganese content in ternary material waste material C weighed in step (4a)
5-20%, weigh the nickel acetate, manganese acetate, cobalt acetate of corresponding amount；
4c) the ratio for being 1:1.03 according to the molar ratio of nickel cobalt manganese total mole number and lithium in step (4a), step (4b) deducts
After lithium in step (4a) member positive material waste C, it is supplemented weighing the soluble lithium salt of corresponding amount；
4d) weigh the step (4b), nickel acetate in step (4c), manganese acetate, cobalt acetate, lithium acetate total mole number
The 1.5-2 times of citric acid measured；
4e) by step (4b), step (4c), the weighed nickel acetate of step (4d), manganese acetate, cobalt acetate, lithium acetate and lemon
It is sour, soluble in water and be sufficiently mixed, blackish green solution is formed, the solution that metal ion total concentration is 2-4mol/l is configured to；
4f) under conditions of mechanical stirring, step (4a) weighed ternary material is added to step (4e) the blackish green solution
Waste material C and fluxing agent, and be vigorously stirred, it is adjusted to uniform suspension, the pH value for then adjusting solution with ammonium hydroxide adds to 7-8
Heat obtains gelinite D to 60-100 DEG C and continuous evaporation water；
4g) by step (4f) the gelinite D, vacuum rotating is 6-10 hours dry at 80~150 DEG C, obtains xerogel body E；
(5) tertiary cathode material materials recycling: the xerogel body E that step (4g) obtains is distributed into crucible or saggar, then
It is transferred to high temperature sintering furnace, is warming up between 750-1000 DEG C with the rate of 2-5 DEG C/min, under oxidizing atmosphere, sintering 10-20 is small
When.Then to get the tertiary cathode material finished product arrived after regeneration after supercooling, broken, screening.
2. a kind of reclaiming method of waste and old power lithium-ion battery tertiary cathode material according to claim 1,
It is characterized in that, in the method for purification of step (2) the tertiary cathode material waste material, the oxidizing atmosphere can be air, oxygen
Or the mixed atmosphere of air and oxygen；The temperature of the high temperature incineration processing is between 200-600 DEG C, it is preferable that at burning
The temperature of reason is between 300-500 DEG C.
3. a kind of reclaiming method of waste and old power lithium-ion battery tertiary cathode material according to claim 1,
It is characterized in that, the main element analysis method of tertiary cathode material waste material described in step (3), can be chemical titration, ICP-
One of AES, AAS or a variety of.
4. a kind of reclaiming method of waste and old power lithium-ion battery tertiary cathode material according to claim 1,
It is characterized in that, desiccant gel preparation method described in step (4), the fluxing agent is selected from zirconium tetrafluoride, bifluoride magnesium, borontrifluoride
One of aluminium, boron oxide, boric acid, lithium metaborate, lithium borate are a variety of, and the fluxing agent dosage is the tertiary cathode material
The 0.1-5% of waste material C mass；Preferably, the dosage of the fluxing agent is the 0.5- of the tertiary cathode material waste material C mass
2%.
5. a kind of reclaiming method of waste and old power lithium-ion battery tertiary cathode material according to claim 1,
It is characterized in that, in desiccant gel the preparation method described in step (4), the soluble nickel salt, cobalt salt, manganese salt are respectively nickel, cobalt, manganese
One of nitrate, acetate, chlorate and sulfate corresponding to three kinds of metals is a variety of；The soluble nickel salt, cobalt
Salt, manganese salt total metal ion be the tertiary cathode material waste material in nickel cobalt manganese total mole number 5%-20% it
Between.
6. a kind of reclaiming method of waste and old power lithium-ion battery tertiary cathode material according to claim 1,
It is characterized in that, in desiccant gel the preparation method described in step (4), the soluble lithium salt is one of lithium acetate, lithium nitrate
Or two kinds.
7. a kind of reclaiming method of waste and old power lithium-ion battery tertiary cathode material according to claim 1,
It is characterized in that, in desiccant gel the preparation method described in step (4), the molar ratio of lithium and (Ni+Mn+Co) in the desiccant gel E
For 1.01-1.05.
8. a kind of reclaiming method of waste and old power lithium-ion battery tertiary cathode material according to claim 1,
It is characterized in that, tertiary cathode material materials recycling described in step (5) is realized by high temperature sintering；The high temperature sintering
Oxidizing atmosphere can be the mixed atmosphere of air, oxygen or air and oxygen；The sintering temperature is 750-1000 DEG C, sintering
Time 10-20 hour.
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| CN112194201A (en) * | 2020-05-08 | 2021-01-08 | 江苏载驰科技股份有限公司 | Method for recycling valuable metals of waste lithium ion batteries and regenerating ternary cathode materials |
| CN113636605A (en) * | 2021-07-07 | 2021-11-12 | 华中科技大学 | Physical repair method for completely-failed ternary positive electrode material under low-cost air condition |
| CN114361399A (en) * | 2022-01-12 | 2022-04-15 | 河北科技大学 | Lithium-supplement cathode material and preparation method thereof |
| CN114597534A (en) * | 2022-03-29 | 2022-06-07 | 西安交通大学 | Method for in-situ repairing of waste ternary lithium battery cathode material through supercritical water |
| CN115140785A (en) * | 2022-08-31 | 2022-10-04 | 湖南五创循环科技有限公司 | Method for recycling and reusing anode of waste lithium ion battery |
| CN115286246A (en) * | 2022-09-29 | 2022-11-04 | 天津包钢稀土研究院有限责任公司 | High-temperature energy-saving material prepared from nickel-hydrogen battery waste and preparation method thereof |
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| CN112194201A (en) * | 2020-05-08 | 2021-01-08 | 江苏载驰科技股份有限公司 | Method for recycling valuable metals of waste lithium ion batteries and regenerating ternary cathode materials |
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| CN113636605A (en) * | 2021-07-07 | 2021-11-12 | 华中科技大学 | Physical repair method for completely-failed ternary positive electrode material under low-cost air condition |
| CN114361399A (en) * | 2022-01-12 | 2022-04-15 | 河北科技大学 | Lithium-supplement cathode material and preparation method thereof |
| CN114597534A (en) * | 2022-03-29 | 2022-06-07 | 西安交通大学 | Method for in-situ repairing of waste ternary lithium battery cathode material through supercritical water |
| CN115140785A (en) * | 2022-08-31 | 2022-10-04 | 湖南五创循环科技有限公司 | Method for recycling and reusing anode of waste lithium ion battery |
| CN115286246A (en) * | 2022-09-29 | 2022-11-04 | 天津包钢稀土研究院有限责任公司 | High-temperature energy-saving material prepared from nickel-hydrogen battery waste and preparation method thereof |
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