WO2017190367A1

WO2017190367A1 - Secondary battery and preparation method therefor

Info

Publication number: WO2017190367A1
Application number: PCT/CN2016/081349
Authority: WO
Inventors: 唐永炳; 季必发; 张帆
Original assignee: 深圳先进技术研究院
Priority date: 2016-05-06
Filing date: 2016-05-06
Publication date: 2017-11-09
Also published as: CN109155433A

Abstract

The present invention relates to the battery field, and in particular, to a secondary battery and a preparation method therefor. The secondary battery comprises a battery negative electrode, a battery positive electrode and an all-solid electrolyte layer, the battery negative electrode comprising a negative electrode current collector and not comprising a negative electrode active material, the all-solid electrolyte layer being an inorganic solid electrolyte, the battery positive electrode comprising a positive electrode current collector and a positive electrode active material layer, the positive electrode active material layer comprising a positive electrode active material that freely and reversibly deintercalates lithium ions, sodium ions or magnesium ions. By using the all-solid electrolyte layer, the secondary battery does not easily corrode electrode materials and is able to maintain a chemical stability over a wide temperature range, increasing the service life of the battery; meanwhile, by using the all-solid electrolyte layer, the secondary battery needs no separator, reducing the volume and overall mass of the battery, and increasing the energy density of the battery; and by excluding negative electrode active substance, the secondary battery not only reduces the production cost of the battery, but also effectively improves the capacity and energy density of the battery, and shows a good charge and discharge cycle performance.

Description

Secondary battery and preparation method thereof

Technical field

The present invention relates to the field of batteries, and in particular to a secondary battery and a method of fabricating the same.

Background technique

A secondary battery, also called a rechargeable battery, is a battery that can be repeatedly charged and discharged and used multiple times. Compared with a non-reusable primary battery, the secondary battery has the advantages of low cost of use and low environmental pollution. At present, the main secondary battery technologies are lead-acid batteries, nickel-chromium batteries, nickel-hydrogen batteries, and lithium-ion batteries. Among them, lithium ion batteries are the most widely used. Lithium-ion batteries have become the power source for electric vehicles and power tools because of their high power density, low self-discharge rate, no memory effect and stable discharge voltage. The core components of a lithium ion battery usually contain a positive electrode, a negative electrode, an electrolyte, and a separator. Typical cathode materials are usually lithium cobaltate (LiCoO ₂ ), lithium nickelate (LiNiO ₂ ), lithium manganate (LiMn ₂ O ₄ ), lithium iron phosphate (LiFePO ₄ ), lithium nickel cobaltate binary material (LiNi _{1 -x} Co _x O ₂ ), spinel structure (LiMn _2-x M _x O ₄ , M=Ni, Co, Cr, etc.), lithium nickel cobalt manganese ternary material [Li(Ni, Co, Mn)O ₂ ], a layered lithium-rich high manganese material [Li ₂ MnO ₃ -Li(NiCoMn)O ₂ or the like. At present, batteries with high specific capacity, high voltage, and high energy density use almost all kinds of liquid organic electrolytes. Commonly used liquid electrolytes have disadvantages such as low specific energy, easy corrosion of electrode materials, difficulty in design and assembly, poor safety, and low service life. In all batteries using a liquid organic electrolyte, it is also necessary to use a porous polymer separator which functions to allow ions to pass while physically isolating the positive and negative active materials. Polyethylene or polypropylene film as a separator of a battery has the following problems: its heat resistance is poor, and at the same time, in order to make the film have sufficient strength, the film must have a certain thickness lower limit, which limits the further increase in battery capacity. If the film thickness is simply reduced, the local strength of the film will be insufficient, and at the same time, the shape defects will be caused at high temperatures, so the space for reducing the thickness of these films is limited. The organic electrolyte secondary battery needs to further reduce the volume, increase the specific capacity and voltage, and further reduce the thickness of the separator. Therefore, there is a need to provide a secondary battery to solve the problems of low-energy, easy-corrosion electrode materials, poor design and assembly, poor safety, low service life, and the necessity of using a separator. In addition, the negative electrode of the conventional lithium ion battery must contain a negative active material and a negative current collector, wherein the negative active material occupies a large part of the volume and weight, which limits the battery capacity and energy density of the lithium ion battery.

Summary of the invention

In order to overcome the above technical problems, the present invention provides a secondary battery and a preparation method thereof, which are intended to solve the problems of low specific energy, easy corrosion of electrode materials, poor design and assembly, poor safety, and low service life of existing liquid electrolytes. Problems such as diaphragms must be used. In addition, the present invention directly solves the problem of low battery capacity and energy density by using the negative electrode current collector as the negative electrode.

In a first aspect, the present invention provides a secondary battery including a battery negative electrode and a battery positive electrode; and further comprising an all-solid electrolyte layer, wherein

The negative electrode of the battery includes a negative current collector, and does not include a negative active material; the negative current collector includes a metal, a metal alloy or a metal composite conductive material;

The all solid electrolyte layer includes an inorganic solid electrolyte;

The positive electrode of the battery includes a positive current collector and a positive active material layer, the positive current collector includes a metal, a metal alloy or a metal composite conductive material, and the positive active material layer includes a positive electrode capable of reversibly deintercalating lithium, sodium or magnesium ions. Active material.

Preferably, the anode current collector comprises one of aluminum, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese or a composite of any one of them or an alloy of any one of them .

Preferably, the anode current collector is aluminum.

Preferably, the structure of the anode current collector is a multi-layer composite structure of porous aluminum or aluminum coated with aluminum foil or porous aluminum or carbon material.

Preferably, the cathode current collector comprises one of aluminum, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese or a composite of any one of them or an alloy of any one of them .

Preferably, the cathode current collector is aluminum.

Preferably, the inorganic solid electrolyte comprises a perovskite crystalline electrolyte, an inverse perovskite crystalline electrolyte, a superionic conductor type crystalline electrolyte, a fast ion conductive crystalline electrolyte, a garnet crystalline electrolyte or nitrogen. One or more of a lithium-type crystalline electrolyte, a lithium phosphorus-oxygen-nitrogen amorphous electrolyte, an amorphous sulfide amorphous electrolyte, and a composite electrolyte.

Preferably, the positive electrode active material comprises lithium cobaltate, lithium nickelate, lithium manganate, lithium iron phosphate, lithium nickel cobaltate binary material, spinel structure oxide, lithium nickel cobalt manganese ternary material, layer A composite material of one or more or any one of lithium-rich high manganese materials.

Preferably, the positive electrode active material layer further comprises a conductive agent and a binder, the positive electrode active material is contained in an amount of 60 to 95% by weight, the conductive agent is contained in an amount of 0.1 to 30% by weight, and the binder is contained in an amount of 0.1 to 10% by weight. %.

In a second aspect, the present invention also provides a method for preparing a secondary battery, the method comprising:

Preparing a battery negative electrode, cutting a metal, metal alloy or metal composite conductive material into a desired size, and then washing the surface of the cut metal, metal alloy or metal composite conductive material, the washed metal, a metal alloy or a metal composite conductive material as a battery negative electrode;

Preparing a solid electrolyte, and cutting the above inorganic solid electrolyte layer into a certain shape and size for use;

Prepare the positive electrode of the battery, weigh the living positive material, the conductive agent and the binder according to a certain ratio, add it into a suitable slurry and fully grind it into a uniform slurry, and then uniformly apply it to the surface of the positive current collector, and then cut the slurry after it is completely dried. Cutting to obtain a positive electrode of a desired size, the positive active material being a metal oxide or a metal compound;

Assembly is performed using the battery negative electrode, the solid electrolyte layer, and the battery positive electrode.

Compared with the prior art, the invention has the beneficial effects that the solid electrolyte layer is used instead of the common liquid organic electrolyte, the electrode material is not easily corroded, the chemical stability can be maintained over a wide temperature range, and the use of the battery is increased. Life expectancy and greatly improve the safety of the battery and reduce the battery The cost of packaging, in addition to the cation diffusion rate (ion conductivity) in the solid state is higher than that of the liquid electrolyte, theoretically it can achieve higher output; because the solid electrolyte layer is used, no diaphragm is needed, which reduces the volume of the battery and reduces the volume. The overall quality of the battery increases the energy density of the battery; at the same time, the secondary battery provided by the invention cancels the negative active material, and directly uses the metal or the metal alloy or the metal composite as the negative electrode and the current collector, thereby not only reducing the cost of the battery production, but also simplifying The production process can also effectively improve the battery capacity and energy density of the battery, and exhibit good charge and discharge cycle performance.

DRAWINGS

FIG. 1 is a schematic structural view of a secondary battery according to an embodiment of the present invention.

detailed description

The present invention will be further described in detail below in conjunction with the drawings and specific embodiments. The following are the preferred embodiments of the present invention, and it should be noted that those skilled in the art can also make several improvements and retouchings without departing from the principles of the embodiments of the present invention. It is also considered to be the scope of protection of the present invention.

FIG. 1 is a schematic structural diagram of a secondary battery according to an embodiment of the present invention. Referring to FIG. 1 , a secondary battery provided by an embodiment of the present invention includes a battery negative electrode 4, an all-solid electrolyte layer 3, and a battery positive electrode, wherein the battery negative electrode includes a negative electrode current collector and does not include a negative electrode active material; the negative electrode current collector is metal, Metal alloy or metal composite conductive material. The all-solid electrolyte layer includes an inorganic solid electrolyte; the battery positive electrode includes a positive electrode current collector 1 and a positive electrode active material layer 2, the positive electrode current collector is a metal, a metal alloy or a metal composite conductive material, and the positive electrode active material includes a reversible deintercalation lithium ion A positive electrode active material of sodium ion or magnesium ion, as long as lithium ion, sodium ion or magnesium ion is allowed to freely escape and intercalate, such as lithium, sodium or magnesium transition metal oxide and its doped binary or ternary transition Metal oxides, etc.

The working principle of the secondary battery provided by the embodiment of the present invention is: the secondary battery provided by the embodiment of the present invention does not contain the negative current collector, and during the charging process, the positive active material is delithiated, sodium or magnesium, and directly connected with the all solid electrolyte layer. The metal or metal alloy of the negative electrode reacts to form a lithium-metal alloy, a sodium-metal alloy or a magnesium-metal alloy; during discharge, the lithium-metal alloy of the negative electrode, the sodium-metal alloy or the delithium, sodium or magnesium The charge and discharge process is realized by embedding an all-solid electrolyte layer in the positive electrode active material.

The secondary battery provided by the embodiment of the invention replaces the common liquid organic electrolyte by using the all-solid electrolyte layer, and is not easy to corrode the electrode material, can maintain chemical stability over a wide temperature range, and increases the service life of the battery, and The safety performance of the battery is greatly improved, and the packaging cost of the battery is lowered. In addition, the diffusion speed (ion conductivity) of the cation in the solid state is higher than that of the liquid electrolyte, which can achieve higher output; The diaphragm is required, the battery volume is reduced, the overall quality of the battery is reduced, and the energy density of the battery is increased. Meanwhile, the secondary battery provided by the invention cancels the negative active material, and directly uses a metal or a metal alloy or a metal composite as a negative electrode and a set. The fluid not only reduces the cost of battery production, but also simplifies the production process, and at the same time effectively increases the battery capacity and energy density of the battery, and exhibits good charge and discharge cycle performance.

In the embodiment of the present invention, preferably, the anode current collector comprises one or a combination of any one of aluminum, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese or any one of them. Several alloys. Further, the anode current collector is preferably aluminum.

In the embodiment of the present invention, more preferably, the anode current collector is a multi-layer composite material of porous aluminum and other aluminum coated with aluminum foil or porous aluminum or carbon material. The lithium ion which uses the porous aluminum foil to remove the positive active material is more fully reacted with the metal aluminum alloy to increase the battery capacity; and the carbon layer coated porous aluminum foil structure maintains the capacity of the battery, and the aluminum foil is maintained by the protection of the carbon layer. The structure further improves the cycle stability of the battery; the use of the multi-layer aluminum composite material is also advantageous for suppressing and improving the volume expansion effect of the aluminum foil and improving the cycle performance of the battery.

In the embodiment of the present invention, preferably, the cathode current collector comprises one or a combination of any one of aluminum, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese or any one of them. Several alloys. Further, the cathode current collector is preferably aluminum.

In an embodiment of the invention, the inorganic solid electrolyte comprises a perovskite crystalline electrolyte, an inverse perovskite crystalline electrolyte, a superionic conductor crystalline electrolyte, a fast ion conductive crystalline electrolyte, and a garnet crystal. One or more of a state electrolyte or a lithium nitride type crystalline electrolyte, a lithium phosphorus oxynitride amorphous electrolyte, an amorphous sulfide amorphous electrolyte, and a composite electrolyte, for example, Li _0.5 La _0.5 TiO ₃ , Li _3x La _2/3-x TiO ₃ (x=0.11), Li _3-x-δ M _x/2 O(A _1-z A _z' ) _1-δ , Li _3-n (OH _n )Cl(0.83 ≤n≤2), Li _3-n (OH _n )Br(1≤n≤2), AM ₁ M ₂ P ₃ O ₁₂ (A=Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , H ⁺ , H ₃ O ⁺ , NH ₄ ⁺ , Cu ⁺ , Cu ²⁺ , Ag ⁺ , Pb ²⁺ , Cd ²⁺ , Mn ²⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ , Al ³⁺ , Ln ³⁺ (Ln is a rare earth element), Ge ⁴⁺ , Zr ⁴⁺ , Hf ⁴⁺ or vacancies; M=Zn ²⁺ , Cd ²⁺ , Ni ²⁺ , Mn ²⁺ , Co ²⁺ , Fe ³⁺ , Sc ³⁺ , Ti ³⁺ , V ³⁺ , Cr ³⁺ , Al ³⁺ , In ³⁺ , Ga ³⁺ , Y ³⁺ , Ln ^{3 +} , Ti ⁴⁺ , Zr ⁴⁺ , Hf ⁴⁺ , Sn ⁴⁺ , Si ^{4 +} , Ge ⁴⁺ , V ⁵⁺ , Nb ⁵⁺ , Ta ⁵⁺ , Sb ⁵⁺ , As ⁵⁺ ), Li _2+2x Zn _1-x GeO ₄ , Li _3+x X _x Y _1-x O ₄ (X=Si, Sc, Ge, Ti; Y=P, As, V, Cr), Li _3+x X _x Y _1-x S ₄ (X=Si, Sc, Ge, Ti; Y=P, As , V, Cr), Li ₅ La ₃ M ₂ O ₁₂ (M=Ta, Nb), Li ₃ N, Li ₃ N-LiXLiX (X=Cl, Br, I), Li _9-nx M _x N ₂ Cl ₃ (M=Na, K, Rb, Cs, Mg, Al), 3Li ₃ N-MI (M=Li, Na, K), LiPON, Li ₂ S, Li ₂ SM _x S _y (M=Al, Si , P), Li ₂ S-SiS ₂ -Li _x MO _y (M=Si, P, B, Al, Ga, In), Li ₂ SP ₂ S ₅ , Al ₂ O ₃ and LiI and other types of composites One or several.

Preferably, in the embodiment of the present invention, the positive electrode active material in the positive electrode active layer is also not particularly limited as long as the anion can be reversibly extracted or embedded. For example, if the inorganic solid electrolyte is a lithium salt electrolyte, the positive electrode active material is selected from lithium cobaltate (LiCoO ₂ ), lithium nickelate (LiNiO ₂ ), lithium manganate (LiMn ₂ O ₄ ), lithium iron phosphate (LiFePO ₄ ). , lithium nickel cobaltate binary material (LiNi _1-x Co _x O ₂ ), spinel structure (LiMn _2-x M _x O ₄ , M=Ni, Co, Cr, etc.), lithium cobalt cobalt manganate ternary Material [Li(Ni,Co,Mn)O ₂ ], layered lithium-rich high manganese material [Li ₂ MnO ₃ -Li(NiCoMn)O ₂ ], NAS 3ION structure Li ₃ M ₂ (PO ₄ ) ₃ (M= A composite material of one or more of V, Fe, Ti, etc. or any one or any of them. If the inorganic solid electrolyte is a sodium salt electrolyte, the positive electrode active material may be a sodium phosphate polyanion compound, a ferricyanide and a Prussian blue complex, an active redox polymer, a tunnel structure compound, a spinel oxide, One or more of the layered transition metal oxides. For example: it can be Na ₂ V ₃ (PO ₄ ) ₃ , Na ₂ Zn ₃ [Fe(CN) ₆ ] _2` xH ₂ O, Na ₂ Fe(SO ₄ ) ₂ , NaMn ₂ O ₄ , Na _0.61 [Mn _0.27 One or more of Fe _0.34 Ti _0.39 ]O ₂ and NaCoO ₂ .

In the embodiment of the present invention, the positive electrode active material layer further includes a conductive agent and a binder, the content of the positive electrode active material is 60-95 wt%, the content of the conductive agent is 0.1-30 wt%, and the content of the binder is 0.1-10 wt%. . Meanwhile, the conductive agent and the binder are not particularly limited and may be used in the art. The conductive agent is one or more of conductive carbon black, Super P conductive carbon sphere, conductive graphite KS6, carbon nanotube, conductive carbon fiber, graphene, and reduced graphene oxide. The binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, and polyolefin.

In a second aspect, the embodiment of the invention further provides a method for preparing the above secondary battery, comprising:

Step 101: Prepare a battery negative electrode.

Cutting a metal, metal alloy or metal composite conductive material into a desired size, and then washing the surface of the cut metal, metal alloy or metal composite conductive material, and cleaning the metal, metal alloy or metal a composite conductive material as a battery negative electrode;

Specifically, the metal, metal alloy or metal composite conductive material comprises one or a combination of any one of aluminum, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese or Any alloy may be a metal or metal alloy foil.

Step 102, preparing a solid electrolyte, and cutting the inorganic solid electrolyte layer into a certain shape and size for use;

Step 103, preparing a battery positive electrode. The preparation of the positive electrode of the battery comprises: weighing the positive positive electrode material, the conductive agent and the binder according to a certain ratio, adding the appropriate slurry to the uniform slurry, and uniformly coating the surface of the positive current collector, and then performing the slurry completely after drying. The battery is cut to obtain a positive electrode of a desired size, and the positive electrode active material is a metal oxide or a metal compound.

Preferably, if the inorganic solid electrolyte is a lithium salt electrolyte, the positive electrode active material capable of deintercalating lithium ions may be selected from lithium cobaltate (LiCoO ₂ ), lithium nickelate (LiNiO ₂ ), lithium manganate (LiMn ₂ O ₄ ), Lithium iron phosphate (LiFePO ₄ ), lithium nickel cobaltate binary material (LiNi _1-x Co _x O ₂ ), spinel structure (LiMn _2-x M _x O ₄ , M=Ni, Co, Cr, etc.), Lithium nickel cobalt manganese oxide ternary material [Li(Ni, Co, Mn)O ₂ ], layered lithium-rich high manganese material [Li ₂ MnO ₃ -Li(NiCoMn)O ₂ ], Li ₃ M _{2 of} NASCION structure ( One or more of PO ₄ ) ₃ (M=V, Fe, Ti, etc.) or the like or a composite thereof.

Step 104: assembling using the battery negative electrode, the all-solid electrolyte layer, and the battery positive electrode.

Preferably, the prepared negative electrode, solid or gel electrolyte layer, and battery positive electrode are sequentially closely stacked in an inert gas or anhydrous oxygen-free environment, and then packaged into a battery case to complete battery assembly.

It should be noted that although the above steps 101-103 describe the operation of the preparation method of the present invention in a specific order, it is not required or implied that these operations must be performed in this particular order. The preparation of steps 101-103 can be performed simultaneously or in any order.

The secondary battery preparation method and the foregoing secondary battery are based on the same inventive concept, and the secondary battery obtained by the secondary battery preparation method has all the effects of the foregoing secondary battery, and details are not described herein again.

The above secondary battery preparation method will be further described below by way of specific examples, but it should be understood that these examples are for the purpose of illustration only, and are not intended to limit the invention in any way.

Example 1

Preparation of battery negative electrode: Take aluminum foil with a thickness of 0.02 mm, cut into a 12 mm diameter disc, wash the aluminum foil with ethanol, and dry it as a negative current collector for use.

A solid electrolyte is prepared, and the Li _0.5 La _0.5 TiO ₃ electrolyte layer is cut into a certain shape and size for use;

Preparation of battery positive electrode: 0.4 g of lithium cobaltate, 0.05 g of carbon black, 0.05 g of polyvinylidene fluoride was added to a 2 m] nitromethylpyrrolidone solution, and fully ground to obtain a uniform slurry; then the slurry was uniformly coated on the surface of the aluminum foil. And dried in a vacuum. The electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, and compacted as a battery positive electrode.

Battery assembly: In the inert gas-protected glove box, the prepared negative electrode current collector, The solid electrolyte layer and the positive electrode of the battery are closely stacked in sequence, and then the stacked portion is packaged into a button battery case to complete battery assembly.

Example 2-26

The procedure of the preparation process of the secondary batteries of Examples 2-26 and Example 1 was the same as that of Example 1, except that the materials were prepared differently or the content of the materials was different. See Table 1 for details.

Table 1 Example 1-26 Comparison of anode material, cathode material and solid electrolyte layer

Comparative example

Prepare the battery negative electrode: take 0.4g graphite, 0.05g carbon black, 0.05g polyvinylidene fluoride into 2ml nitromethylpyrrolidone solution, fully grind to obtain a uniform slurry; then uniformly apply the slurry on the surface of aluminum foil and vacuum dry . The electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, and compacted as a battery negative electrode.

Preparation of the separator: The polymer polyethylene was cut into a disk having a diameter of 16 mm, and dried for use as a separator.

The electrolyte was prepared: 0.75 g of lithium hexafluorophosphate was weighed and added to 2.5 ml of ethylene carbonate and 2.5 ml of dimethyl carbonate, and the mixture was thoroughly stirred until lithium hexafluorophosphate was completely dissolved, and then it was used as an electrolyte.

Preparation of battery positive electrode: 0.4 g of lithium cobaltate positive electrode material, 0.05 g of carbon black, 0.05 g of polyvinylidene fluoride was added to 2 ml of nitromethylpyrrolidone solution, and fully ground to obtain a uniform slurry; then the slurry was uniformly coated on aluminum foil. The surface was dried under vacuum. The electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, and compacted as a battery positive electrode.

Battery assembly: In the inert gas-protected glove box, the prepared negative electrode current collector, separator, and battery positive electrode are closely stacked in sequence, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the button battery case. , complete battery assembly.

Battery performance test:

Charging-discharging test: The secondary battery prepared in the above embodiment of the secondary battery preparation method was charged by a constant current of 100 mA/g of the positive electrode active material until its voltage reached 4.8 V, and then discharged at the same current until the voltage reached 3V, measuring its battery capacity and energy density, testing its cycle stability, expressed in cycles, the number of cycles is the number of times the battery is charged and discharged when the battery capacity is attenuated to 85%.

Table 3 battery performance test results

It can be seen from the above experimental data that the anode materials of the present invention use different anode materials (anode current collectors) and cathode active materials of different compositions. In contrast, Example 6 uses a carbon layer to coat porous aluminum as a cathode current collector. The number of cycles of the battery was optimized, in contrast to Example 5 using porous aluminum as the negative electrode material and Example 1 using aluminum foil as the negative electrode material to obtain a larger battery capacity.

In the case of using the same negative electrode current collector, Examples 7-12 used different positive electrode active materials, and in combination with the corresponding inorganic solid electrolyte, good battery capacity and cycle performance of the battery were achieved.

In the case of using the same negative current collector and positive active material, Examples 12, 17, 18, 19 Good battery capacity and cycle performance of the battery are achieved using different inorganic solid electrolytes.

The above embodiments are merely preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention belong to the present invention. The scope of the claim.

Claims

A secondary battery comprising a battery negative electrode and a battery positive electrode; characterized in that it further comprises an all-solid electrolyte layer, wherein

The negative electrode of the battery includes a negative current collector, and does not include a negative active material; the negative current collector includes a metal, a metal alloy or a metal composite conductive material;

The all solid electrolyte layer includes an inorganic solid electrolyte;

The positive electrode of the battery includes a positive current collector and a positive active material layer, the positive current collector includes a metal, a metal alloy or a metal composite conductive material, and the positive active material layer includes reversible deintercalation of lithium ions, sodium ions or magnesium ions Positive active material.
The secondary battery according to claim 1, wherein the anode current collector comprises one or any one of aluminum, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese. A metal composite or an alloy of any of them.
The secondary battery according to claim 2, wherein the anode current collector is preferably aluminum.
The secondary battery according to claim 3, wherein the structure of the anode current collector is a multilayer composite structure of porous aluminum or aluminum coated with aluminum foil or porous aluminum or carbon material.
The secondary battery according to claim 1, wherein said positive electrode current collector comprises one or any one of aluminum, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese. A metal composite or an alloy of any of them.
The secondary battery according to claim 5, wherein the cathode current collector is preferably aluminum.
The secondary battery according to claim 1, wherein said inorganic solid electrolyte comprises a perovskite crystal electrolyte, an inverse perovskite crystal electrolyte, a superionic conductor type crystalline electrolyte, and a fast ion conductor type. One or more of a crystalline electrolyte, a garnet-type crystalline electrolyte, a lithium nitride-based crystalline electrolyte, a lithium phosphorus-oxygen-nitrogen amorphous electrolyte, an amorphous sulfide amorphous electrolyte, and a composite electrolyte.
A secondary battery according to any one of claims 1 to 7, wherein said positive active material Including lithium cobaltate, lithium nickelate, lithium manganate, lithium iron phosphate, lithium nickel cobaltate binary material, spinel structure oxide, lithium nickel cobalt manganese ternary material, layered lithium-rich high manganese material A composite material of one or several or any one of them.
The secondary battery according to any one of claims 1 to 7, wherein the positive electrode active material layer further comprises a conductive agent and a binder, and the content of the positive electrode active material is 60 to 95% by weight, of the conductive agent. The content is from 0.1 to 30% by weight, and the content of the binder is from 0.1 to 10% by weight.
A method for preparing a secondary battery according to any one of claims 1 to 9, characterized in that it comprises:

Preparing a battery negative electrode, cutting a metal, metal alloy or metal composite conductive material into a desired size, and then washing the surface of the cut metal, metal alloy or metal composite conductive material, the washed metal, a metal alloy or a metal composite conductive material as a battery negative electrode;

Preparing a solid electrolyte, and cutting the above inorganic solid electrolyte layer into a certain shape and size for use;

Prepare the positive electrode of the battery, weigh the living positive material, the conductive agent and the binder according to a certain ratio, add it into a suitable slurry and fully grind it into a uniform slurry, and then uniformly apply it to the surface of the positive current collector, and then cut the slurry after it is completely dried. Cutting to obtain a positive electrode of a desired size, the positive active material being a metal oxide or a metal compound;

Assembly is performed using the battery negative electrode, the solid electrolyte, and the battery positive electrode.