CN115051058A - Method for recycling polyvinylidene fluoride and lithium cobaltate positive electrode material from waste lithium cobaltate battery - Google Patents
Method for recycling polyvinylidene fluoride and lithium cobaltate positive electrode material from waste lithium cobaltate battery Download PDFInfo
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract
The invention discloses a method for recovering polyvinylidene fluoride and regenerating a lithium cobaltate positive electrode material from waste lithium cobaltate batteries, which belongs to the technical field of waste lithium ion battery recovery, and is characterized in that a waste lithium cobaltate positive electrode plate is obtained by discharging and disassembling a lithium cobaltate battery, the waste lithium cobaltate positive electrode plate is treated by NMP to separate positive electrode waste materials and aluminum foils and recover PVDF, then mixing the positive electrode waste material with an organic carbon source, carrying out reduction roasting, then carrying out water leaching to separate lithium and cobalt, then obtaining lithium carbonate and cobaltosic oxide through evaporation crystallization and calcination treatment respectively, and finally mixing the obtained lithium carbonate and cobaltosic oxide according to a metering ratio to carry out reaction to obtain regenerated lithium cobaltate. And the obtained regenerated lithium cobaltate has high purity, excellent rate performance and excellent cycle stability.
Description
Technical Field
The invention relates to the technical field of lithium battery positive electrode material recovery, and particularly relates to a method for recovering polyvinylidene fluoride from waste lithium cobalt oxide batteries and regenerating lithium cobalt oxide positive electrode materials.
Background
Lithium ion batteries are important in overcoming the inherent intermittency of renewable energy sources and promoting the development of portable electronic devices, among which LiCoO 2 (LCO) has a high volumetric energy density and a high charge cut-off voltage, and is still dominant in the field of portable electronic devices, although it is expensive. However, with the rapid growth and short term renewal of electronic product consumption, a large number of spent LCO batteries are scrapped every year. On one hand, the waste LCO battery is rich in valuable metals Li and Co, and can create huge economic value by effectively recycling, thereby realizing the sustainable development of strategic resources. On the other hand, toxic electrolytes and heavy metals in these spent lithium ion batteries pose serious threats to human environment and health if not properly handled. Therefore, a clean and efficient waste LCO battery recycling way is sought, and the purpose of changing waste into valuable is imperative.
At present, the recovery process of the waste lithium ion battery can be divided into pyrometallurgical, hydrometallurgical and pyrometallurgical combined hydrometallurgical processes. The pyrometallurgy has the advantages of high efficiency, large treatment capacity, easy scale production and the like, and is widely applied in industry. However, difficulties with high energy consumption, high emissions, difficulty in recovering lithium from slag, etc., remain a current challenge for such technologies. Hydrometallurgy is the mainstream waste battery recycling process in China at present. In the hydrometallurgical process, LiCoO is prepared by using a large amount of strong acid to match with a reducing agent 2 Reduction ofIs Li + And Co 2+ Ions, in order to achieve the desired leaching efficiency, tend to keep the solid-to-liquid ratio at a low level during leaching. Subsequently, the Li is separated stepwise by solvent extraction + And Co 2+ . Thereby generating a large amount of acidic wastewater and causing additional cost for sewage treatment.
For example, chinese patent application No. CN 106868371B discloses a method for recovering a spent lithium cobalt oxide positive electrode material, which comprises removing an aluminum foil from the spent lithium cobalt oxide positive electrode material to obtain a spent lithium cobalt oxide positive electrode material, crushing the spent lithium cobalt oxide positive electrode material, adding hydrochloric acid or sulfuric acid to the spent lithium cobalt oxide positive electrode material using ferrous sulfate as a reducing agent to perform a chemical reaction, adding an inorganic base to neutralize the residual acid after the reaction is completed, and precipitating Fe 3+ . And filtering and separating the precipitate and the filtrate, and continuously adding inorganic base into the filtrate to adjust the pH value to 10.0-14.0 to precipitate cobalt, thereby separating lithium and cobalt. The process is complex, uses a large amount of acid and alkali, and has high cost and no environmental friendliness. Chinese patent application No. CN 106505270A discloses a method for recovering lithium and cobalt from waste lithium ion batteries, in which the waste pole pieces obtained by discharge disassembly are mixed with ammonium sulfate, high-temperature roasting is performed to obtain reduction roasting slag, vibration screening is performed to remove aluminum foil to obtain reduction slag containing lithium and cobalt, then sulfuric acid is used for leaching, sodium carbonate is used for adjusting the pH of the solution, and the precipitate is removed by filtering; adding sodium hydroxide into the obtained lithium and cobalt sulfate precipitate to obtain cobalt hydroxide precipitate, and reducing and roasting the cobalt hydroxide to obtain metal cobalt powder; and adding excessive lithium precipitating agent into the residual lithium-containing solution to obtain a lithium salt product. However, in the process, a large amount of ammonia gas is generated by decomposing ammonium sulfate, and the threat to environmental pollution is caused. The Chinese patent application with the application number of CN110079671A discloses a method for utilizing a gaseous reducing agent (H) 2 Natural gas, liquefied petroleum gas, coal gas and the like) to reduce and roast the crushed materials of the waste lithium ion batteries so as to recover valuable elements. However, in the process, a large amount of flammable and explosive gas is used at high temperature, so that great potential safety hazard is caused. The Chinese patent application with the application number of CN 111430829B discloses a method for regenerating and synthesizing a positive electrode material of a waste lithium ion battery by using a biomass material (corn stalks, rapeseed cakes, chaff, straws, sawdust, sorghum vinasse and the like) to reduce and roast the positive electrode materialA nickel-cobalt-manganese ternary cathode material. However, in the process, impurity elements such as Na, K, Ca, Mg and the like are introduced by using the biomass material, so that the difficulty in recovering high-purity valuable components is increased, and the anode material with excellent electrochemical performance is difficult to regenerate. Chinese patent application No. CN 111430829B discloses a method for recovering lithium from waste lithium ion batteries by using graphite negative electrode powder and the like as a reducing agent. However, the process is only limited to recycling lithium in the waste lithium ion battery, and does not fully utilize valuable resources to realize closed cycle use of resources.
Disclosure of Invention
Based on the above, the invention provides a method for recovering polyvinylidene fluoride from waste lithium cobaltate batteries and regenerating lithium cobaltate positive electrode materials, which comprises the steps of sequentially carrying out solvent soaking, reduction roasting, selective lithium leaching and calcining on disassembled electrode pole pieces to realize the cyclic regeneration of cobalt, lithium and PVDF in the lithium cobaltate positive electrode materials, thereby realizing the recovery of polyvinylidene fluoride from the waste lithium cobaltate batteries and the regeneration of the lithium cobaltate positive electrode materials and further realizing the closed cycle of the waste lithium cobaltate battery materials.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the method for recovering polyvinylidene fluoride and regenerating lithium cobaltate cathode materials from waste lithium cobaltate batteries comprises the following steps:
s1, preprocessing: discharging and disassembling a waste lithium cobaltate battery to obtain a waste lithium cobaltate positive pole piece, soaking the waste lithium cobaltate positive pole piece in an NMP (N-methyl pyrrolidone) solvent, heating, filtering and separating to obtain a filtrate, positive waste and an aluminum foil, evaporating and concentrating the filtrate, collecting gas and a crystallization product to respectively obtain NMP and PVDF (polyvinylidene fluoride);
s2, reduction roasting: mixing the anode waste with organic carbon, and carrying out reduction roasting in an inert atmosphere to obtain a roasted material;
s3, carrying out water leaching on the roasted material, and separating to obtain a lithium-rich solution and insoluble filter residues;
s4, introducing CO into the lithium-rich solution 2 And subjected to evaporative crystallization to obtain Li 2 CO 3 Powder; calcining the insoluble filter residue in air to obtain Co 3 O 4 Powder;
s5, obtaining Li in step S4 2 CO 3 Powder and Co 3 O 4 Mixing the powder according to a metering ratio, and calcining in air to obtain a regenerated lithium cobaltate positive electrode material;
wherein the organic carbon is at least one of glucose, sucrose, starch, maltose and betacyclodextrin.
In some embodiments, in step S2, the organic carbon is added in an amount of 5 to 20% by mass of the positive electrode waste.
In some embodiments, in step S2, the inert atmosphere is an argon atmosphere and/or a nitrogen atmosphere.
In some embodiments, in step S2, the baking temperature is 400 to 800 ℃.
In some embodiments, in step S2, the baking time is 0.5 to 3 hours.
In some embodiments, in step S3, the water-to-solid ratio is 10-100 g/L
In some embodiments, in step S3, the leaching time is 5-60 min.
In some embodiments, in step S4, the calcination temperature of the insoluble filter residue is 500 to 800 ℃.
In some embodiments, in step S4, the calcination time is 0.5 to 3.0 h.
In some embodiments, in step S5, the Li: the molar ratio of Co is 1:1.0 to 1.1.
In some embodiments, the calcination temperature in step S5 is 800-1200 ℃.
In some embodiments, in step S5, the calcination time is 2 to 10 hours.
In some embodiments, in step S1, the waste lithium cobaltate positive electrode piece is soaked in an NMP solvent and then heated to 60-100 ℃.
Hair brushIn the technical scheme, a cheap organic carbon source is innovatively adopted as a reducing agent, and the waste lithium cobaltate material is reduced and decomposed into soluble lithium cobaltate, an insoluble Co simple substance and CoO in the roasting process. The inventor finds that the high-efficiency separation of lithium and cobalt can be realized by simple water leaching, and meanwhile, the recovered Li is subjected to the method 2 CO 3 And Co 3 O 4 Regeneration of the prepared LiCoO 2 The cathode material has excellent rate performance and cycle stability. Specifically, the basic principle of the present invention is as follows:
in the reduction roasting process, at high temperature, organic carbon is pyrolyzed to form a carbon simple substance, the carbon simple substance and cobalt lithium molecules generate oxidation reduction reaction, lithium is converted into soluble salt, cobalt is converted into insoluble cobalt simple substance or cobalt oxide, and the main chemical reaction is as follows:
C+4LiCoO 2 ＝2Li 2 O+4CoO+CO 2 (g) (1)
C+2CoO＝2Co+CO 2 (g) (2)
CO 2 (g)+Li 2 O＝2Li 2 CO 3 (3)
lithium in the roasted material exists in the form of soluble lithium carbonate and lithium oxide, cobalt exists in the form of a cobalt simple substance or cobalt oxide, and the high-efficiency separation of the lithium and the cobalt can be realized by adopting simple water immersion. In the water logging process, lithium oxide reacts with water to generate a lithium hydroxide solution, lithium carbonate is soluble in water to form a lithium carbonate solution, a small amount of carbon dioxide is blown into the solution in the evaporation crystallization process after separation to convert the lithium hydroxide into the lithium carbonate, so that impurities in the lithium carbonate can be effectively reduced, the purity of the regenerated lithium carbonate is increased, and the reaction in the water logging process is as follows:
Li 1 O+H 2 O＝2L i OH (4)
2LiOH+Co 2 ＝Li 2 CO 2 +H 2 O (5)
the insoluble slag obtained by separation after water leaching is Co and CoO, and the insoluble slag is sintered in the air to generate Co 3 O 4 Then mixing Co with 3 O 4 With Li 2 CO 3 According to the measurementReacting in a specific mixing manner to obtain regenerated Li 2 CoO 2 The anode material realizes the recycling of Co and Li in the lithium cobaltate anode material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention can realize the comprehensive recycling of the lithium cobaltate cathode material through a simple process, and is different from the reaction of a large amount of reducing agents in the prior art.
(2) Acid/alkali is not needed in the process, the consumption of corrosive reagents and the working procedures of waste acid/alkali liquor treatment are avoided, impurity ions are not introduced, and the regeneration of high-purity lithium carbonate is simplified.
(3) The method can recover PVDF, cobalt and lithium in the waste lithium cobaltate electrode material, generates lithium carbonate and cobalt oxide with high purity, can be directly used for generating regenerated lithium cobaltate, simultaneously realizes the recycling of PVDF and NMP as a solvent, and realizes the comprehensive closed-loop recycling of the lithium cobaltate cathode material.
(4) The method of the invention has the advantages of safety, environmental protection, simple operation, low cost and high resource utilization rate, the primary recovery rate of lithium can reach more than 98 percent, and the recovery rate of cobalt can reach more than 99 percent.
Drawings
FIG. 1 is an XRD pattern of lithium cobaltate regenerated in example 1;
FIG. 2 is a charge-discharge curve at a 1C rate of lithium cobaltate regenerated in example 1;
FIG. 3 is an SEM photograph of the lithium cobaltate regenerated in example 2;
FIG. 4 is a graph showing the cycle performance at 1C rate of the lithium cobaltate regenerated in example 3;
fig. 5 is a charge/discharge curve at a 0.1C magnification of the lithium cobaltate regenerated in example 4.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
The comprehensive cyclic regeneration method of the waste lithium cobaltate battery comprises the following steps:
s1, discharging and disassembling the waste lithium cobaltate battery to obtain a waste lithium cobaltate positive plate; soaking the obtained waste lithium cobaltate positive plate in an NMP solvent, heating to 80 ℃ to completely separate a positive material from an aluminum foil, taking out the aluminum foil, and filtering to obtain filter residue as waste positive powder and filtrate as an NMP solution containing PVDF; the filtrate is evaporated and concentrated after being repeatedly utilized for many times, the generated gas is condensed and recovered to obtain an NMP solvent, and the evaporated and crystallized solid product is PVDF powder which can be recycled;
s2, taking 10g of the waste anode powder obtained in the step S1, adding 1g of glucose, fully and uniformly mixing, and roasting the mixture at 650 ℃ for 0.5h in an argon atmosphere to obtain roasted product;
s3, weighing 5g of the calcine obtained in the step S2, leaching the calcine for 0.5h by stirring with 100ml of deionized water, and filtering to respectively obtain a lithium-rich leaching solution and insoluble filter residues;
s4, blowing a small amount of carbon dioxide gas into the leaching solution, evaporating and crystallizing to obtain Li 2 CO 3 Powder; sintering insoluble filter residue in air at 800 ℃ for 0.5h to obtain Co 3 O 4 Mixing the materials;
s5, recovering Li 2 CO 3 And Co 3 O 4 According to Li: co is uniformly mixed according to the molar ratio of 1:1.05, calcined for 8 hours at 850 ℃ in air, and regenerated to obtain LiCoO 2 Positive electrode material。
By measurement and calculation by inductively coupled plasma emission spectroscopy (ICP), the water leaching rate of lithium is 98.2%, and the recovery rate of cobalt is 99.1%.
The regenerated lithium cobaltate positive electrode material was tested, and the test results are shown in fig. 1 and 2. Wherein, FIG. 1 shows the regenerated LiCoO of the present example 2 XRD pattern of positive electrode material, and FIG. 2 shows LiCoO obtained by regeneration 2 The charge-discharge curve of the cathode material at a rate of 1C. As shown in FIG. 1, XRD results showed that LiCoO was regenerated 2 The positive electrode material has a good crystal form and no impurity peak; as shown in FIG. 2, the electrochemical test results showed that the regenerated LiCoO was obtained 2 The specific discharge capacity of the cathode material under the rate of 1C reaches 156.9 mAh/g.
Example 2
The comprehensive cyclic regeneration method of the waste lithium cobaltate battery material comprises the following steps:
s1, discharging and disassembling the waste lithium cobaltate battery to obtain a waste lithium cobaltate positive plate; soaking the waste lithium cobaltate positive plate in an NMP solvent, heating to 80 ℃ to completely separate the positive material from the aluminum foil, taking out the aluminum foil, and filtering to obtain filter residue as waste positive powder and filtrate as an NMP solution containing PVDF; the filtrate is evaporated and concentrated after being repeatedly utilized for many times, the generated gas is condensed and recovered to obtain an NMP solvent, and the evaporated and crystallized solid product is PVDF powder;
s2, taking 10g of the waste anode powder, adding 2g of starch, fully and uniformly mixing, and roasting the mixture at 550 ℃ for 0.5h under the argon atmosphere to obtain roasted sand;
s3, weighing 5g of the calcine, and stirring and leaching the calcine for 1 hour by using 200ml of deionized water to obtain a lithium-rich leaching solution and insoluble filter residues;
s4, blowing a small amount of carbon dioxide gas into the leaching solution, evaporating and crystallizing to obtain Li 2 CO 3 Powder; sintering insoluble filter residue in air at 700 ℃ for 1h to obtain Co 3 O 4 Mixing the materials;
s5, recovering the Li 2 CO 3 And Co 3 O 4 According to Li: co is uniformly mixed according to the molar ratio of 1:1.03, calcined for 6 hours at the temperature of 900 ℃ in the air and regenerated to obtain LiCoO 2 And (3) a positive electrode material.
Through measurement and calculation by inductively coupled plasma emission spectroscopy (ICP), the water leaching rate of lithium is 98.6%, and the recovery rate of cobalt is 99.3%;
as shown in FIG. 3, SEM test results show that LiCoO regenerated in this example 2 The morphology of the anode material is irregular secondary particles with the size of 2-15 mu m and composed of primary particles.
Example 3
The comprehensive cyclic regeneration method of the waste lithium cobaltate battery material comprises the following steps:
s1, discharging and disassembling the waste lithium cobaltate battery to obtain a waste lithium cobaltate positive plate; soaking the waste lithium cobaltate positive plate in an NMP solvent, heating to 80 ℃ to completely separate the positive material from the aluminum foil, taking out the aluminum foil, and filtering to obtain filter residue as waste positive powder and filtrate as an NMP solution containing PVDF; the filtrate is evaporated and concentrated after being repeatedly utilized for many times, the generated gas is condensed and recovered to obtain an NMP solvent, and the evaporated and crystallized solid product is PVDF powder;
s2, taking 10g of the waste anode powder, adding 0.5g of cane sugar, fully and uniformly mixing, and roasting the mixture at 750 ℃ for 2h in a nitrogen atmosphere to obtain roasted sand;
s3, weighing 5g of the calcine, and stirring and leaching the calcine for 40min by using 150ml of deionized water to obtain a lithium-rich leaching solution and insoluble filter residues;
s4, blowing a small amount of carbon dioxide gas into the leaching solution, evaporating and crystallizing to obtain Li 2 CO 3 Sintering the powder and insoluble filter residue in air at 700 ℃ for 1h to obtain Co 3 O 4 Mixing the materials;
s5, recovering Li 2 CO 3 And Co 3 O 4 According to Li: co is uniformly mixed according to the molar ratio of 1:1.07, calcined for 10 hours at 800 ℃ in the air and regenerated to obtain LiCoO 2 And (3) a positive electrode material.
Through measurement and calculation by inductively coupled plasma emission spectroscopy (ICP), the water leaching rate of lithium is 97.6 percent, and the recovery rate of cobalt is 99.1 percent;
as shown in FIG. 4, the electrochemical test results showed that LiCoO was regenerated in this example 2 The capacity retention rate of the anode material is 97.8 percent under the condition of 1C multiplying power of 100 cycles.
Example 4
The comprehensive cyclic regeneration method of the waste lithium cobaltate battery material comprises the following steps:
s1, discharging and disassembling the waste lithium cobaltate battery to obtain a waste lithium cobaltate positive plate; soaking the waste lithium cobaltate positive plate in an NMP solvent, heating to 80 ℃ to completely separate the positive material from the aluminum foil, taking out the aluminum foil, and filtering to obtain filter residue as waste positive powder and filtrate as an NMP solution containing PVDF; the filtrate is evaporated and concentrated after being repeatedly utilized for many times, the generated gas is condensed and recovered to obtain an NMP solvent, and the evaporated and crystallized solid product is PVDF powder;
s2, taking 10g of the waste anode powder, adding 1.5g of cane sugar, fully and uniformly mixing, and roasting the mixture for 1h at 550 ℃ in a nitrogen atmosphere to obtain roasted sand;
s3, weighing 5g of the calcine, and stirring and leaching the calcine for 20min by using 200ml of deionized water to obtain a lithium-rich leaching solution and insoluble filter residues;
s4, blowing a small amount of carbon dioxide gas into the leaching solution, evaporating and crystallizing to obtain Li 2 CO 3 Sintering the powder and insoluble filter residue in air at 800 ℃ for 0.5h to obtain Co 3 O 4 Mixing the materials;
s5, recovering Li 2 CO 3 And Co 3 O 4 According to Li: co is uniformly mixed according to the molar ratio of 1:1.1, calcined for 10 hours at the temperature of 900 ℃ in the air, and then LiCoO is obtained through regeneration 2 And (3) a positive electrode material.
By measuring and calculating by using inductively coupled plasma emission spectroscopy (ICP), the water leaching rate of lithium is 97.9 percent, and the recovery rate of cobalt is 99.2 percent;
as shown in FIG. 5, the electrochemical test results showed that LiCoO was regenerated in this example 2 The specific discharge capacity of the cathode material at a multiplying power of 0.1C is 163.3 mAh/g.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. The method for recovering polyvinylidene fluoride and regenerating lithium cobaltate positive electrode materials from waste lithium cobaltate batteries is characterized by comprising the following steps of:
s1, preprocessing: discharging and disassembling a waste lithium cobaltate battery to obtain a waste lithium cobaltate positive pole piece, soaking the waste lithium cobaltate positive pole piece in an NMP solvent, heating, filtering and separating to obtain a filtrate, positive waste and an aluminum foil, evaporating and concentrating the filtrate, collecting gas and a crystallization product to respectively obtain NMP and PVDF;
s2, reduction roasting: mixing the anode waste with organic carbon, and carrying out reduction roasting in an inert atmosphere to obtain a roasted material;
s3, carrying out water leaching on the roasted material, and separating to obtain a lithium-rich solution and insoluble filter residues;
s4, introducing CO into the lithium-rich solution 2 And subjected to evaporative crystallization to obtain Li 2 CO 3 Powder; calcining the insoluble filter residue in air to obtain Co 3 O 4 Powder;
s5, Li obtained in step S4 2 CO 3 Powder and Co 3 O 4 Mixing the powder according to a metering ratio, and calcining in air to obtain a regenerated lithium cobaltate positive electrode material;
wherein the organic carbon is at least one of glucose, sucrose, starch, maltose and betacyclodextrin.
2. The method for recycling polyvinylidene fluoride and recycling lithium cobaltate positive electrode materials from the waste lithium cobaltate batteries according to claim 1, wherein in the step S2, the mass of the added organic carbon is 5-20% of that of the positive electrode waste materials.
3. The method for recycling polyvinylidene fluoride and recycling lithium cobaltate positive electrode materials from waste lithium cobaltate batteries according to claim 1, wherein in the step S2, the inert atmosphere is argon atmosphere and/or nitrogen atmosphere.
4. The method for recycling polyvinylidene fluoride and recycling lithium cobaltate positive electrode materials from the waste lithium cobaltate batteries according to claim 1, wherein in the step S2, the roasting temperature is 400-800 ℃; and/or the roasting time is 0.5-3 h.
5. The method for recycling polyvinylidene fluoride and recycling lithium cobaltate positive electrode materials from the waste lithium cobaltate batteries according to claim 1, wherein in the step S3, the water-to-solid ratio is 10-100 g/L; and/or the leaching time is 5-60 min.
6. The method for recovering polyvinylidene fluoride and regenerating a lithium cobaltate positive electrode material from the waste lithium cobaltate battery according to claim 1, wherein in the step S4, the calcining temperature of the insoluble filter residue is 500-800 ℃; and/or the calcining time is 0.5-3.0 h.
7. The method for recycling polyvinylidene fluoride and recycling lithium cobaltate positive electrode material from waste lithium cobaltate batteries according to claim 1, wherein in step S5, the ratio of Li: the molar ratio of Co is 1:1.0 to 1.1.
8. The method for recycling polyvinylidene fluoride and recycling lithium cobaltate positive electrode materials from the waste lithium cobaltate batteries according to claim 1, wherein in the step S5, the calcination temperature is 800-1200 ℃; and/or the calcining time is 2-10 h.
9. The method for recycling polyvinylidene fluoride and recycling lithium cobaltate positive electrode materials from waste lithium cobaltate batteries according to claim 1, wherein in step S1, the waste lithium cobaltate positive electrode piece is soaked in NMP solvent and then heated to 60-100 ℃.
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