阅读说明：本技术 正极材料及其制备方法、正极及全固态锂离子电池 (Positive electrode material, preparation method thereof, positive electrode and all-solid-state lithium ion battery ) 是由 康飞宇 马家宾 贺艳兵 史沛然 陈立坤 凌华金 郝晓鸽 于 2021-04-01 设计创作，主要内容包括：一种正极材料,含有活性材料、粘结剂、电子导电剂、及填料,所述填料为锆酸镧、及锆酸镧锂中的至少一种,所述锆酸镧的晶体结构内富含有氧空位,所述锆酸镧锂的晶体结构内富含有氧空位,所述锆酸镧锂的表面具有氧缺陷。本发明还提供一种正极材料的制备方法、正极、及全固态锂离子电池。本发明提供的应用该正极材料的全固态锂离子电池具有离子电导率高、和电荷转移能力强的优点。(A positive electrode material contains an active material, a binder, an electron conductive agent, and a filler, wherein the filler is at least one of lanthanum zirconate and lanthanum lithium zirconate, oxygen vacancies are enriched in the crystal structure of the lanthanum lithium zirconate, and the surface of the lanthanum lithium zirconate has oxygen defects. The invention also provides a preparation method of the cathode material, a cathode and an all-solid-state lithium ion battery. The all-solid-state lithium ion battery using the cathode material provided by the invention has the advantages of high ionic conductivity and strong charge transfer capability.)

1. The positive electrode material is characterized by comprising an active material, a binder, an electron conductive agent, and a filler, wherein the filler is at least one of lanthanum zirconate and lanthanum lithium zirconate, oxygen vacancies are enriched in the crystal structure of the lanthanum lithium zirconate, and the surface of the lanthanum lithium zirconate has oxygen defects.

2. The cathode material according to claim 1, wherein the lanthanum zirconate is in the form of a one-dimensional nanowire having a diameter of 100nm to 300 nm; and/or

The form of the lanthanum lithium zirconate is a one-dimensional nanowire, and the diameter of the one-dimensional nanowire is 100 nm-300 nm.

3. The positive electrode material according to claim 1, wherein the active material is at least one of lithium bis (trifluoromethanesulfonyl) imide, lithium bis fluorosulfonimide, lithium iron phosphate, and nickel cobalt manganese; and/or

The binder is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyethylene carbonate; and/or

The electronic conductive agent is at least one of graphene, graphite, carbon black, acetylene black, carbon fiber and carbon nano tubes; and/or

The mass ratio of the active material, the electronic conductive agent, the binder and the filler is 5-9: 1-4: 1-3: 0.2-0.5.

4. A preparation method of a positive electrode material comprises the following steps:

providing an active material, an electron conductive agent, a filler, a binder, and a first solvent, wherein the filler is at least one of lanthanum zirconate and lanthanum lithium zirconate, oxygen vacancies are enriched in the crystal structure of the lanthanum lithium zirconate, and the surface of the lanthanum lithium zirconate has oxygen defects;

mixing the active material, the electronic conductive agent, the filler, the binder and the first solvent to obtain positive electrode slurry; and

and drying the positive electrode slurry to obtain the positive electrode material.

5. The preparation method of the cathode material according to claim 4, wherein the lanthanum zirconate is in the form of a one-dimensional nanowire, and the diameter of the one-dimensional nanowire is 100nm to 300 nm; and/or

The form of the lanthanum lithium zirconate is a one-dimensional nanowire, and the diameter of the one-dimensional nanowire is 100 nm-300 nm.

6. The method for producing a positive electrode material according to claim 4, wherein the active material is at least one of lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium iron phosphate, and nickel cobalt manganese; and/or

The binder is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyethylene carbonate; and/or

The electronic conductive agent is at least one of graphene, graphite, carbon black, acetylene black, carbon fiber and carbon nano tubes; and/or

The first solvent is at least one of N-methyl pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile and diethylformamide; and/or

The mass ratio of the active material, the binder, the electronic conductive agent and the filler is 5-9: 1-4: 1-3: 0.2-0.5.

7. The method for preparing a positive electrode material according to claim 4, wherein the preparation of lanthanum zirconate comprises the following steps:

providing a lanthanum salt, a zirconium salt, a complexing agent, a polymer, and a second solvent;

dissolving the lithium salt, lanthanum salt, zirconium salt, complexing agent and polymer in a second solvent to obtain a precursor solution;

spinning the precursor solution to obtain a precursor fiber film;

pre-oxidizing the precursor fiber film; and

and sintering the precursor fiber film subjected to preoxidation treatment to obtain the lanthanum zirconate.

8. The method for preparing a positive electrode material according to claim 7, wherein the lanthanum salt is at least one of lanthanum nitrate hexahydrate and lanthanum carbonate; and/or

The zirconium salt is at least one of zirconyl nitrate and zirconium nitrate; and/or

The complexing agent is at least one of acetic acid and citric acid; and/or

The polymer is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyethylene carbonate; and/or

The second solvent is at least one of isopropanol, acetic acid, acetone, N dimethylformamide, N-methylpyrrolidone and polyvinylpyrrolidone; and/or

The molar ratio of lanthanum to zirconium to oxygen in the precursor solution is 1-4: 2-4: 5 to 9.

9. The method for preparing the positive electrode material according to claim 4, wherein the preparation of the lanthanum lithium zirconate comprises the following steps:

providing a lithium salt, a lanthanum salt, a zirconium salt, a complexing agent, a polymer, and a third solvent;

dissolving the lithium salt, lanthanum salt, zirconium salt, complexing agent and polymer in a third solvent to obtain a precursor solution;

spinning the precursor solution to obtain a precursor fiber film;

pre-oxidizing the precursor fiber film; and

and sintering the precursor fiber film subjected to the pre-oxidation treatment to obtain the lanthanum lithium zirconate.

10. The method for producing a positive electrode material according to claim 9, wherein the lithium salt is at least one of lithium nitrate, lithium hydroxide, and lithium carbonate; and/or

The lanthanum salt is at least one of lanthanum nitrate hexahydrate and lanthanum carbonate; and/or

The zirconium salt is at least one of zirconyl nitrate and zirconium nitrate; and/or

The complexing agent is at least one of acetic acid and citric acid; and/or

The polymer is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyethylene carbonate; and/or

The third solvent is at least one of isopropanol, acetic acid, acetone, N dimethylformamide, N-methylpyrrolidone and polyvinylpyrrolidone; and/or

The molar ratio of lithium, lanthanum, zirconium and oxygen in the precursor solution is 5-9: 1-5: 1-4: 10 to 14.

11. A positive electrode, characterized in that, the positive electrode comprises a current collector and a positive electrode film coated on the current collector, the material of the positive electrode film is the positive electrode material according to any one of claims 1 to 3.

12. An all-solid-state lithium ion battery comprising the positive electrode according to claim 11, a negative electrode, and a solid electrolyte between the positive electrode and the negative electrode.

13. The all solid-state lithium ion battery according to claim 12, wherein the solid electrolyte contains a polymer and a lithium salt dispersed in the polymer.

14. The all solid-state lithium ion battery according to claim 13, wherein the polymer is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinyl pyrrolidone, polypropylene carbonate, chlorinated polyethylene, and polyvinyl carbonate; and/or

The lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium difluorooxalato borate, lithium bis (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bis (fluorosulfonato) imide; and/or

The solid electrolyte further contains at least one of lanthanum zirconate and lanthanum lithium zirconate.

Technical Field

The invention relates to the technical field of lithium ion batteries, in particular to a positive electrode material, a preparation method of the positive electrode material, a positive electrode applying the positive electrode material and an all-solid-state lithium ion battery applying the positive electrode.

Background

Currently, lithium ion batteries are developing towards high capacity, high power, long life, and greater safety. The lithium ion battery includes a lithium ion battery using an organic liquid electrolyte and a solid lithium ion battery using a solid electrolyte. The lithium ion battery adopting the organic liquid electrolyte has many defects, such as easy short circuit, easy explosion and the like, and the application of the lithium ion battery in the fields of electric automobiles and new energy industries is limited.

The solid lithium ion battery adopting the solid electrolyte not only can overcome the defects, but also has the advantages of high energy density, high mechanical strength, large capacity and the like, and has great application value and development prospect in the field of lithium ion batteries. However, the positive electrode and the negative electrode of the all-solid-state lithium ion battery are separated by the solid electrolyte, so that the all-solid-state lithium ion battery has the disadvantages of low ionic conductivity, poor charge transfer capability and the like.

Disclosure of Invention

In view of the above, it is necessary to provide a positive electrode material to solve the problems of low ion conductivity and poor charge transfer capability of the all-solid-state lithium ion battery.

In addition, a preparation method of the cathode material is also needed.

In addition, it is necessary to provide a positive electrode.

In addition, it is also necessary to provide an all-solid-state lithium ion battery.

A positive electrode material contains an active material, a binder, an electron conductive agent, and a filler, wherein the filler is at least one of lanthanum zirconate and lanthanum lithium zirconate, oxygen vacancies are enriched in the crystal structure of the lanthanum lithium zirconate, and the surface of the lanthanum lithium zirconate has oxygen defects.

Further, the lanthanum zirconate is in a one-dimensional nanowire form, and the diameter of the one-dimensional nanowire is 100 nm-300 nm; and/or

The form of the lanthanum lithium zirconate is a one-dimensional nanowire, and the diameter of the one-dimensional nanowire is 100 nm-300 nm.

Further, the active material is at least one of lithium bis (trifluoromethanesulfonyl) imide, lithium bis fluorosulfonimide, lithium iron phosphate and nickel cobalt manganese; and/or

The binder is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyethylene carbonate; and/or

The electronic conductive agent is at least one of graphene, graphite, carbon black, acetylene black, carbon fiber and carbon nano tubes; and/or

The mass ratio of the active material, the electronic conductive agent, the binder and the filler is 5-9: 1-4: 1-3: 0.2-0.5.

A preparation method of a positive electrode material comprises the following steps:

providing an active material, an electron conductive agent, a filler, a binder, and a first solvent, wherein the filler is at least one of lanthanum zirconate and lanthanum lithium zirconate, oxygen vacancies are enriched in the crystal structure of the lanthanum lithium zirconate, and the surface of the lanthanum lithium zirconate has oxygen defects;

mixing the active material, the electronic conductive agent, the filler, the binder and the first solvent to obtain positive electrode slurry; and

and drying the positive electrode slurry to obtain the positive electrode material.

Further, the lanthanum zirconate is in a one-dimensional nanowire form, and the diameter of the one-dimensional nanowire is 100 nm-300 nm; and/or

The form of the lanthanum lithium zirconate is a one-dimensional nanowire, and the diameter of the one-dimensional nanowire is 100 nm-300 nm.

Further, the active material is at least one of lithium bis (trifluoromethanesulfonyl) imide, lithium bis fluorosulfonimide, lithium iron phosphate and nickel cobalt manganese; and/or

The binder is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyethylene carbonate; and/or

The electronic conductive agent is at least one of graphene, graphite, carbon black, acetylene black, carbon fiber and carbon nano tubes; and/or

The first solvent is at least one of N-methyl pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile and diethylformamide; and/or

The mass ratio of the active material, the binder, the electronic conductive agent and the filler is 5-9: 1-4: 1-3: 0.2-0.5.

Further, the preparation of lanthanum zirconate comprises the following steps:

providing a lanthanum salt, a zirconium salt, a complexing agent, a polymer, and a second solvent;

dissolving the lithium salt, lanthanum salt, zirconium salt, complexing agent and polymer in a second solvent to obtain a precursor solution;

spinning the precursor solution to obtain a precursor fiber film;

pre-oxidizing the precursor fiber film; and

and sintering the precursor fiber film subjected to preoxidation treatment to obtain the lanthanum zirconate.

Further, the lanthanum salt is at least one of lanthanum nitrate hexahydrate and lanthanum carbonate; and/or

The zirconium salt is at least one of zirconyl nitrate and zirconium nitrate; and/or

The complexing agent is at least one of acetic acid and citric acid; and/or

The polymer is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyethylene carbonate; and/or

The second solvent is at least one of isopropanol, acetic acid, acetone, N dimethylformamide, N-methylpyrrolidone and polyvinylpyrrolidone; and/or

The molar ratio of lanthanum to zirconium to oxygen in the precursor solution is 1-4: 2-4: 5 to 9.

Further, the preparation of the lithium lanthanum zirconate comprises the following steps:

providing a lithium salt, a lanthanum salt, a zirconium salt, a complexing agent, a polymer, and a third solvent;

dissolving the lithium salt, lanthanum salt, zirconium salt, complexing agent and polymer in a third solvent to obtain a precursor solution;

spinning the precursor solution to obtain a precursor fiber film;

pre-oxidizing the precursor fiber film; and

and sintering the precursor fiber film subjected to the pre-oxidation treatment to obtain the lanthanum lithium zirconate.

Further, the lithium salt is at least one of lithium nitrate, lithium hydroxide and lithium carbonate; and/or

The lanthanum salt is at least one of lanthanum nitrate hexahydrate and lanthanum carbonate; and/or

The zirconium salt is at least one of zirconyl nitrate and zirconium nitrate; and/or

The complexing agent is at least one of acetic acid and citric acid; and/or

The polymer is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyethylene carbonate; and/or

The third solvent is at least one of isopropanol, acetic acid, acetone, N dimethylformamide, N-methylpyrrolidone and polyvinylpyrrolidone; and/or

The molar ratio of lithium, lanthanum, zirconium and oxygen in the precursor solution is 5-9: 1-5: 1-4: 10 to 14.

The positive electrode comprises a current collector and a positive electrode film coated on the current collector, wherein the positive electrode film is made of the positive electrode material.

An all-solid-state lithium ion battery comprises a positive electrode, a negative electrode and a solid electrolyte arranged between the positive electrode and the negative electrode.

Further, the solid electrolyte contains a polymer and a lithium salt dispersed in the polymer.

Further, the polymer is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyethylene carbonate; and/or

The lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium difluorooxalato borate, lithium bis (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bis (fluorosulfonato) imide; and/or

The solid electrolyte further contains at least one of lanthanum zirconate and lanthanum lithium zirconate.

The positive electrode material provided by the invention contains an active material, a binder, an electronic conductive agent and a filler, wherein the filler is at least one of lanthanum zirconate and lanthanum lithium zirconate, the crystal structure of the lanthanum zirconate is rich in oxygen vacancies, the crystal structure of the lanthanum lithium zirconate is rich in oxygen vacancies, and the surface of the lanthanum lithium zirconate has oxygen defects. The crystal structure of the lanthanum zirconate is rich in oxygen vacancies which can be used as a transmission channel of lithium ions, so that the transmission efficiency of the lithium ions can be improved, and the all-solid-state lithium ion battery using the cathode material has higher ion conductivity. And the surface of the lanthanum zirconate can generate lithiation reaction in the circulation process of the all-solid-state lithium ion battery to form a lithium transfer interface layer, so that the transmission efficiency of lithium ions and the ionic conductivity of the all-solid-state lithium ion battery using the cathode material are further improved. Anions for promoting the dissociation of lithium salt can be adsorbed in the oxygen vacancies of the lanthanum zirconate, so that the transmission efficiency of lithium ions and the ion conductivity of the all-solid-state lithium ion battery applying the cathode material are improved. Moreover, the large number of oxygen vacancies in the lanthanum zirconate can also ensure that lithium ions are uniformly distributed in the lanthanum zirconate so as to improve the charge transfer capacity of the all-solid-state lithium ion battery applying the cathode material. The crystal structure of the lanthanum lithium zirconate is rich in oxygen vacancies which can be used as a transmission channel of lithium ions, so that the transmission efficiency of the lithium ions can be improved, and the all-solid-state lithium ion battery using the cathode material has higher ion conductivity. Anions used for promoting the dissociation of lithium salt can be adsorbed in oxygen vacancies of the lanthanum lithium zirconate, so that the transmission efficiency of lithium ions and the ionic conductivity of the all-solid-state lithium ion battery using the cathode material are further improved. Moreover, the large number of oxygen vacancies in the lanthanum lithium zirconate can promote the lithium ions to be uniformly distributed in the lanthanum lithium zirconate so as to improve the charge transfer capability of the all-solid-state lithium ion battery applying the cathode material. Further, the surface of the lanthanum lithium zirconate has a large number of oxygen defects, anions can be adsorbed in the oxygen defects, so that the dissociation of lithium salt is further promoted, and the lithium ion transmission efficiency and the ion conductivity of the all-solid-state lithium ion battery applying the cathode material are improved.

Drawings

Fig. 1 is an SEM image of lanthanum zirconate provided by an embodiment of the present invention.

Fig. 2 is an SEM image of lanthanum lithium zirconate provided in the embodiment of the present invention.

Figure 3 is an XRD pattern of lanthanum zirconate provided by embodiments of the present invention.

Fig. 4 is an XRD of lanthanum lithium zirconate provided by an embodiment of the present invention.

Fig. 5 is a cross-sectional view of an all solid-state lithium ion battery provided in an embodiment of the present invention.

Fig. 6 is a lithium ion transmission path diagram of an all-solid-state lithium ion battery according to an embodiment of the present invention.

Fig. 7 is a cycle performance diagram of the all solid-state lithium ion battery according to the first embodiment of the invention.

Fig. 8 is a cycle performance diagram of an all solid-state lithium ion battery according to a second embodiment of the present invention.

Fig. 9 is a cycle performance diagram of an all solid-state lithium ion battery according to a third embodiment of the present invention.

Fig. 10 is a cycle performance diagram of an all solid-state lithium ion battery according to a fourth embodiment of the present invention.

Fig. 11 is a cycle performance diagram of an all solid-state lithium ion battery according to example five of the present invention.

Fig. 12 is a cycle performance diagram of an all solid-state lithium ion battery according to example six of the present invention.

Fig. 13 is a cycle performance diagram of an all solid-state lithium ion battery according to example seven of the present invention.

Description of the main elements

All-solid-state lithium ion battery	100	Current collector	31
				Positive electrode	10	Lithium metal layer	33
Current collector	11	Support piece	50
				Positive electrode film	13	Solid electrolyte	70
Negative electrode	30	Battery case	90

The following detailed description will further illustrate the invention in conjunction with the above-described figures.

Detailed Description

So that the manner in which the above recited objects, features and advantages of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings. In addition, the embodiments and features of the embodiments of the present application may be combined with each other without conflict. In the following description, numerous specific details are set forth to provide a thorough understanding of the present invention, and the described embodiments are merely a subset of the embodiments of the present invention, rather than a complete embodiment. 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.

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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes all and any combination of one or more of the associated listed items.

In various embodiments of the present invention, for convenience in description and not in limitation, the term "coupled" as used in the specification and claims of the present application is not limited to physical or mechanical couplings, either direct or indirect. "upper", "lower", "left", "right", and the like are used merely to indicate relative positional relationships, and when the absolute position of the object being described is changed, the relative positional relationships are changed accordingly.

The embodiment of the invention provides a positive electrode material.

The positive electrode material contains an active material, a binder, an electronic conductive agent and a filler, wherein the filler is at least one of lanthanum zirconate and lanthanum lithium zirconate, oxygen vacancies are enriched in the crystal structure of the lanthanum lithium zirconate, and a large number of oxygen defects are arranged on the surface of the lanthanum lithium zirconate. Wherein the structural formula of the lanthanum zirconate is La₂Zr₂O₇The structural formula of the lanthanum lithium zirconate is Li₇La₃Zr₂O₁₂。

Referring to fig. 1, the lanthanum zirconate has a pyrochlore structure and is in the form of one-dimensional nanowires. The diameter of the one-dimensional nanowire is 100nm to 300nm, for example: 100nm, 150nm, 200nm, 250nm, or 300 nm.

Referring to fig. 2, the lithium lanthanum zirconate has a garnet structure in the form of a one-dimensional nanowire. The diameter of the one-dimensional nanowire is 100nm to 300nm, for example: 100nm, 150nm, 200nm, 250nm, or 300 nm.

The active material is at least one of lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium iron phosphate and nickel-cobalt-manganese (NCM 811).

The binder is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyethylene carbonate.

The electronic conductive agent is at least one of graphene, graphite, carbon black, acetylene black, carbon fiber and carbon nano tubes.

The mass ratio of the active material to the electronic conductive agent to the binder to the filler is 5-9: 1-4: 1-3: 0.2 to 0.5, preferably 7: 2: 1: 0.2.

the positive electrode material provided by the invention contains an active material, a binder, an electronic conductive agent and a filler, wherein the filler is at least one of lanthanum zirconate and lanthanum lithium zirconate, the crystal structure of the lanthanum zirconate is rich in oxygen vacancies, the crystal structure of the lanthanum lithium zirconate is rich in oxygen vacancies, and the surface of the lanthanum lithium zirconate has oxygen defects. The crystal structure of the lanthanum zirconate is rich in oxygen vacancies which can be used as a transmission channel of lithium ions, so that the transmission efficiency of the lithium ions can be improved, and the all-solid-state lithium ion battery 100 applying the cathode material has higher ion conductivity. And the surface of the lanthanum zirconate can generate lithiation reaction in the circulation process of the all-solid-state lithium ion battery 100, anions which can promote the dissociation of lithium salt can be adsorbed in the oxygen vacancy of the lanthanum zirconate, the transmission efficiency of the lithium ions can be improved, the ion conductivity of the all-solid-state lithium ion battery 100 applying the anode material can adsorb the anions in the oxygen vacancy of the lanthanum zirconate, the anions can promote the dissociation of the lithium salt, the transmission efficiency of the lithium ions and the ion conductivity of the all-solid-state lithium ion battery 100 applying the anode material can be improved to form a lithium transfer interface layer, and the transmission efficiency of the lithium ions and the ion conductivity of the all-solid-state lithium ion battery 100 applying the anode material are further improved. Anions for promoting the dissociation of lithium salts can be adsorbed in the oxygen vacancies of the lanthanum zirconate, so that the transmission efficiency of lithium ions and the ion conductivity of the all-solid-state lithium ion battery 100 using the cathode material are improved. Moreover, the large number of oxygen vacancies in the lanthanum zirconate can also enable lithium ions to be uniformly distributed in the lanthanum zirconate so as to improve the charge transfer capability of the all-solid-state lithium ion battery 100 applying the cathode material. The crystal structure of the lanthanum lithium zirconate is rich in oxygen vacancies which can be used as a transmission channel of lithium ions, so that the transmission efficiency of the lithium ions can be improved, and the all-solid-state lithium ion battery 100 applying the cathode material has higher ion conductivity. The oxygen vacancies of the lanthanum lithium zirconate can adsorb anions for promoting the dissociation of lithium salt, so that the transmission efficiency of lithium ions and the ionic conductivity of the all-solid-state lithium ion battery 100 using the cathode material are further improved. Moreover, the large number of oxygen vacancies in the lanthanum lithium zirconate can promote the uniform distribution of lithium ions in the lanthanum lithium zirconate, so as to improve the charge transfer capability of the all-solid-state lithium ion battery 100 applying the cathode material. Further, the surface of the lanthanum lithium zirconate has a large number of oxygen defects, and anions can be adsorbed in the oxygen defects, so that the dissociation of lithium salt is further promoted, and the lithium ion transmission efficiency and the ion conductivity of the all-solid-state lithium ion battery 100 using the cathode material are improved.

Because the all-solid-state lithium ion battery 100 using the cathode material has higher lithium ion transmission efficiency, ionic conductivity and charge transfer capacity, the all-solid-state lithium ion battery 100 further has lower polarizability, better cycle capacity, rate capability and high-temperature stability.

The invention also provides a preparation method of the cathode material, which comprises the following steps:

step S1: providing an active material, an electron conductive agent, a filler, a binder, and a first solvent, wherein the filler is at least one of lanthanum zirconate and lanthanum lithium zirconate, the lanthanum zirconate is rich in oxygen vacancies in a crystal structure, the lanthanum lithium zirconate is rich in oxygen vacancies in a crystal structure, and the surface of the lanthanum lithium zirconate has a large number of oxygen defects;

step S2: mixing the active material, the electronic conductive agent, the filler, the binder and the first solvent to obtain positive electrode slurry; and

step S3: and drying the positive electrode slurry to obtain the positive electrode material.

Referring to fig. 1, the lanthanum zirconate has a pyrochlore structure and is in the form of one-dimensional nanowires. The diameter of the one-dimensional nanowire is 100nm to 300nm, for example: 100nm, 150nm, 200nm, 250nm, or 300 nm.

Referring to fig. 2, the lithium lanthanum zirconate has a garnet structure in the form of a one-dimensional nanowire. The diameter of the one-dimensional nanowire is 100nm to 300nm, for example: 100nm, 150nm, 200nm, 250nm, or 300 nm.

The active material is at least one of lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium iron phosphate and nickel cobalt manganese.

The binder is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyethylene carbonate.

The electronic conductive agent is at least one of graphene, graphite, carbon black, acetylene black, carbon fiber and carbon nano tubes.

The first solvent is at least one of N-methyl pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile and diethylformamide.

The mass ratio of the active material to the electronic conductive agent to the binder to the filler is 5-9: 1-4: 1-3: 0.2 to 0.5, preferably 7: 2: 1: 0.2.

in one embodiment, the active material may be weighed under a nitrogen atmosphere.

In one embodiment, the positive electrode slurry may be stirred for 12 to 24 hours to uniformly mix the components.

The positive electrode material prepared by the preparation method of the positive electrode material provided by the invention contains an active material, a binder, an electronic conductive agent and a filler, wherein the filler is at least one of lanthanum zirconate and lanthanum lithium zirconate, the lanthanum zirconate is rich in oxygen vacancies in a crystal structure, the lanthanum lithium zirconate is rich in oxygen vacancies in a crystal structure, and the surface of the lanthanum lithium zirconate has a large number of oxygen defects. The crystal structure of the lanthanum zirconate is rich in oxygen vacancies which can be used as a transmission channel of lithium ions, so that the transmission efficiency of the lithium ions can be improved, and the all-solid-state lithium ion battery 100 applying the cathode material has higher ion conductivity. And the surface of the lanthanum zirconate can generate lithiation reaction in the circulation process of the all-solid-state lithium ion battery 100, anions which can promote the dissociation of lithium salt can be adsorbed in the oxygen vacancy of the lanthanum zirconate, the transmission efficiency of the lithium ions can be improved, the ion conductivity of the all-solid-state lithium ion battery 100 applying the anode material can adsorb the anions in the oxygen vacancy of the lanthanum zirconate, the anions can promote the dissociation of the lithium salt, the transmission efficiency of the lithium ions and the ion conductivity of the all-solid-state lithium ion battery 100 applying the anode material can be improved to form a lithium transfer interface layer, and the transmission efficiency of the lithium ions and the ion conductivity of the all-solid-state lithium ion battery 100 applying the anode material are further improved. Anions for promoting the dissociation of lithium salts can be adsorbed in the oxygen vacancies of the lanthanum zirconate, so that the transmission efficiency of lithium ions and the ion conductivity of the all-solid-state lithium ion battery 100 using the cathode material are improved. Moreover, the large number of oxygen vacancies in the lanthanum zirconate can also enable lithium ions to be uniformly distributed in the lanthanum zirconate so as to improve the charge transfer capability of the all-solid-state lithium ion battery 100 applying the cathode material. The crystal structure of the lanthanum lithium zirconate is rich in oxygen vacancies which can be used as a transmission channel of lithium ions, so that the transmission efficiency of the lithium ions can be improved, and the all-solid-state lithium ion battery 100 applying the cathode material has higher ion conductivity. The oxygen vacancies of the lanthanum lithium zirconate can adsorb anions for promoting the dissociation of lithium salt, so that the transmission efficiency of lithium ions and the ionic conductivity of the all-solid-state lithium ion battery 100 using the cathode material are further improved. Moreover, the large number of oxygen vacancies in the lanthanum lithium zirconate can promote the uniform distribution of lithium ions in the lanthanum lithium zirconate, so as to improve the charge transfer capability of the all-solid-state lithium ion battery 100 applying the cathode material. Further, the surface of the lanthanum lithium zirconate has a large number of oxygen defects, and anions can be adsorbed in the oxygen defects, so that the dissociation of lithium salt is further promoted, and the lithium ion transmission efficiency and the ion conductivity of the all-solid-state lithium ion battery 100 using the cathode material are improved.

Because the all-solid-state lithium ion battery 100 using the cathode material has higher lithium ion transmission efficiency, ionic conductivity and charge transfer capacity, the all-solid-state lithium ion battery 100 further has lower polarizability, better cycle capacity, rate capability and high-temperature stability.

In addition, in the preparation method of the cathode material provided by the embodiment of the invention, the cathode material can be obtained only by mixing the active material, the electronic conductive agent, the filler, the binder and the first solvent and then drying the cathode slurry, so that the preparation method of the cathode material provided by the invention has the advantages of simple process, convenience in operation and suitability for large-scale production.

Further, the preparation of lanthanum zirconate comprises the following steps:

step S111: providing a lanthanum salt, a zirconium salt, a complexing agent, a polymer, and a second solvent;

step S112: dissolving the lithium salt, lanthanum salt, zirconium salt, complexing agent and polymer in a second solvent, and stirring for 24-48 h at room temperature to obtain a transparent precursor solution;

step S113: spinning the precursor solution to obtain a precursor fiber film;

step S114: pre-oxidizing the precursor fiber film; and

step S115: and sintering the precursor fiber film subjected to preoxidation treatment to obtain the lanthanum zirconate.

The lanthanum salt is at least one of lanthanum nitrate hexahydrate and lanthanum carbonate.

The zirconium salt is at least one of zirconyl nitrate and zirconium nitrate.

The complexing agent is used for complexing metal cations and is selected from at least one of acetic acid and citric acid.

The polymer can enable the precursor solution to have certain viscosity, provides a framework for subsequent spinning, and is selected from at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyvinyl carbonate, preferably polymethyl ethylene carbonate, and more preferably polyvinylpyrrolidone.

The second solvent is at least one of isopropanol, acetic acid, acetone, N dimethylformamide, N-methylpyrrolidone and polyvinylpyrrolidone.

The molar ratio of lanthanum to zirconium to oxygen in the precursor solution is 1-4: 2-4: 5-9, preferably 2: 2: 7.

further, the spinning treatment is electrostatic spinning, air-blowing spinning, or centrifugal spinning. The embodiment of the present invention describes the step S113 by electrostatic spinning. In this embodiment, the step S113 includes the following steps:

step S1131: after the precursor solution is placed in an injector, the injector is installed in an electrostatic spinning device; and

step S1132: setting the high voltage at 20kV to 25kV, the low voltage at-1 kV to 2kV, the acceptance distance at 15cm to 20cm, and propelling the injector at the speed of 1.0mL/h to 2.0mL/h to carry out electrostatic spinning.

It will be appreciated that in the electrospinning process, the precursor solution is drawn into filaments under high pressure to form a precursor fiber film. The main component of the precursor fiber film is a polymer loaded with lanthanum salt and zirconium salt.

During the electrospinning, the air humidity was set to be less than 30%.

Further, between the step S113 and the step S114, the method also comprises the step of drying the precursor fiber film in an oven at 60-80 ℃ for 12-24 h. The thickness of the precursor fiber film after drying treatment is 2mm to 5mm, for example, 2mm, 3mm, 4mm, or 5 mm.

Further, the step S114 includes the steps of:

step S1141: providing a high temperature resistant vessel;

step S1142: cutting the precursor fiber films, stacking the precursor fiber films in a high-temperature-resistant vessel, and placing carbon paper between every two layers of precursor fiber films for isolation; and

step S1143: heating the precursor fiber film to 260-300 ℃ at the heating rate of 1-2 ℃/min, and then preserving the heat for 2-6 h to oxidize the polymer in the precursor fiber film, thereby improving the mechanical property of the precursor fiber film.

Further, the step S115 includes the steps of:

step S1151: removing the carbon paper in the high-temperature-resistant vessel; and

step S1152: and putting the high-temperature-resistant vessel carrying the pre-oxidized precursor fiber film into a muffle furnace for sintering treatment.

In one embodiment, the sintering process is to heat the preoxidized precursor fiber film to 1150-1200 ℃ at a heating rate of 5-10 ℃/min, and then to preserve heat for 6-12 h. In the sintering process, the polymer is decomposed, and the lanthanum zirconate is in a phase, so that the pure lanthanum zirconate nanowire with the pyrochlore structure is obtained, and the shape retention rate of the lanthanum zirconate nanowire is high. The decomposition residual rate of the polymer at high temperature is low, so that the phase purity of the lanthanum zirconate is high. Referring to FIG. 3, lanthanum zirconate which forms a phase at a sintering temperature of 1200 ℃ has a preferred phase.

Further, the preparation of the lithium lanthanum zirconate comprises the following steps:

step S121: providing a lithium salt, a lanthanum salt, a zirconium salt, a complexing agent, a polymer, and a third solvent;

step S122: dissolving the lithium salt, lanthanum salt, zirconium salt, complexing agent and polymer in a third solvent, and stirring for 24-48 h at room temperature to obtain a transparent precursor solution;

step S123: spinning the precursor solution to obtain a precursor fiber film;

step S124: pre-oxidizing the precursor fiber film; and

step S125: and sintering the precursor fiber film subjected to the pre-oxidation treatment to obtain the lanthanum lithium zirconate.

The lithium salt is at least one of lithium nitrate, lithium hydroxide and lithium carbonate.

The lanthanum salt is at least one of lanthanum nitrate hexahydrate and lanthanum carbonate.

The zirconium salt is at least one of zirconyl nitrate and zirconium nitrate.

The complexing agent is used for complexing metal cations and is selected from at least one of acetic acid and citric acid.

The polymer can enable the precursor solution to have certain viscosity, provides a framework for subsequent spinning, and is selected from at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyvinyl carbonate, preferably polymethyl ethylene carbonate, and more preferably polyvinylpyrrolidone.

The third solvent is at least one of isopropanol, acetic acid, acetone, N dimethylformamide, N-methylpyrrolidone and polyvinylpyrrolidone.

The molar ratio of lithium, lanthanum, zirconium and oxygen in the precursor solution is 5-9: 1-5: 1-4: 10-14, preferably 7: 3: 2: 12.

further, the spinning treatment is electrostatic spinning, air-blowing spinning, or centrifugal spinning. The embodiment of the present invention describes the step S123 by electrostatic spinning. In this embodiment, the step S123 includes the following steps:

step S1231: after the precursor solution is placed in an injector, the injector is installed in an electrostatic spinning device; and

step S1232: setting the high voltage at 20kV to 25kV, the low voltage at-1 kV to 2kV, the acceptance distance at 15cm to 20cm, and propelling the injector at the speed of 1.0mL/h to 2.0mL/h to carry out electrostatic spinning.

It will be appreciated that in the electrospinning process, the precursor solution is drawn into filaments under high pressure to form a precursor fiber film. The main component of the precursor fiber film is a polymer loaded with lithium salt, lanthanum salt and zirconium salt.

During the electrospinning, the air humidity was set to be less than 30%.

Further, between the step S123 and the step S124, the method also comprises the step of drying the precursor fiber film in an oven at 60-80 ℃ for 12-24 h. The thickness of the precursor fiber film after drying treatment is 2mm to 5mm, for example, 2mm, 3mm, 4mm, or 5 mm.

Further, the step S124 includes the steps of:

step S1241: providing a high temperature resistant vessel;

step S1242: cutting the precursor fiber films, stacking the precursor fiber films in a high-temperature-resistant vessel, and placing carbon paper between every two layers of precursor fiber films for isolation; and

step S1243: heating the precursor fiber film to 260-300 ℃ at the heating rate of 1-2 ℃/min, and then preserving the heat for 2-6 h to oxidize the polymer in the precursor fiber film, thereby improving the mechanical property of the precursor fiber film.

Further, the step S125 includes the steps of:

step S1251: removing the carbon paper in the high-temperature-resistant vessel; and

step S1252: and putting the high-temperature-resistant vessel carrying the pre-oxidized precursor fiber film into a tube furnace for sintering treatment.

In one embodiment, the sintering treatment is to heat the preoxidized precursor fiber film to 800-900 ℃ at a heating rate of 5-10 ℃/min by using argon or nitrogen as a protective gas, and then to preserve heat for 6-12 h. In the sintering process, the polymer is decomposed, and the lanthanum lithium zirconate forms a phase to obtain the lanthanum lithium zirconate nanowire with the garnet structure, and the shape retention rate of the lanthanum lithium zirconate nanowire is high. The decomposition residual rate of the polymer at high temperature is low, so that the phase purity of the lanthanum lithium zirconate is high. Referring to fig. 4, the lithium lanthanum zirconate obtained by sintering has a better phase when argon is used as the shielding gas.

Referring to fig. 5, an anode 10 is further provided in the embodiment of the invention. The positive electrode 10 comprises a current collector 11 and a positive electrode film 13 coated on the current collector 11, and the material of the positive electrode film 13 is the positive electrode material.

The current collector 11 may be an aluminum foil or a carbon-coated aluminum foil.

The thickness of the positive electrode film 13 is 60 μm to 120 μm, for example, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, or 120 μm.

Since the positive electrode 10 adopts all technical solutions of all the above embodiments, at least all the beneficial effects brought by the technical solutions of the above embodiments are achieved, and no further description is given here.

Referring to fig. 5 to 6, an all solid-state lithium ion battery 100 is further provided according to an embodiment of the present invention. The all-solid-state lithium ion battery 100 includes the positive electrode 10, the negative electrode 30, the solid electrolyte 70 located between the positive electrode 10 and the negative electrode 30, and a battery case 90 for accommodating the positive electrode 10, the negative electrode 30, and the solid electrolyte 70.

In one embodiment, the all-solid-state lithium ion battery 100 is an integrated all-solid-state lithium ion battery.

The negative electrode 30 includes a current collector 31, and a lithium metal layer 33 provided on a side of the current collector 31 close to the positive electrode film 13. The current collector 31 may be a copper foil or a carbon-coated copper foil.

The all-solid-state lithium ion battery 100 further includes a support 50 disposed on a side of the current collector 31 away from the positive electrode film 13. The support 50 is used to support the current collector 31, the support 50 may be a spring plate or a support plate with a shape matching with the current collector 31, and the support plate may be made of copper foam, iron foam, nickel foam, or iron nickel foam.

The solid electrolyte 70 contains a polymer and a lithium salt dispersed in the polymer.

The lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium difluorooxalato borate, lithium bis (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bis (fluorosulfonato) imide.

The polymer is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyethylene carbonate.

The solid electrolyte 70 may further contain a filler, which is at least one of lanthanum zirconate and lanthanum lithium zirconate, to further improve the transmission efficiency of lithium ions and the ion conductivity of the all-solid lithium ion battery 100 using the solid electrolyte 70.

The lanthanum zirconate in the solid electrolyte 70 has a pyrochlore structure and is in the form of a one-dimensional nanowire. The diameter of the one-dimensional nanowire is 100nm to 300nm, for example: 100nm, 150nm, 200nm, 250nm, or 300 nm.

The lanthanum lithium zirconate in the solid electrolyte 70 has a garnet structure and is in the form of a one-dimensional nanowire. The diameter of the one-dimensional nanowire is 100nm to 300nm, for example: 100nm, 150nm, 200nm, 250nm, or 300 nm.

In one embodiment, the mass ratio of the lithium salt, the polymer, and the filler in the solid electrolyte 70 is 7-9: 4-6: 1 to 2, for example, 8: 5: 1.

since the all-solid-state lithium ion battery 100 adopts all the technical solutions of all the embodiments, at least all the beneficial effects brought by the technical solutions of the embodiments are also achieved, and no further description is given here.

In one embodiment, the material of the binder in the positive electrode film 13 is the same as the material of the polymer in the solid electrolyte 70, for example, when the binder in the positive electrode film 13 is polyvinylidene fluoride, the polymer in the solid electrolyte 70 is also selected to be polyvinylidene fluoride, so as to eliminate the potential difference between the contact interfaces of the positive electrode film 13 and the solid electrolyte 70. Since the binder in the positive electrode film 13 is made of the same material as the polymer in the solid electrolyte 70, the contact interface between the positive electrode film 13 and the solid electrolyte 70 can be fused, so that lithium ions can be rapidly transferred in the contact interface.

Referring to fig. 6, in the embodiment of the present invention, the all-solid-state lithium ion battery 100 has three lithium ion transmission paths, which greatly increases the transmission efficiency of lithium ions. Wherein the first transmission path is oxygen vacancy in the lanthanum zirconate and/or the lanthanum lithium zirconate, the second transmission path is a lithium transfer interface layer on the surface of the lanthanum zirconate, and the third transmission path is a contact interface of the positive electrode film 13 and the solid electrolyte 70.

The invention also provides a preparation method of the all-solid-state lithium ion battery 100, which comprises the following steps:

step S101: assembling the positive electrode 10, the negative electrode 30, the support member 50, and the solid electrolyte 70 in a battery can 90; and

step S102: the assembled battery is post-processed to obtain the all-solid lithium ion battery 100.

In at least one embodiment, the post-treatment is at least one of a fusion treatment, a lamination treatment, and a rolling treatment.

The fusion treatment is to keep the temperature of the assembled battery at 60-80 ℃ for 12-24 h so as to fuse the contact interface of the positive electrode film 13 and the solid electrolyte 70.

And the pressing treatment is to press the assembled battery for 1 to 10 hours under the pressure of 5 to 10MPa so that the contact interface of the positive electrode film 13 and the solid electrolyte 70 is well contacted.

The rolling process is to perform a rolling process on the assembled battery to reduce the voids in the positive electrode 10 and further tighten the contact and fusion of the positive electrode film 13 with the solid electrolyte 70.

In the preparation method of the all-solid-state lithium ion battery 100 according to the embodiment of the present invention, the fusion treatment, the lamination treatment, and the rolling treatment are sequentially performed on the assembled all-solid-state lithium ion battery 100, so that the contact interfaces of the positive electrode film 13 and the solid electrolyte 70 can be fused with each other and have good contact, and the vacancy in the positive electrode 10 is reduced, thereby enabling the all-solid-state lithium ion battery 100 to have higher lithium ion transmission efficiency.

The present invention will be specifically described below with reference to specific examples.

Example one

The preparation method of the all-solid-state lithium ion battery of the first embodiment comprises the following steps:

placing 41mg of lithium bis (trifluoromethanesulfonyl) imide, 100mg of polyethylene oxide, 20mg of lanthanum zirconate, 100mg of conductive carbon black, 800mg of lithium iron phosphate and 5mL of acetonitrile in a stirring bottle, and stirring for 12 hours to obtain positive electrode slurry;

coating the positive electrode slurry on a carbon-coated aluminum foil, and drying at the temperature of 60 ℃ for 6h to obtain a positive electrode;

providing a negative electrode, a support and a solid electrolyte, wherein the negative electrode comprises a carbon-coated copper foil and a lithium metal layer arranged on the carbon-coated copper foil, the support is a spring plate, and the solid electrolyte contains 287.5mg of lithium bis (trifluoromethanesulfonyl) imide and 700mg of polyethylene oxide; and

and (3) assembling the positive electrode, the negative electrode, the support piece and the solid electrolyte into a battery case, standing for 24 hours at the temperature of 60 ℃, and performing high-temperature fusion to obtain the all-solid-state lithium ion battery of the first embodiment.

Referring to fig. 7, the all solid-state lithium ion battery of the first embodiment can still output a specific discharge capacity of 110mAh/g after being cycled for 800 cycles at a rate of 0.1C, which indicates that the all solid-state lithium ion battery of the first embodiment has excellent cycling stability.

Example two

The preparation of the all solid-state lithium ion battery of example two includes the following steps:

placing 41mg of lithium bis (trifluoromethanesulfonyl) imide, 100mg of polyethylene oxide, 20mg of lanthanum lithium zirconate, 100mg of conductive carbon black, 800mg of lithium iron phosphate and 5mL of acetonitrile in a stirring bottle, and stirring for 12 hours to obtain positive electrode slurry;

coating the positive electrode slurry on a carbon-coated aluminum foil, and drying at the temperature of 60 ℃ for 6h to obtain a positive electrode;

providing a negative electrode, a support and a solid electrolyte, wherein the negative electrode comprises a carbon-coated copper foil and a lithium metal layer arranged on the carbon-coated copper foil, the support is a spring plate, and the solid electrolyte contains 287.5mg of lithium bis (trifluoromethanesulfonyl) imide and 700mg of polyethylene oxide; and

and (3) assembling the positive electrode, the negative electrode, the support piece and the solid electrolyte into a battery case, standing for 24 hours at the temperature of 60 ℃, and performing high-temperature fusion to obtain the all-solid-state lithium ion battery of the second embodiment.

Referring to fig. 8, after the all-solid-state lithium ion battery of the second embodiment is cycled for 50 cycles at the rate of 0.1C, the all-solid-state lithium ion battery of the second embodiment can still output a specific discharge capacity of 100mAh/g, which indicates that the all-solid-state lithium ion battery of the second embodiment has excellent cycling stability.

EXAMPLE III

The preparation of the all solid-state lithium ion battery of example three included the following steps:

placing 41mg of lithium bis (trifluoromethanesulfonyl) imide, 100mg of polyethylene oxide, 20mg of lanthanum zirconate, 100mg of conductive carbon black, 800mg of NCM811 and 5mL of acetonitrile in a stirring bottle, and stirring for 12 hours to obtain positive electrode slurry;

coating the positive electrode slurry on a carbon-coated aluminum foil, and drying at the temperature of 60 ℃ for 6h to obtain a positive electrode;

providing a negative electrode, a support and a solid electrolyte, wherein the negative electrode comprises a carbon-coated copper foil and a lithium metal layer arranged on the carbon-coated copper foil, the support is a spring plate, and the solid electrolyte contains 287.5mg of lithium bis (trifluoromethanesulfonyl) imide and 700mg of polyethylene oxide; and

and (3) assembling the positive electrode, the negative electrode, the support piece and the solid electrolyte into a battery case, standing for 24 hours at the temperature of 60 ℃, and performing high-temperature fusion to obtain the all-solid-state lithium ion battery of the third embodiment.

Referring to fig. 9, after the all-solid-state lithium ion battery of the third embodiment is cycled for 20 cycles at the rate of 0.05C, the all-solid-state lithium ion battery of the third embodiment can still output a specific discharge capacity of 130mAh/g, which indicates that the all-solid-state lithium ion battery of the third embodiment has excellent cycling stability.

Example four

The preparation of the all solid-state lithium ion battery of example four included the following steps:

placing 41mg of lithium bis (trifluoromethanesulfonyl) imide, 100mg of polyethylene oxide, 20mg of lanthanum lithium zirconate, 100mg of conductive carbon black, 800mg of NCM811 and 5mL of acetonitrile in a stirring bottle, and stirring for 12 hours to obtain positive electrode slurry;

coating the positive electrode slurry on a carbon-coated aluminum foil, and drying at the temperature of 60 ℃ for 6h to obtain a positive electrode;

providing a negative electrode, a support and a solid electrolyte, wherein the negative electrode comprises a carbon-coated copper foil and a lithium metal layer arranged on the carbon-coated copper foil, the support is a spring plate, and the solid electrolyte contains 287.5mg of lithium bis (trifluoromethanesulfonyl) imide and 700mg of polyethylene oxide; and

and (3) assembling the positive electrode, the negative electrode, the support piece and the solid electrolyte into a battery case, standing for 24 hours at the temperature of 60 ℃, and performing high-temperature fusion to obtain the all-solid-state lithium ion battery of the fourth embodiment.

Referring to fig. 10, the all-solid-state lithium ion battery of the fourth embodiment can still output a specific discharge capacity of 100mAh/g after being cycled for 25 cycles at a rate of 0.1C, which indicates that the all-solid-state lithium ion battery of the fourth embodiment has excellent cycling stability.

EXAMPLE five

The preparation of the all solid-state lithium ion battery of example v includes the following steps:

placing 66mg of lithium bis (trifluoromethanesulfonyl) imide, 100mg of polyvinylidene fluoride, 20mg of lanthanum zirconate, 100mg of conductive carbon black, 800mg of NCM811 and 5mL of N, N-dimethylformamide in a stirring bottle, and stirring for 12 hours to obtain positive electrode slurry;

coating the positive electrode slurry on a carbon-coated aluminum foil, and drying at the temperature of 60 ℃ for 6h to obtain a positive electrode;

providing a negative electrode, a support and a solid electrolyte, wherein the negative electrode comprises a carbon-coated copper foil and a lithium metal layer arranged on the carbon-coated copper foil, the support is a spring plate, and the solid electrolyte contains 268mg of lithium bis (trifluoromethanesulfonyl) imide and 400mg of polyvinylidene fluoride; and

and (3) assembling the positive electrode, the negative electrode, the support piece and the solid electrolyte into a battery case, standing for 24 hours at the temperature of 60 ℃, and performing high-temperature fusion to obtain the all-solid-state lithium ion battery of the fifth embodiment.

Referring to fig. 11, the all solid-state lithium ion battery of the fifth embodiment can still output a specific discharge capacity of 110mAh/g after being cycled for 100 cycles at a rate of 0.5C, which indicates that the all solid-state lithium ion battery of the fifth embodiment has excellent cycling stability.

EXAMPLE six

The preparation of the all solid-state lithium ion battery of example six comprises the following steps:

placing 66mg of lithium bis (trifluoromethanesulfonyl) imide, 100mg of polyvinylidene fluoride, 20mg of lanthanum lithium zirconate, 100mg of conductive carbon black, 800mg of NCM811 and 5mL of N, N-dimethylformamide in a stirring bottle, and stirring for 12 hours to obtain positive electrode slurry;

coating the positive electrode slurry on a carbon-coated aluminum foil, and drying at the temperature of 60 ℃ for 6h to obtain a positive electrode;

providing a negative electrode, a support and a solid electrolyte, wherein the negative electrode comprises a carbon-coated copper foil and a lithium metal layer arranged on the carbon-coated copper foil, the support is a spring plate, and the solid electrolyte contains 268mg of lithium bis (trifluoromethanesulfonyl) imide and 400mg of polyvinylidene fluoride; and

and (3) assembling the positive electrode, the negative electrode, the support piece and the solid electrolyte into a battery case, standing for 24 hours at the temperature of 60 ℃, and performing high-temperature fusion to obtain the all-solid-state lithium ion battery of the sixth embodiment.

Referring to fig. 12, the all-solid-state lithium ion battery of the sixth embodiment can still output a specific discharge capacity of 180mAh/g after being cycled for 40 cycles at a rate of 0.1C, which indicates that the all-solid-state lithium ion battery of the sixth embodiment has excellent cycling stability.

EXAMPLE seven

The preparation of the all solid-state lithium ion battery of example seven included the following steps:

placing 41mg of lithium bis (trifluoromethanesulfonyl) imide, 100mg of polyvinylidene fluoride, 20mg of lanthanum zirconate, 100mg of conductive carbon black, 800mg of NCM811 and 5mL of acetonitrile in a stirring bottle, and stirring for 12 hours to obtain positive electrode slurry;

coating the positive electrode slurry on a carbon-coated aluminum foil, and drying at the temperature of 60 ℃ for 6h to obtain a positive electrode;

providing a negative electrode, a support and a solid electrolyte, wherein the negative electrode comprises a carbon-coated copper foil and a lithium metal layer arranged on the carbon-coated copper foil, the support is a spring plate, and the solid electrolyte contains 287.5mg of lithium bis (trifluoromethanesulfonyl) imide, 70mg of lanthanum zirconate and 400mg of polyvinylidene fluoride; and

and (3) assembling the positive electrode, the negative electrode, the support piece and the solid electrolyte into a battery case, standing for 24 hours at the temperature of 60 ℃, and performing high-temperature fusion to obtain the all-solid-state lithium ion battery of the seventh embodiment.

Referring to fig. 13, the all solid-state lithium ion battery of the seventh embodiment can still output a specific discharge capacity of 120mAh/g after being cycled for 250 cycles at a rate of 0.1C, which indicates that the all solid-state lithium ion battery of the seventh embodiment has excellent cycling stability.

Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention.