CN112490527B - Method for regenerating lithium ion battery positive electrode material, positive electrode material and lithium ion battery - Google Patents
Method for regenerating lithium ion battery positive electrode material, positive electrode material and lithium ion battery Download PDFInfo
- Publication number
- CN112490527B CN112490527B CN202011395335.XA CN202011395335A CN112490527B CN 112490527 B CN112490527 B CN 112490527B CN 202011395335 A CN202011395335 A CN 202011395335A CN 112490527 B CN112490527 B CN 112490527B
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- lithium
- electrode material
- ion battery
- lithium ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 65
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title abstract description 33
- 230000001172 regenerating effect Effects 0.000 title abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 64
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 48
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 238000011069 regeneration method Methods 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000010926 waste battery Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 11
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 23
- 238000011084 recovery Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 10
- 230000008929 regeneration Effects 0.000 abstract description 10
- 239000002699 waste material Substances 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 3
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 239000010405 anode material Substances 0.000 description 20
- 239000010406 cathode material Substances 0.000 description 15
- 238000002156 mixing Methods 0.000 description 10
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- OIAKUYQUAMNLMV-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Fe+2].[Li+].[Al+3].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Fe+2].[Li+].[Al+3].P(=O)([O-])([O-])[O-] OIAKUYQUAMNLMV-UHFFFAOYSA-H 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- -1 nickel-cobalt-manganese-aluminum Chemical group 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 1
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明提供了一种锂离子电池正极材料再生方法、正极材料和锂离子电池，该再生方法包括以下步骤：将废电池的正极片直接粉碎后得到粉末材料；将粉末材料煅烧得到前驱体；将前驱体与锂源混合后球磨均匀，然后煅烧，制得可以再次利用的锂离子电池正极材料。本发明的再生方法，避免了废旧锂离子电池的正极活性材料与集流体的分离工序，正极片中铝集流体经过煅烧，与其他金属共同组成新型多元正极材料，铝的掺杂不仅减少传统正极材料回收中复杂的剥离工序，而且铝掺杂进入再生正极材料中可以提高正极材料结构稳定性；该方法提出了极其简易的废旧电池材料的回收和再生工艺，实现电池材料的低成本、大规模、高回收率再生，有良好的经济收益。
The invention provides a method for regenerating a positive electrode material of a lithium ion battery, a positive electrode material and a lithium ion battery. The regeneration method comprises the following steps: directly pulverizing the positive electrode sheet of a waste battery to obtain powder material; calcining the powder material to obtain a precursor; The precursor is mixed with a lithium source, and then ball-milled uniformly, and then calcined to obtain a lithium-ion battery positive electrode material that can be reused. The regeneration method of the invention avoids the separation process of the positive electrode active material and the current collector of the waste lithium ion battery. The aluminum current collector in the positive electrode sheet is calcined to form a new multi-component positive electrode material together with other metals, and the doping of aluminum not only reduces the traditional positive electrode material The complex stripping process in material recycling, and the doping of aluminum into the recycled positive electrode material can improve the structural stability of the positive electrode material; this method proposes an extremely simple recycling and regeneration process for waste battery materials, and realizes low-cost, large-scale battery materials. , High recovery rate regeneration, good economic benefits.
Description
Technical Field
The invention relates to the technical field of lithium ion battery material recovery and restoration regeneration, in particular to a lithium ion battery anode material regeneration method, an anode material and a lithium ion battery.
Background
With the rapid increase of the application of the lithium ion battery, the problem of processing the waste lithium ion battery is gradually highlighted. The waste lithium ion battery contains a large amount of valuable metal resources, and whether the recovery technology is excellent or not directly influences the continuous development of the lithium ion battery industry. The current lithium ion battery anode material mainly comprises: nickel cobalt manganese ternary, lithium iron phosphate and lithium cobaltate. At present, the recovery of the anode of the lithium ion battery mainly comprises dry recovery and wet recovery; the dry recovery is to drop active substances from a current collector by a physical method to obtain a precursor and then recover metal elements, or to add lithium sources with corresponding mass according to the content and proportion of each metal in the precursor and to perform high-temperature calcination to obtain a target product. Mainly through a physical separation method and a high-temperature pyrolysis method, other chemical reactions are not performed, but the simple physical separation effect is poor, the separation degree is low, and the time consumption is long. The wet recovery technology is complex in process, and the wet method takes various acid-base solutions as transfer media to transfer metal ions from electrode materials into leachate, and extracts metal elements from the solution by utilizing various chemical reactions and physical and chemical separation means. At present, the recovery of the lithium battery positive electrode material is all endeavored to remove the aluminum foil current collector and other auxiliary materials in the positive electrode plate so as to remove unnecessary impurities and further obtain the positive electrode recovery components with higher purity. Therefore, in order to avoid the metal and impurities from being separated out, the pH value of the solution needs to be controlled in the metal recovery process, the control conditions in the recovery process are increased, a large amount of reaction materials and reagents need to be consumed in the complex process flow and reaction, and the recovery cost is increased. Most of the prior art needs to separate the current collector from the active material, and the process for separating the current collector is complex, so that the separation effect is low, and the recovery cost of the material can be greatly improved.
Based on the current situation of recycling lithium ion cathode materials in the prior art, improvement is needed, the recycling process is simplified, the production procedures of the materials are greatly reduced, the improvement of the recycling process of the lithium ion battery is realized, and economic benefits are realized.
Disclosure of Invention
In view of the above, the present invention provides a method for regenerating a positive electrode material of a lithium ion battery, a positive electrode material and a lithium ion battery, so as to solve the above problems or at least partially solve the above problems.
In a first aspect, the present invention provides a method for regenerating a lithium ion battery cathode material, comprising the following steps:
crushing the positive plate of the waste battery to obtain a powder material;
calcining the powder material at 490-520 ℃ for 1-2 h to obtain a precursor;
and mixing the precursor with a lithium source, uniformly ball-milling, and calcining to complete the regeneration of the anode material.
Optionally, the lithium ion battery cathode material regeneration method specifically includes: calcining for 4-6 hours at 490-520 ℃, and then calcining for 10-20 hours at 600-1000 ℃.
Optionally, in the method for regenerating the positive electrode material of the lithium ion battery, the positive electrode material in the positive electrode plate of the waste battery includes one of a lithium iron phosphate material, a nickel-cobalt-manganese ternary material, and a lithium cobaltate material.
Optionally, in the method for regenerating the positive electrode material of the lithium ion battery, the recovered positive electrode material contains a doped aluminum component, and the aluminum comes from an aluminum current collector.
Optionally, in the method for regenerating a positive electrode material of a lithium ion battery, the lithium source includes lithium carbonate or lithium hydroxide.
Optionally, in the method for regenerating the lithium ion battery cathode material, the ratio of the sum of the amounts of the metal elements in the precursor to the amount of the lithium source is 1: 0.5-1.5.
Optionally, in the method for regenerating the lithium ion battery positive electrode material, the positive electrode sheet of the waste battery is placed in a ball mill and crushed for 30-60 min to obtain the powder material.
Optionally, in the method for regenerating the lithium ion battery anode material, the precursor and a lithium source are mixed and then placed in a ball mill for ball milling for 30-60 min.
In a second aspect, the invention also provides a positive electrode material prepared by the regeneration method.
In a third aspect, the invention also provides a lithium ion battery, which comprises the cathode material.
Compared with the prior art, the method for regenerating the lithium ion battery anode material has the following beneficial effects:
(1) the method for regenerating the lithium ion battery anode material uses the scrapped lithium ion battery anode plate, directly calcines the anode plate crushed material to obtain the powder material LiaMAlxO2(a < 1), and then adding a lithium source to perform secondary sintering, namely completing the regeneration of the lithium ion battery material, and obtaining the aluminum-doped positive electrode material; by the regeneration method, the separation of the anode active material and the current collector of the waste lithium ion battery is avoided, aluminum is oxidized into trivalent through high temperature and is lithiated together with other metals to form a novel multi-element anode material, the oxidation of trivalent aluminum is weaker than that of other metal ions, the anode active material is prevented from oxidizing electrolyte, the stability of the anode material is improved, and lithium-containing aluminum oxide has excellent lithium ion conductivity and conductivity; the aluminum foil is doped into the active material to form a novel multi-element anode material battery, the material after impurity removal is calcined at high temperature to supplement lithium, and the regenerated multi-element anode material is synthesized, so that the separation and a large number of reaction process are omitted, the conductivity and structural stability of the material are effectively improved, the process flow is simpler, the recovery rate is high, and good economic benefits are realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a flow chart of the preparation process of the method for regenerating the lithium ion battery anode material of the present invention;
FIG. 2 is an XRD spectrum of the Ni-Co-Mn ternary material in the waste battery used in example 1 of the present invention;
fig. 3 is an XRD chart of the aluminum-doped cathode material prepared by the regeneration method of example 1 according to the present invention;
FIG. 4 is a charge-discharge curve diagram of a lithium ion battery assembled by the Al-doped Ni-Co-Mn-Li positive electrode material prepared by the regeneration method in example 1;
fig. 5 is a cycle curve diagram of a lithium ion battery assembled by the positive electrode material prepared by the regeneration method in example 1;
FIG. 6 is a graph showing the charging and discharging curves of a lithium ion battery assembled from the aluminum-doped lithium cobalt oxide cathode material prepared by the regeneration method in example 2 according to the present invention;
fig. 7 is a cycle curve diagram of a lithium ion battery assembled from the positive electrode material prepared by the regeneration method in example 2 according to the present invention.
Fig. 8 is a charge-discharge curve diagram of a lithium ion battery assembled by the aluminum-doped lithium iron phosphate positive electrode material prepared by the regeneration method in example 3 according to the present invention;
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The invention provides a method for regenerating a lithium ion battery anode material, which comprises the following steps as shown in figure 1:
s1, crushing the positive plate of the waste battery to obtain a powder material;
s2, calcining the powder material at 490-520 ℃ for 1-2 h to obtain a precursor;
and S3, mixing the precursor with a lithium source, uniformly ball-milling, and calcining to complete the regeneration of the anode material.
In the present embodiment, the positive electrode sheet of the waste battery includes an active material, a positive electrode material, a binder, a conductive agent, an aluminum current collector, and the like. The binder is PVDF, the conductive agent adopts a Super-P material, and the active substances are as follows: adhesive: the ratio of the conductive agent is 8:1: 1. The positive electrode material in the positive plate of the waste battery comprises one of lithium iron phosphate, nickel-cobalt-manganese ternary, lithium cobaltate and the like;
in the embodiment of the present application, the lithium source is a lithium-containing compound, and the specific lithium source is lithium carbonate, lithium hydroxide, or the like.
Specifically, in this embodiment of the present application, S1 specifically includes: and (3) disassembling the waste battery to obtain a positive plate, and then placing the positive plate in a ball mill to be crushed for 30min to obtain a powder material.
Specifically, in this embodiment of the present application, S2 specifically includes: and calcining the powder material at 500 ℃ for 2h, and removing impurities such as a binder, conductive carbon black and the like in the powder material to obtain a precursor.
Specifically, in this embodiment of the present application, S3 specifically includes: and mixing the precursor with a lithium source, placing the mixture in a ball mill for ball milling for 30min, uniformly mixing, calcining at 500 ℃ for 5h, and calcining at 800 ℃ for 15h to obtain the regenerated lithium ion cathode material.
Specifically, in S3, the ratio of the sum of the amounts of the metal elements in the precursor to the amount of the lithium source material is 1:0.5 to 1.5, specifically, if the positive electrode material in the positive electrode sheet is lithium iron phosphate, the metal elements in the precursor are Fe and Al, and the ratio of the sum of the amounts of the Fe and Al to the amount of the Li material in the lithium source ((Fe + Al): Li) is 1:0.5 to 1.5; if the positive electrode material in the positive electrode plate is a nickel-cobalt-manganese ternary material, the metal elements in the precursor are Ni, Co, Mn and Al, and the ratio of the sum of the mass of the Ni, Co, Mn and Al to the mass of the Li in the lithium source ((Ni + Co + Mn + Al): Li) is 1 (0.5-1.5); when the positive electrode material in the positive electrode sheet is a lithium cobaltate material, the metal elements in the precursor are Co and Al, and the ratio of the sum of the amounts of Co and Al to the amount of Li in the lithium source ((Co + Al): Li) is 1 (0.5 to 1.5).
Specifically, in the positive plate, the positive material is a nickel-cobalt-manganese ternary material, the lithium source is lithium carbonate, and the ratio of the sum of the amounts of metal element substances in the precursor to the amount of lithium in the lithium source is 1: 1.
The scrapped positive plate (including active material, positive material, binder, conductive agent, aluminum current collector and the like) of the lithium ion battery is used in the application, and the broken material of the positive plate is directly carried outCalcining to obtain powder material LiaMAlxO2(a < 1), and adding a lithium source to perform secondary sintering to complete the regeneration of the lithium ion battery material and obtain the aluminum-doped positive electrode material comprising aluminum lithium iron phosphate (LiAl)xFePO4) Lithium aluminum cobaltate (LiCoAl)xO2) Quaternary nickel-cobalt-manganese-aluminum (LiNiCoMnAl)xO2) A material; by the regeneration method, the separation of the positive active material and the current collector of the waste lithium ion battery is avoided, and aluminum is oxidized into trivalent through high temperature and is lithiated together with other metals to form a novel multi-element positive material; the aluminum foil is doped into the active material to form a novel multi-element anode material battery, the material after impurity removal is calcined at high temperature to supplement lithium, and the regenerated multi-element anode material is synthesized, so that the separation and a large number of reaction process are omitted, the conductivity and structural stability of the material are effectively improved, the process flow is simpler, the recovery rate is high, and good economic benefits are realized.
At present, one of the existing lithium ion batteries is a nickel-cobalt-aluminum ternary battery, which is widely applied to the field of lithium ion power batteries, so that aluminum element can be used as one of the positive electrode material components. Therefore, the aluminum-containing cathode material prepared by reducing the stripping process of the current collector has important commercial application significance, can greatly solve the pain point in the existing battery material recovery process, namely artificially increasing the stripping and aluminum removing processes, and realizes large-scale and low-cost battery material regeneration and recovery.
Based on the same invention concept, the invention also provides a positive electrode material prepared by the preparation method.
Based on the same inventive concept, the invention also provides a lithium battery which comprises the prepared cathode material.
Example 2
The invention provides a method for regenerating a lithium ion battery anode material, which comprises the following steps as shown in figure 1:
s1, crushing the positive plate of the waste battery to obtain a powder material;
s2, calcining the powder material at 490-520 ℃ for 1-2 h to obtain a precursor;
and S3, mixing the precursor with a lithium source, uniformly ball-milling, and calcining to complete the regeneration of the anode material.
Specifically, in this embodiment of the present application, S1 specifically includes: and (3) disassembling the waste battery to obtain a positive plate, and then placing the positive plate in a ball mill to be crushed for 30min to obtain a powder material.
Specifically, in this embodiment of the present application, S2 specifically includes: and calcining the powder material at 500 ℃ for 2h, and removing impurities such as a binder, conductive carbon black and the like in the powder material to obtain a precursor.
Specifically, in this embodiment of the present application, S3 specifically includes: and mixing the precursor with a lithium source, placing the mixture in a ball mill for ball milling for 30min, uniformly mixing, calcining at 500 ℃ for 5h, and calcining at 800 ℃ for 15h to obtain the regenerated lithium ion cathode material.
Specifically, in S3, in the positive electrode sheet of the present application, the positive electrode material is lithium cobaltate, the lithium source is lithium carbonate, and the ratio of the sum of the amounts of the respective metal element substances in the precursor to the amount of lithium in the lithium source is 1:1, that is, if the metal elements in the precursor are Co and Al, the ratio of the sum of the amounts of Co and Al to the amount of Li in the lithium source ((Co + Al): Li) is 1: 1.
Based on the same invention concept, the invention also provides a positive electrode material prepared by the preparation method.
Based on the same inventive concept, the invention also provides a lithium battery which comprises the prepared cathode material.
Example 3
The invention provides a method for regenerating a lithium ion battery anode material, which comprises the following steps as shown in figure 1:
s1, directly crushing the lithium iron phosphate positive plate of the waste battery to obtain a powder material;
s2, calcining the powder material at 490-520 ℃ for 1-2 h to obtain a precursor;
and S3, mixing the precursor with a lithium source, uniformly ball-milling, and calcining to complete the regeneration of the anode material, thereby obtaining the lithium aluminum iron phosphate material.
Specifically, in this embodiment of the present application, S1 specifically includes: and (3) disassembling the waste battery to obtain a positive plate, and then placing the positive plate in a ball mill to be crushed for 30min to obtain a powder material.
Specifically, in this embodiment of the present application, S2 specifically includes: and calcining the powder material at 500 ℃ for 2h, and removing impurities such as a binder, conductive carbon black and the like in the powder material to obtain a precursor.
Specifically, in this embodiment of the present application, S3 specifically includes: and mixing the precursor with a lithium source, placing the mixture in a ball mill for ball milling for 30min, uniformly mixing, calcining at 500 ℃ for 5h, and calcining at 900 ℃ for 24h to obtain the regenerated lithium ion cathode material.
Specifically, in S3, in the positive electrode sheet of the present application, the positive electrode material is lithium iron phosphate, the lithium source is lithium carbonate, and the ratio of the sum of the amounts of the respective metal element substances in the precursor to the amount of lithium in the lithium source is 1:1, that is, if the metal elements in the precursor are Fe and Al, the ratio of the sum of the amounts of the Fe and Al substances to the amount of Li in the lithium source ((Fe + Al): Li) is 1: 1.
Based on the same invention concept, the invention also provides a positive electrode material prepared by the preparation method.
Based on the same inventive concept, the invention also provides a lithium battery which comprises the prepared cathode material.
XRD patterns of the nickel-cobalt-manganese ternary material in the waste battery used in example 1 and the positive electrode material prepared by the regeneration method in example 1 were respectively tested, and the results are shown in fig. 2 and fig. 3. As can be seen from fig. 2 and 3, fig. 2 shows that after the ternary cathode material undergoes several electrochemical processes, the structure of the material is significantly changed, and therefore, the capacity is attenuated. Fig. 3 shows that the recovery of the doped aluminum is good, and the layered crystal structure of the nickel-cobalt-manganese material is not affected by the doping of the aluminum.
Assembling the positive electrode material prepared by the regeneration method in the embodiment 1 into a lithium ion battery; the charging and discharging curves of the lithium ion battery are tested, and the result is shown in fig. 4; the cycle curve of the lithium ion battery was tested, and the results are shown in fig. 5; it can be known from fig. 4 that the quaternary material obtained by co-regenerating and calcining the waste nickel cobalt lithium manganate ternary material and the aluminum current collector can realize normal charging and discharging, the voltage is high, and the recovered electrode material has stable electrochemical performance as can be known from fig. 5.
Assembling the positive electrode material prepared by the regeneration method in the embodiment 2 into a lithium ion battery; the charging and discharging curves of the lithium ion battery are tested, and the result is shown in fig. 6; the cycling curve of the lithium ion battery was tested and the results are shown in fig. 7; from fig. 6, it can be seen that the lithium cobalt aluminate positive electrode material obtained by doping the aluminum current collector into the lithium cobalt aluminate positive electrode material can exhibit higher charge and discharge voltages and 120mAh g-1As can be seen from fig. 7, the regenerated lithium cobalt aluminate had good charge/discharge stability.
Assembling the positive electrode material prepared by the regeneration method in the embodiment 3 into a lithium ion battery; the charging and discharging curves of the lithium ion battery are tested, and the result is shown in fig. 8; from fig. 8, it can be seen that the aluminum current collector is doped into the lithium iron phosphate positive electrode material to obtain the aluminum-doped lithium iron phosphate positive electrode material, and the material can show higher charging and discharging voltage and show 110mAh g-1The aluminum material does not change the structure of the lithium iron phosphate according to the analysis of the charge-discharge curve, and the capacity performance is better.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011395335.XA CN112490527B (en) | 2020-12-03 | 2020-12-03 | Method for regenerating lithium ion battery positive electrode material, positive electrode material and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011395335.XA CN112490527B (en) | 2020-12-03 | 2020-12-03 | Method for regenerating lithium ion battery positive electrode material, positive electrode material and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112490527A CN112490527A (en) | 2021-03-12 |
| CN112490527B true CN112490527B (en) | 2022-04-01 |
Family
ID=74939024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011395335.XA Active CN112490527B (en) | 2020-12-03 | 2020-12-03 | Method for regenerating lithium ion battery positive electrode material, positive electrode material and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112490527B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113193188A (en) * | 2021-04-30 | 2021-07-30 | 云南脉冲科技有限公司 | Quaternary positive electrode material of sodium-ion battery and preparation method thereof |
| CN114068909B (en) * | 2021-11-10 | 2023-03-28 | 中南大学 | Method for regenerating NCMA (non-volatile memory) anode material by using retired NCM anode material |
| CN114572955B (en) * | 2022-03-24 | 2023-06-13 | 广东光华科技股份有限公司 | Battery-grade aluminum-containing ferric phosphate and preparation method thereof, lithium iron phosphate positive electrode material and preparation method thereof, and battery |
| CN114671424B (en) * | 2022-03-28 | 2023-04-11 | 东莞理工学院 | Method for regenerating lithium ion battery positive electrode material, positive electrode material and lithium ion battery |
| CN115172924B (en) * | 2022-07-22 | 2023-12-15 | 浙江大学 | Recycling and repairing method of lithium ion battery anode material |
| CN115632189A (en) * | 2022-11-22 | 2023-01-20 | 株洲冶炼集团股份有限公司 | A method for pretreatment and recycling of non-liquid-injected lithium iron phosphate waste pole pieces |
| CN116315216B (en) * | 2023-02-09 | 2024-02-13 | 湖南金凯循环科技股份有限公司 | Regeneration method of waste ternary material |
| CN116404286A (en) * | 2023-03-06 | 2023-07-07 | 广东环境保护工程职业学院 | A method for directly regenerating and preparing high-performance lithium-ion cathode materials |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004349210A (en) * | 2003-05-26 | 2004-12-09 | Toyota Motor Corp | Method for regenerating positive electrode active material for lithium secondary battery |
| JP2012193424A (en) * | 2011-03-17 | 2012-10-11 | Shinkoo Flex:Kk | Method for recovering manganese alloy from manganese oxide waste |
| CN106450555A (en) * | 2016-11-24 | 2017-02-22 | 荆门市格林美新材料有限公司 | Method for reparative regeneration of lithium cobalt oxide anode material in waste batteries |
| CN108878837A (en) * | 2018-06-28 | 2018-11-23 | 山东理工大学 | The method for preparing the modified tertiary cathode material of lithium aluminate based on waste lithium cell positive electrode |
| CN109755539A (en) * | 2019-02-21 | 2019-05-14 | 湖南邦普循环科技有限公司 | Utilize the method for lithium ion cell anode waste production aluminium doping ternary precursor |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4491085B2 (en) * | 1999-06-01 | 2010-06-30 | 多摩化学工業株式会社 | Method for recovering positive electrode material from waste secondary battery and method for producing non-aqueous electrolyte secondary battery using the same |
| WO2011079409A1 (en) * | 2009-12-28 | 2011-07-07 | 深圳市雄韬电源科技股份有限公司 | Method of recycling and reusing spent lithium iron phosphate power battery |
| US8807466B2 (en) * | 2011-06-06 | 2014-08-19 | Raw Materials Company Inc. | Method and system for reclamation of battery constituents |
| CN111403695B (en) * | 2019-11-11 | 2022-10-14 | 余姚市鑫和电池材料有限公司 | Preparation method of carbon-aluminum-coated lithium iron phosphate positive electrode material |
| CN111370801B (en) * | 2020-03-03 | 2021-03-23 | 湖南雅城新材料有限公司 | Method for recovering waste lithium iron phosphate positive plate |
-
2020
- 2020-12-03 CN CN202011395335.XA patent/CN112490527B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004349210A (en) * | 2003-05-26 | 2004-12-09 | Toyota Motor Corp | Method for regenerating positive electrode active material for lithium secondary battery |
| JP2012193424A (en) * | 2011-03-17 | 2012-10-11 | Shinkoo Flex:Kk | Method for recovering manganese alloy from manganese oxide waste |
| CN106450555A (en) * | 2016-11-24 | 2017-02-22 | 荆门市格林美新材料有限公司 | Method for reparative regeneration of lithium cobalt oxide anode material in waste batteries |
| CN108878837A (en) * | 2018-06-28 | 2018-11-23 | 山东理工大学 | The method for preparing the modified tertiary cathode material of lithium aluminate based on waste lithium cell positive electrode |
| CN109755539A (en) * | 2019-02-21 | 2019-05-14 | 湖南邦普循环科技有限公司 | Utilize the method for lithium ion cell anode waste production aluminium doping ternary precursor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112490527A (en) | 2021-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112490527B (en) | Method for regenerating lithium ion battery positive electrode material, positive electrode material and lithium ion battery | |
| CN112374553B (en) | Method for recycling and regenerating retired lithium ion battery anode material | |
| US10189083B2 (en) | Method for recycling electrode materials of lithium ion batteries | |
| CN109546254B (en) | Treatment method of waste nickel cobalt lithium manganate ion battery positive electrode material | |
| CN112142029B (en) | Method for repairing and regenerating anode material of waste lithium iron phosphate battery | |
| CN111270072B (en) | Recycling method of waste lithium iron phosphate battery positive electrode material | |
| CN110061225B (en) | Single-crystal high-capacity nickel cobalt lithium manganate positive electrode material and preparation method thereof | |
| CN115472948B (en) | A method for regenerating sodium positive electrode material using waste lithium manganate | |
| CN114242968A (en) | Carbon-coated sodium iron fluorophosphate material and preparation method and application thereof | |
| CN110526301B (en) | A method for reproducing the failed lithium cobalt oxide structure of the positive electrode of a lithium battery | |
| CN112707447A (en) | Method for recycling and regenerating anode material from waste lithium cobalt oxide battery | |
| WO2023060992A1 (en) | Method for synthesizing high-safety positive electrode material by recycling positive electrode leftover materials, and application | |
| CN111009699A (en) | Method for recycling lithium manganate waste battery | |
| CN115676794A (en) | Co-precipitation method and application of lithium manganese iron phosphate cathode material | |
| CN113582254A (en) | Layered positive electrode material and preparation method and application thereof | |
| WO2023155544A1 (en) | Preparation method for polyanionic positive electrode material | |
| WO2023040010A1 (en) | Method for repairing cathode material of spent lithium ion battery | |
| CN117712544B (en) | Resource utilization method of waste lithium iron phosphate battery | |
| CN112777648A (en) | High-performance cathode material regenerated by simple solid phase recovery method and preparation method thereof | |
| CN117199598A (en) | Regeneration method for treating waste lithium ion battery cathode material by pyrolysis-roasting two-stage method | |
| CN117096486A (en) | Repairing and regenerating method for waste lithium ion battery anode material | |
| CN113948788B (en) | Lithium cobalt oxide positive electrode material and regeneration and repair method and application thereof | |
| CN113428905B (en) | Method for recycling waste lithium cobaltate battery | |
| CN115275415A (en) | A method for recovering lithium from decommissioned lithium batteries and regenerating cathode materials | |
| CN113943021A (en) | Regenerated lithium cobaltate and repairing method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |