阅读说明：本技术 一种聚合有机无机复合固体电解质及原位组装全固态电池 (Polymeric organic-inorganic composite solid electrolyte and in-situ assembled all-solid-state battery ) 是由 郭新 李卓 于 2019-08-14 设计创作，主要内容包括：本发明涉及一种聚合有机无机复合固体电解质及原位组装全固态电池,属于离子电池制备技术领域。聚合固体电解质的制备方法为将聚合物单体和交联剂充分混匀后,再加入电解质盐和引发剂,得到电解质前驱体；将该电解质前驱体进行引发,即得到聚合固体电解质。将电解质前驱体滴在正极上,然后在所述电解质前驱体上覆盖负极,再进行引发,电解质前驱体固化后,即得到原位组装全固态电池。该固体电解质的室温电导率达到1.6×10<Sup>-4</Sup>S cm<Sup>-1</Sup>,且电化学窗口大于6V。基于该固体电解质的全固态电池,在0.5C的充放电倍率下,放电容量密度为145mAh/g,0.1C时放电容量为176mAh/g,0.5C下,100次循环后容量保持率为88％。(The invention relates to a polymerized organic-inorganic composite solid electrolyte and an in-situ assembled all-solid-state battery, belonging to the technical field of ionic battery preparation.A preparation method of the polymerized solid electrolyte comprises the steps of fully mixing a polymer monomer and a cross-linking agent, adding electrolyte salt and an initiator to obtain an electrolyte precursor, initiating the electrolyte precursor to obtain the polymerized solid electrolyte, dripping the electrolyte precursor on a positive electrode, covering a negative electrode on the electrolyte precursor, initiating, and curing the electrolyte precursor to obtain the in-situ assembled all-solid-state battery, wherein the room-temperature conductivity of the solid electrolyte reaches 1.6 multiplied by 10 -4 S cm -1 , the electrochemical window is more than 6V, and the capacity retention rate of the all-solid-state battery based on the solid electrolyte is 88% under the charge and discharge rate of 0.5C, the discharge capacity density is 145mAh/g under the condition of 0.1C, and the discharge capacity is 176mAh/g under the condition of 0.5C and the capacity retention rate is 88% after 100 cycles.)

1. A method for preparing a polymeric solid electrolyte, comprising the steps of:

(1) Fully and uniformly mixing a polymer monomer and a cross-linking agent, adding electrolyte salt and an initiator, and completely dissolving to obtain an electrolyte precursor;

(2) And (2) heating the electrolyte precursor obtained in the step (1), or carrying out ultraviolet radiation, so that the initiator initiates the polymer monomer and the cross-linking agent to carry out cross-linking polymerization reaction to form a polymer, and then the polymeric solid electrolyte is obtained.

2. The method of claim 1, further comprising a step of adding an inorganic ceramic filler for improving conductivity and stability of the electrolyte salt after the electrolyte salt and the initiator are completely dissolved in the step (1).

3. the method for preparing the polymeric solid electrolyte according to claim 1, wherein the heating temperature is 60 ℃ to 100 ℃ and the heating time is 60s to 120s, the power of the ultraviolet light is 50mW/cm ² to 2000mW/cm ², and the irradiation time is 60s to 120 s;

The electrolyte salt is lithium salt, sodium salt, potassium salt or zinc salt; the polymer monomer is polyethylene glycol dimethacrylate or polyethylene glycol diacrylate; the cross-linking agent is tetraethyleneglycol diacrylate; the initiator is a thermal initiator or a photoinitiator;

preferably, the thermal initiator is azobisisobutyronitrile and the photoinitiator is 2-hydroxy-2-methyl propiophenone.

4. The method for producing a polymeric solid electrolyte according to claim 2, wherein the concentration of the electrolyte salt in the electrolyte precursor is 0.5mol/L to 2 mol/L; the mass ratio of the polymer monomer to the cross-linking agent is (12-19): (1-8); the mass of the initiator is 1-5% of the sum of the mass of the polymer monomer and the mass of the cross-linking agent; the mass of the inorganic ceramic filler is less than or equal to 20% of the sum of the mass of the polymer monomer and the mass of the cross-linking agent;

the inorganic ceramic filler is lanthanum lithium zirconate nano-particles doped with metal ions, and the metal ions are gallium ions, neodymium ions, tantalum ions or niobium ions.

5. a polymeric solid electrolyte prepared by the method of any one of claims 1 to 4.

6. A preparation method of an in-situ assembled all-solid-state battery is characterized by comprising the following steps:

(1) Fully and uniformly mixing a polymer monomer and a cross-linking agent, adding electrolyte salt and an initiator, and completely dissolving to obtain an electrolyte precursor;

(2) Dropping the electrolyte precursor obtained in the step (1) on a positive electrode, then covering a negative electrode on the electrolyte precursor, heating or carrying out ultraviolet radiation to enable the initiator to initiate the polymer monomer and the cross-linking agent to carry out cross-linking polymerization reaction to form a polymer, and curing the electrolyte precursor to obtain the in-situ assembled all-solid-state battery.

7. The method of preparing an in-situ assembled all-solid battery according to claim 6, wherein the step (1) further comprises a step of adding an inorganic ceramic filler for improving conductivity and stability of the electrolyte salt after the electrolyte salt and the initiator are completely dissolved.

8. The method for preparing an in-situ assembled all-solid battery according to claim 1, wherein the heating temperature is 60 ℃ to 100 ℃ and the heating time is 60s to 120s, the power of the ultraviolet light is 50mW/cm ² to 2000mW/cm ², and the irradiation time is 60s to 120 s;

The electrolyte salt is lithium salt, sodium salt, potassium salt or zinc salt; the polymer monomer is polyethylene glycol dimethacrylate or polyethylene glycol diacrylate; the cross-linking agent is tetraethyleneglycol diacrylate; the initiator is a thermal initiator or a photoinitiator;

Preferably, the thermal initiator is azobisisobutyronitrile and the photoinitiator is 2-hydroxy-2-methyl propiophenone.

9. The method of manufacturing an in-situ assembled all-solid battery according to claim 7, wherein the concentration of the electrolyte salt in the electrolyte precursor is 0.5mol/L to 2 mol/L; the mass ratio of the polymer monomer to the cross-linking agent is (12-19): (1-8); the mass of the initiator is 1-5% of the sum of the mass of the polymer monomer and the mass of the cross-linking agent; the mass of the inorganic ceramic filler is less than or equal to 20% of the sum of the mass of the polymer monomer and the mass of the cross-linking agent;

The inorganic ceramic filler is lanthanum lithium zirconate nano-particles doped with metal ions, and the metal ions are gallium ions, neodymium ions, tantalum ions or niobium ions.

10. An in-situ assembled all-solid-state battery prepared by the method of any one of claims 6 to 9.

Technical Field

The invention belongs to the technical field of ionic cell preparation, and particularly relates to a polymeric organic-inorganic composite solid electrolyte and an in-situ assembled all-solid-state cell.

Background

the lithium ion battery is widely applied to the fields of mobile electronic equipment, electric automobiles and the like as a novel energy storage device. At present, the traditional commercial lithium ion battery mainly adopts liquid organic electrolyte, so that serious safety problems such as combustion, leakage and the like are easily caused. Meanwhile, the stability of the liquid electrolyte is poor, and the electrochemical window is narrow, so that the energy density of the liquid electrolyte is low. The solid electrolyte has higher safety and thermal stability than a liquid electrolyte. Meanwhile, the solid electrolyte is stable to metal lithium, and can well inhibit the growth of lithium dendrites. In addition, the solid electrolyte has a wider electrochemical window, and can be well applied to high-voltage lithium metal batteries, so that the energy density of the lithium ion batteries is further improved.

At present, solid electrolytes are mainly classified into two types, i.e., inorganic ceramic electrolytes and organic polymer electrolytes. In general, ceramic electrolytes have better lithium ion conductivity and transport number, and better electrochemical stability. However, the brittleness of ceramics increases their processing difficulty. More importantly, the large interfacial resistance between the electrolyte and the electrodes is almost a gap that is difficult for a solid-state battery to overcome. The polymer electrolyte has small interface resistance, is easy to process and form and is suitable for large-scale production. But the electrochemical stability of the polymer electrolyte is poor, and the ionic conductivity and the transference number are low. Therefore, the organic-inorganic composite electrolyte seems to be the best choice. The composite electrolyte takes polymer as a matrix and has good flexibility. And by adding the inorganic electrolyte particles, the ionic conductivity and the electrochemical stability of the electrolyte can be effectively improved.

currently, polyethylene oxide (PEO) -based solid composite electrolytes are most studied. However, the oxidation potential of PEO is less than 4V, resulting in a narrow electrochemical window, which is difficult to apply to high voltage positive electrode materials. The polymer electrolyte with a cross-linked structure has good chemical stability, but the synthesis method is complicated, toxic organic solvents are introduced, or the requirement on the external environment is high. Nevertheless, the problem of interfacial resistance is still in need of solution due to the defects on the surface of the solid electrolyte or electrode material.

Disclosure of Invention

the invention solves the problems of low conductivity of polymer solid electrolyte and large interface resistance of an all-solid-state battery in the prior art, and provides a polymeric organic-inorganic composite solid electrolyte and an in-situ assembled all-solid-state battery. Fully and uniformly mixing a polymer monomer and a cross-linking agent, and then adding electrolyte salt and an initiator to obtain an electrolyte precursor; heating the electrolyte precursor or carrying out ultraviolet radiation to enable the initiator to initiate the polymer monomer and the cross-linking agent to carry out cross-linking polymerization reaction to form a polymer, and obtaining the polymer solid electrolyte. The ionic conductivity of the polymer composite solid electrolyte prepared by the invention is greatly improved, and the interface resistance of the all-solid-state battery assembled by utilizing the in-situ polymerization technology is greatly reduced, so that the battery performance is more excellent.

According to a first aspect of the present invention, there is provided a method of preparing a polymeric solid electrolyte comprising the steps of:

(1) fully and uniformly mixing a polymer monomer and a cross-linking agent, adding electrolyte salt and an initiator, and completely dissolving to obtain an electrolyte precursor;

(2) And (2) heating the electrolyte precursor obtained in the step (1), or carrying out ultraviolet radiation, so that the initiator initiates the polymer monomer and the cross-linking agent to carry out cross-linking polymerization reaction to form a polymer, and then the polymeric solid electrolyte is obtained.

Preferably, in the step (1), after the electrolyte salt and the initiator are completely dissolved, a step of adding an inorganic ceramic filler is further included, and the inorganic ceramic filler is used for improving the conductivity and stability of the electrolyte salt.

Preferably, the heating temperature is 60-100 ℃, the heating time is 60-120 s, the power of the ultraviolet light is 50mW/cm ² -2000mW/cm ², and the radiation time is 60-120 s;

The electrolyte salt is lithium salt, sodium salt, potassium salt or zinc salt; the polymer monomer is polyethylene glycol dimethacrylate or polyethylene glycol diacrylate; the cross-linking agent is tetraethyleneglycol diacrylate; the initiator is a thermal initiator or a photoinitiator;

preferably, the thermal initiator is azobisisobutyronitrile and the photoinitiator is 2-hydroxy-2-methyl propiophenone.

Preferably, the concentration of the electrolyte salt in the electrolyte precursor is 0.5mol/L-2 mol/L; the mass ratio of the polymer monomer to the cross-linking agent is (12-19): (1-8); the mass of the initiator is 1-5% of the sum of the mass of the polymer monomer and the mass of the cross-linking agent; the mass of the inorganic ceramic filler is less than or equal to 20% of the sum of the mass of the polymer monomer and the mass of the cross-linking agent;

The inorganic ceramic filler is lanthanum lithium zirconate nano-particles doped with metal ions, and the metal ions are gallium ions, neodymium ions, tantalum ions or niobium ions.

According to another aspect of the present invention there is provided a polymeric solid electrolyte prepared by any of the methods described herein.

According to another aspect of the present invention, there is provided a method of manufacturing an in-situ assembled all-solid battery, including the steps of:

(1) Fully and uniformly mixing a polymer monomer and a cross-linking agent, adding electrolyte salt and an initiator, and completely dissolving to obtain an electrolyte precursor;

(2) Dropping the electrolyte precursor obtained in the step (1) on a positive electrode, then covering a negative electrode on the electrolyte precursor, heating or carrying out ultraviolet radiation to enable the initiator to initiate the polymer monomer and the cross-linking agent to carry out cross-linking polymerization reaction to form a polymer, and curing the electrolyte precursor to obtain the in-situ assembled all-solid-state battery.

Preferably, in the step (1), after the electrolyte salt and the initiator are completely dissolved, a step of adding an inorganic ceramic filler is further included, and the inorganic ceramic filler is used for improving the conductivity and stability of the electrolyte salt.

Preferably, the heating temperature is 60-100 ℃, the heating time is 60-120 s, the power of the ultraviolet light is 50mW/cm ² -2000mW/cm ², and the radiation time is 60-120 s;

The electrolyte salt is lithium salt, sodium salt, potassium salt or zinc salt; the polymer monomer is polyethylene glycol dimethacrylate or polyethylene glycol diacrylate; the cross-linking agent is tetraethyleneglycol diacrylate; the initiator is a thermal initiator or a photoinitiator;

Preferably, the thermal initiator is azobisisobutyronitrile and the photoinitiator is 2-hydroxy-2-methyl propiophenone.

Preferably, the concentration of the electrolyte salt in the electrolyte precursor is 0.5mol/L-2 mol/L; the mass ratio of the polymer monomer to the cross-linking agent is (12-19): (1-8); the mass of the initiator is 1-5% of the sum of the mass of the polymer monomer and the mass of the cross-linking agent; the mass of the inorganic ceramic filler is less than or equal to 20% of the sum of the mass of the polymer monomer and the mass of the cross-linking agent;

The inorganic ceramic filler is lanthanum lithium zirconate nano-particles doped with metal ions, and the metal ions are gallium ions, neodymium ions, tantalum ions or niobium ions.

According to another aspect of the present invention, there is provided an in-situ assembled all-solid-state battery prepared by any one of the methods.

Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:

(1) The invention provides a technology for preparing a solid composite electrolyte and assembling an all-solid-state lithium ion battery by in-situ polymerization. By utilizing the fluidity of the liquid precursor and the good wettability to the electrode material, the defects and gaps caused by solid-solid contact can be reduced, and the tightness of interface contact is increased, so that the aim of reducing the interface resistance is fulfilled.

(2) The invention utilizes the in-situ technology, directly solidifies between the anode and the cathode, reduces the defects and gaps caused by solid-solid contact and increases the tightness of interface contact by utilizing the liquidity of the liquid precursor and the wettability of the liquid precursor to the electrode, thereby effectively reducing the interface resistance. (interfacial resistance is reduced to one-half of that of ex-situ technology).

(3) according to the invention, the cross-linking agent is introduced, and the constructed composite electrolyte with a cross-linking structure further reduces the crystallinity of the polymer, so that the lithium ion conductivity of the composite electrolyte is greatly increased. In addition, the cross-linked structure can increase the action among polymer chain segments, can effectively improve the mechanical strength and the thermal stability of the composite electrolyte, ensure the reliability of the composite electrolyte in the assembly process of the all-solid battery, simultaneously improve the capability of the composite electrolyte for inhibiting the growth of lithium dendrites, and ensure the safety of the all-solid battery in the use process.

(4) The in-situ polymerization process provided by the invention is simple, has low equipment requirement (only stirring equipment and a heat source/ultraviolet light source are needed), has short polymerization time (<90s), has low polymerization temperature (<100 ℃) or ultraviolet light power (<200W), and has the characteristics of low equipment investment, short production period and low energy consumption requirement. The invention uses electrolyte salt and active filler in other ion batteries, and the polymerization is also applicable to other ion batteries, such as: sodium ion batteries, potassium ion batteries, zinc ion batteries, and the like. The electrolyte prepared by the invention has flexibility and can be assembled into a flexible all-solid-state battery. Therefore, the method is suitable for the leading-edge application fields of flexible devices such as microelectronic mechanical systems, electric automobiles and wearable electronic equipment besides the traditional application fields.

(5) In the present invention, it is preferable to introduce inorganic ceramic particles as a filler, uniformly dispersed in a precursor of the polymer electrolyte. The electrochemical window of the prepared polymer electrolyte reaches 6V, so that the polymer electrolyte can be well applied to high-voltage metal batteries. The precursor used in the invention has simple components, does not need to introduce toxic and harmful organic solvents, can realize zero emission, and has the characteristic of environmental friendliness. In addition, the component of the zero organic solvent eliminates the side reaction possibly existing between the precursor and the electrolyte salt or the active filler.

^-4(6) According to the in-situ solidified electrolyte provided by the invention, the inorganic ceramic filler of the active nano particles is added into the electrolyte, so that the ionic conductivity of the electrolyte is improved, and finally, the energy storage device with excellent electrochemical characteristics, adjustable forming, safety and stability is obtained.

(7) According to the invention, preferably, the polymer monomer is polyethylene glycol dimethacrylate or polyethylene glycol diacrylate, the polymer monomer forms a basic matrix of the composite electrolyte after polymerization, and the cross-linking agent is tetraethyleneglycol diacrylate, so that a three-dimensional network structure is constructed, and the electrochemical stability of the electrolyte and the migration of lithium ions are enhanced. The thermal initiator is azodiisobutyronitrile, the photoinitiator is 2-hydroxy-2-methyl propiophenone, and the polymerization of the monomers is initiated.

(8) The room-temperature conductivity of the solid electrolyte reaches 1.6 multiplied by 10 ^-4 S cm ^-1, the electrochemical window is larger than 6V, and the all-solid-state battery based on the solid electrolyte has the discharge capacity density of 145mAh/g under the charge-discharge rate of 0.5C, the discharge capacity of 176mAh/g under 0.1C and the capacity retention rate of 88 percent after 100 cycles under 0.5C.

Drawings

FIG. 1 is a graph showing the lithium ion conductivity of electrolytes prepared according to the present invention, taking as an example samples prepared in examples 1,2,3,4, 5.

FIG. 2 is an example of a sample prepared in example 1 showing the electrochemical window of an electrolyte prepared according to the present invention.

FIG. 3 is a diagram illustrating the charge and discharge test of a symmetrical battery in which the electrolyte membrane prepared according to the present invention uses metallic lithium as an electrode, taking the sample prepared in example 1 as an example.

fig. 4 is a schematic diagram of a charge/discharge test of a solid-state lithium ion battery prepared according to the present invention, taking the sample prepared in example 1 as an example.

Fig. 5 is a schematic diagram of the discharge capacity of the solid-state lithium ion battery prepared according to the present invention at different rates, taking the sample prepared in example 1 as an example.

FIG. 6 is a schematic view of cycle life analysis of a solid-state lithium ion battery prepared according to the present invention, taking the sample prepared in example 1 as an example.

Detailed Description

in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

The main advantage of the in-situ polymerization technique is that the interfacial resistance of the all-solid battery can be effectively reduced. The conventional battery assembly method is mainly to assemble a positive electrode, an electrolyte and a negative electrode in a laminated manner. Therefore, the contact between the electrode and the electrolyte is poor, resulting in a large interface resistance between the electrode and the electrolyte. The problem of interfacial resistance is almost the largest barrier to the development of all-solid-state batteries at present. The in-situ polymerization technology utilizes the fluidity and the wettability of the liquid precursor, effectively eliminates the defects of the electrode surface, and increases the tightness of interface contact, so that the interface resistance can be effectively reduced.

The ionic conductivity and the electrochemical stability of the composite electrolyte with the cross-linked structure are greatly improved, the mechanical strength of the prepared electrolyte and the capability of inhibiting the generation of lithium dendrites are also enhanced, and the reliability and the safety of the battery in the processes of packaging, charging and discharging are ensured.

based on the structure, the invention provides a polymeric organic-inorganic composite solid electrolyte and an in-situ assembled all-solid-state battery. Preferably, the components thereof comprise a liquid electrolyte precursor and an active ceramic electrolyte filler, said active ceramic electrolyte filler being homogeneously dispersed in said liquid electrolyte precursor, wherein:

The liquid electrolyte comprises a polymer monomer, a cross-linking agent, an initiator and an electrolyte salt dissolved in the liquid monomer. The polymer monomer and the cross-linking agent are subjected to polymerization reaction to form a polymer matrix with a net-shaped cross-linking structure, and the initiator is used for initiating the cross-linking polymerization reaction.

The active ceramic electrolyte filler is ceramic powder with electrolyte salt ion conductivity; can be used to improve the conductivity and electrochemical stability of lithium ions in the electrolyte. The electrolyte salt is dissolved in the matrix, mainly increasing the concentration of the freely movable electrolyte salt ions.

The in-situ polymerization technology of the invention is to directly polymerize the liquid electrolyte precursor on the anode/cathode to form the all-solid-state battery, thereby achieving the purposes of eliminating the interface defect and reducing the interface resistance.

in some embodiments of the present invention, polyethylene glycol dimethacrylate (pegmda) or polyethylene glycol diacrylate (PEGDA) is a monomer, tetraethylene glycol diacrylate (TEGDA) is a cross-linking agent, azobisisobutyronitrile is a thermal initiator, or a photoinitiator is used, and the mass ratio of the polymer monomer to the cross-linking agent is (12-19): (1-8); the mass of the initiator is 1-5% of the sum of the mass of the polymer monomer and the mass of the cross-linking agent, and the concentration of the electrolyte salt is 0.5-2 mol/L.

The active ceramic electrolyte filler of the present invention is preferably various active nanoparticles capable of improving lithium ion conductivity. In some embodiments, the active nanoparticles are lanthanum lithium zirconate nanoparticles doped with metal ions, the metal ions being Ga, Zr, Nb, Ru, and the like. The active nano-particles can be obtained according to a conventional preparation method, salts corresponding to the active nano-particles can be sequentially added into ethylene glycol, and then citric acid monohydrate is added to be stirred to obtain a clear solution; and heating, refluxing, aging and carbonizing the obtained clear solution, and then calcining at high temperature to obtain the active nano particles. Or directly synthesizing the ceramic powder by a solid phase method.

In some embodiments, the inorganic ceramic filler has a mass equal to or less than 20% of the sum of the masses of the polymer monomer and the crosslinker.

The invention also provides a method for preparing the solid electrolyte and the all-solid-state battery by the in-situ polymerization technology, which comprises the following steps:

(1) The negative electrode comprises a metallic lithium plate with a thickness of 300 microns, and is directly purchased.

(2) The active substances of the positive electrode material are mainly LiNi _0.6 Co _0.2 Mn _0.2 O ₂ (NCM), LiNi _0.85 Co _0.05 Al _0.1 O ₂ (NCA) and LiFePO ₄ (LFP), the conductive agent is mainly Super-P, the binder is polyvinylidene fluoride (PVDF), and the methyl pyrrolidone (NMP) is polyvinylidene fluoride (PVDF) solvent, the proportion of the active material, the Super-P and the polyvinylidene fluoride (PVDF) is 8:1:1, and the mass concentration of the polyvinylidene fluoride (PVDF) in the methyl pyrrolidone (NMP) is 2%.

(3) the in-situ solidification technology of the solid electrolyte is to directly drip the precursor of the electrolyte liquid on the electrode and then solidify the precursor into the solid electrolyte under the heat source/light source to form the lamination of the anode, the solid electrolyte and the cathode.

(4) And arranging a current collector on the lamination layer and compacting to obtain the all-solid-state lithium ion battery.

The polymerization method is thermal polymerization or photo polymerization, and the needed devices respectively correspond to a heating device and an ultraviolet lamp.

The current collector can adopt various conventional lithium battery current collectors, including a positive electrode current collector which is a carbon-coated aluminum foil and a negative electrode current collector which is a copper foil.

The lithium salt used for the electrolyte salt mainly comprises LiClO ₄, LiPF ₆ or LiTFSI.

The invention adopts an in-situ polymerization technology to prepare a solid lithium battery, which comprises the following steps:

(1) Preparing a liquid precursor: uniformly mixing the liquid polymer monomer and the cross-linking agent according to a certain proportion, then adding the solid organic lithium salt and the initiator, and stirring until the solid organic lithium salt and the initiator are completely dissolved. Then adding ceramic electrolyte filler, and stirring until the mixture is uniformly dispersed to obtain a completely and uniformly mixed liquid precursor;

(2) preparing an active ceramic electrolyte filler: corresponding salts can be sequentially added into ethylene glycol, and then citric acid monohydrate is added to be stirred to obtain a clear solution; and heating, refluxing, aging and carbonizing the obtained clear solution, and then calcining at high temperature to obtain the active nano particles. In some embodiments, the heat treatment temperature of the carbide is set to 600 to 900 ℃, the temperature rise rate is 5 ℃/min, and the carbonization time is 24 to 48 hours. The active ceramic electrolyte filler can also be formed by solid phase reaction or the nanofiber filler can be prepared by electrospinning.

(3) Preparing a composite positive electrode: PVDF and NMP in a given proportion are mixed and stirred until the PVDF is completely dissolved, then an active electrode material and a conductive agent super-P are respectively added, and then the mixture is stirred to form a completely and uniformly mixed positive electrode slurry. And then coating the positive electrode slurry on a positive electrode current collector, and heating and drying to obtain the positive electrode film.

(4) In-situ curing of the solid electrolyte: dropping liquid electrolyte precursor onto the positive electrode, lightly covering the metal lithium sheet negative electrode, carefully moving the metal lithium sheet negative electrode on a heat/ultraviolet radiation device, and after 90s, completely curing the electrolyte, namely forming an integrated lamination comprising the positive electrode, the electrolyte and the negative electrode in situ.

(5) Assembling the solid lithium ion battery: and attaching a negative current collector to the negative electrode which comprises the positive current collector, the positive layer, the electrolyte and the negative integrated lamination, and then packaging on a packaging machine to obtain the in-situ polymerized all-solid-state battery.

Preferably, the present invention provides a method for preparing a solid-state lithium ion battery by using an in-situ polymerization technique, comprising: the method comprises the steps of directly polymerizing a polymer monomer capable of ring-opening polymerization, a cross-linking agent, an initiator, lithium salt and a ceramic electrolyte filler on a positive electrode and a negative electrode of a lithium ion battery, thereby preparing the all-solid-state lithium ion battery. The technology can realize the integrated molding of various solid lithium ion batteries with macro microstructures, and effectively solves the interface compatibility and process compatibility among the anode, the cathode and the solid electrolyte material. The electrochemical energy storage device which has excellent electrochemical characteristics, mechanical flexibility, safety and stability, controllable shape and rapid forming can be obtained through the invention. The solid-state lithium ion battery is not only suitable for the traditional application field of the lithium ion battery, but also suitable for the front-edge application field of integrated circuits, electric automobiles, wearable electronic equipment and the like with higher requirements on shapes and forming speeds.