CN109326773B

CN109326773B - Electrode active material, battery electrode and semiconductor nano battery

Info

Publication number: CN109326773B
Application number: CN201710648674.6A
Authority: CN
Inventors: 金元国; 陈捷; 傅士军; 石井信; 中岛润二
Original assignee: Tianji New Energy Industrial Shenzhen Co ltd
Current assignee: SHENZHEN THINK TECHNOLOGY CO.,LTD.
Priority date: 2017-08-01
Filing date: 2017-08-01
Publication date: 2021-12-28
Anticipated expiration: 2037-08-01
Also published as: CN109326773A

Abstract

The invention provides an electrode active material, a battery electrode and a semiconductor nano battery containing the battery electrode. The electrode active material comprises a silicon active material, graphene and graphite; the particle size of the silicon active material is 30-200 nm; the quantity of the silicon active material, the graphene and the graphite is more than or equal to 20/more than or equal to 3, the quantity of the silicon active material/the weight of the graphene is more than or equal to 30/more than or equal to 4, the absorption and storage efficiency of ions (cations) or cavities of the electrode is improved, meanwhile, an electronic storage layer can be formed, and the graphene and the silicon active material are difficult to be used as heating elements, so that even if the battery is internally short-circuited, the heating is difficult, the rupture of the battery can be inhibited, the safety and the service life of the battery can be improved, the battery is like a bipolar power supply with two batteries, and the battery has high safety, long service life, high power and high capacity.

Description

Electrode active material, battery electrode and semiconductor nano battery

Technical Field

The invention relates to the field of secondary batteries, in particular to an electrode active material, a battery electrode and a semiconductor nano battery containing the battery electrode.

Background

The development of mankind is always accompanied by the innovation of various new technologies and the application of new energy, such as the first industrial revolution accompanied by the popularization of steam engines; the second industrial revolution is the application of electricity. In the modern society, fossil fuels such as petroleum, natural gas, and coal are widely used, and have a history of over two hundred years, with the rise in the price of fossil fuels and the energy crisis. In addition, various petrochemical fuels are non-renewable energy sources, and the storage capacity is extremely limited. And various toxic gases and dust are discharged to the atmosphere while fossil energy is combusted, and the life and health of people are seriously influenced by acid rain, haze, greenhouse effect and the like. In addition, for the high energy and portability of electronic products, the popularization of electronic products such as portable computers and mobile phones also requires a portable energy source with high energy density. There are various reasons that compel people to start looking at the development of new clean energy and new energy storage devices. This also makes the lithium ion battery stand out.

The portability and high energy density of lithium ion batteries relative to other secondary batteries has led the portable battery market over the past twenty years. Today, research on lithium ion batteries is focusing on lithium ion batteries as a power source for hybrid vehicles, plug-in hybrid vehicles, and electric vehicles, and lithium ion battery technology has been considered as a secondary renewable energy source comparable to wind energy, tidal energy.

A general lithium ion secondary battery disclosed in japanese patent application laid-open No. 2015-002167 contains a positive electrode active material, a negative electrode active material, a nonaqueous electrolytic solution, and a separator, wherein the positive electrode active material is generally a transition metal oxide containing lithium, and the negative electrode active material is generally a material capable of absorbing/releasing lithium ions (for example, lithium metal, lithium alloy, metal oxide, and carbon material), however, the conventional lithium ion secondary battery has reached limits in terms of power and capacity per weight, but with the spread of electric vehicles, further improvement in high power and quick charging performance is expected. In addition, although the patent literature can achieve a lifetime of 5000 cycles, the patent literature is still insufficient for the popularization of electric vehicles and smart grids.

Disclosure of Invention

The invention provides an electrode active material, a battery electrode and a semiconductor nano battery containing the battery electrode, which can realize high power, high capacity and excellent cycle performance, and aims to overcome the technical problem that the power, capacity and cycle performance of the conventional lithium ion battery cannot meet the requirements.

A first object of the present invention is to provide an electrode active material comprising, a silicon active material, graphene and graphite; the particle size of the silicon active material is 30-200 nm; the amount of the silicon active material, the graphene and the graphite is more than or equal to 20/3, and more than or equal to 30/4.

A second object of the present invention is to provide a battery electrode comprising a current collector and an active material layer attached to the current collector, the active material layer containing an electrode active material, the electrode active material being the above-mentioned electrode active material.

The third purpose of the invention is to provide a semiconductor nano battery, which comprises a first electrode, a second electrode and an electrolyte positioned between the first electrode and the second electrode, wherein the second electrode is the battery electrode.

The inventors of the present invention have found that since the second electrode of the present invention contains graphene and a specific silicon active material, the second electrode releases cations and moves to the first electrode through an electrolyte when the battery is discharged. As the cell is charged, the first electrode releases cations which move through the electrolyte to the second electrode. The positive ions move from the first electrode to the second electrode, and the structure of the electrode active material of the first electrode and the second electrode can be changed while the potential of the first electrode is higher than that of the second electrode. During charging, electrons are inserted into the second electrode, whereby holes are generated by excess cations in the first electrode and move to the second electrode, and the holes generated by the first electrode in the ion-conducting member, such as an electrolyte, and the hole-conducting member, such as a separator, collide with each other, are deviated from the material capable of becoming multivalent cations contained in the hole-conducting member or the portion containing the ion-conducting member, and multivalent cations are transported and collide with each other in the second electrode, thereby generating holes. While holes in the second electrode proceed in a direction perpendicular to the direction of the electric field of the first electrode, electrons and holes are accumulated in opposite directions. Generally, the first electrode contains a p-type semiconductor material, in the embodiment of the invention, the first electrode preferably contains a doped p-type semiconductor material, the second electrode contains a silicon active material, and the silicon active material is an n-type semiconductor material, so that rapid charging can be realized; when the battery discharges, the dielectric polarization reaction occurs, electrons in the electron storage layer in the second electrode are rapidly released from the inside of the electrode to the outside, and holes in the second electrode move to the first electrode, so that the battery has high power performance. The above-mentioned phenomenon between the first electrode and the second electrode, such as the presence of a bipolar power source of two batteries, allows the batteries to have high safety, long life, high power and high capacity performance. The secondary battery of the present invention has both characteristics of a chemical battery in which cations are transported through an ion conducting member and a semiconductor battery in which holes are conducted from a p-type semiconductor first electrode through a hole conducting member. The secondary battery may be a hybrid battery of a chemical battery and a physical battery (semiconductor battery), or may be a battery having a bipolar power source in which the second electrode is a semiconductor battery and the first electrode is a trigger for the semiconductor battery. The positive ions discharged from the first electrode or the second electrode of the secondary battery of the present invention move between the first electrode and the second electrode through the ion-conducting member to secure a high capacity of the battery. Meanwhile, the holes of the secondary battery move between the first electrode and the second electrode through the hole conducting component, and the holes are smaller than ions and have higher moving speed, so that the high power of the battery is ensured. Meanwhile, in the hole conducting component and the ion conducting component, cations and holes have a replacement effect, so that the high safety, the long service life and the high power of the battery can be ensured. In the secondary battery of the present invention, if the electrolyte is used as the ion transfer member, the amount of use can be reduced, the safety performance of the battery can be further improved, and even if the first electrode and the second electrode are in contact with each other to cause an internal short circuit, the temperature rise of the secondary battery can be suppressed, thereby preventing the occurrence of safety accidents such as ignition of the battery. Meanwhile, the secondary battery has high capacity retention rate after multiple rapid charging and discharging, and the cycle performance of the battery is excellent.

Drawings

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

Wherein: a first electrode 10; a second electrode 20; an ionically conductive member 30; a hole-conducting member 40; a perovskite structure layer 50; a secondary battery 100; a first current collector 110; a second current collector 120.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following 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.

The invention provides an electrode active material, which comprises a silicon active material, graphene and graphite; the particle size of the silicon active material is 30-200 nm; the quantity of the silicon active material, the graphene and the graphite is more than or equal to 20/more than or equal to 3, the quantity of the silicon active material/the weight of the graphene is more than or equal to 30/more than or equal to 4, the absorption and storage efficiency of ions (cations) or cavities of the electrode is improved, meanwhile, an electronic storage layer can be formed, and the graphene and the silicon active material are difficult to be used as heating elements, so that even if the battery is internally short-circuited, the heating is difficult, the rupture of the battery can be inhibited, the safety and the service life of the battery can be improved, the battery is like a bipolar power supply with two batteries, and the battery has high safety, long service life, high power and high capacity.

The electrode active material is capable of occluding and releasing cations and holes. The graphite is not limited in the present invention, and may be one or more of various natural graphite or artificial graphite. Silicon active material the present invention is not limited, and can be various silicon active materials commonly used by those skilled in the art, such as simple substance of silicon, oxide of silicon, silicide, etc., and preferably, the silicon active material is selected from one or more of silicon, oxide of silicon such as siox (xa < 2), and alloy of silicon. Preferably, the graphene is a multilayer structure, and preferably the graphene is nanoscale layer graphene with less than 10 layers. Further improving the performance of the battery. The electrode active material may contain other active materials, for example, various alloys such as titanium alloy may be mixed, and Carbon Nanotubes (CNTs) may be contained.

In addition, the electrode active material may be doped, for example, with a metal element, where the metal element may be an alkali metal or a transition metal element, specifically, for example, one or more of copper, lithium, sodium, potassium, titanium, or zinc may be doped, and preferably, graphene containing lithium is doped; and/or, the silicon active material comprises a lithium-doped silicon active material; and/or, graphite comprises lithium doped graphite; the doping may be performed by preparing the silicon active material alone and then mixing the silicon active material, the graphene, and the graphite, or by mixing the silicon active material, the graphene, and the graphite with organic lithium and then heating the mixture, or by using collision heat generated by high-speed dispersion of the filmix during mixing. The doping of lithium may also be performed by preparing an active material layer by mixing a silicon active material, graphene, and graphite, and then attaching lithium metal to the surface of the active material layer. Phosphorus oxide and/or sulfur oxide doping may also be used. And/or, the electrode active material is doped with halogen, which can further improve the battery life, even if lithium hexafluorophosphate in the electrolyte generates fluoric acid during charge and discharge, the halogen can inhibit the characteristic change of the electrode active material. Specifically, a halide such as a fluorine-containing halide may be used so that the electrode active material contains SiOxaF, although an iodine-containing halide may also be used.

The mixing of the silicon active material, graphene and graphite is not limited in the present invention, and various mixing methods may be used, for example, dispersion by a high shear disperser, or a ilmix manufactured by primix co.

The invention also provides a battery electrode which comprises a current collector and an active material layer attached to the current collector, wherein the active material layer contains an electrode active material, and the electrode active material is the electrode active material. The electrode active material forms an n-type semiconductor.

The current collector is not limited in the present invention, and may be a negative current collector commonly used in the art, such as copper foil, stainless steel, nickel, or the like. The active material layer is generally adhered to the current collector by a binder using a mixture of an electrode active material and a binder, and may further contain a conductive material. In the present invention, the battery electrode may be prepared by drawing a slurry containing the electrode active material for a current collector. The slurry is uniformly mixed with the electrode active material, the binder and a suitable solvent in a certain ratio, the binder and the solvent are not particularly limited, and the binder and the solvent are generally known binders and solvents used for preparing a negative electrode of a lithium ion battery, and preferably, the binder of the negative electrode is formed by mixing carboxymethyl cellulose (CMC) having a thickening effect, specifically, MAC-350HC of Nippon paper-making Co., Ltd., modified acrylonitrile rubber particle binder (BM-451B of Zeon corporation, Japan, etc.), and soluble modified acrylonitrile rubber (BM-720 of Zeon Limited, Japan).

Further, preferably, lithium metal is further attached to the surface of the active material layer, so that lithium is doped in the active material layer, and the performance of the battery is further improved.

And/or the active material layer contains phosphorus oxide and/or sulfur oxide;

and/or, a perovskite structure layer is attached to the surface of the active material layer, and the pressure generated by the expansion of the silicon active material during charging is transmitted to the perovskite structure layer, so that the cation conduction speed and the hole conduction speed can be increased. Preferably, the perovskite structure layer is CH_３ＮＨ_３ＰｂＩ_３The layer, which allows the electrode active material to be doped with halogen, can further improve the battery life.

The invention also provides a semiconductor nano battery, which comprises a first electrode, a second electrode and an electrolyte positioned between the first electrode and the second electrode, wherein the second electrode is the battery electrode, namely a battery cathode.

The electrolyte is an ion conducting member for ionic conduction between the first electrode and the second electrode, and may take the form of a liquid, a gel, a solid, or the like. For example, it is possible to use a liquid form, that is, a commonly used electrolyte solution containing an electrolyte formed by dissolving a salt in a solvent. The salt is selected from LiPF_６、ＬｉＢＦ_４、ＬｉＣｌＯ_４、ＬｉＳｂＦ_６、ＬｉＡｓＦ_６、ＬｉＣＦ_３ＳＯ_３、ＬｉＮ（ＳＯ_２ＣＦ_３）_２、ＬｉＮ（ＳＯ_２Ｃ_２Ｆ_５）_２、ＬｉＣ（ＳＯ_２ＣＦ_３）_３、ＬｉＮ（ＳＯ_３ＣＦ_３）_２、ＬｉＣ_４Ｆ_９ＳＯ_３、ＬｉＡｌＯ_４、ＬｉＡｌＣｌ_４LiCl, LiI, lithium bis (pentafluoroethanesulfonyl) imide (LiN (SO)_２Ｃ_２Ｆｂ）_２: lithium Bis (pentafluoro-ethane-sulfo) Imide: LiBETI), Lithium Bis (Trifluoromethanesulfonyl) Imide (Lithium Bis (trifluoromethane sulfonyl) Imide: LiTFS). The solvent may be selected from the group consisting of Ethylene Carbonate (EC), Fluorinated Ethylene Carbonate (FEC), Dimethyl Carbonate (DMC), Diethyl Carbonate (DEC), and ethyl methyl Carbonate (Me)thyyl Ethyl Carbonate: MEC). In addition, in order to secure overcharge safety, Vinylene Carbonate (VC), Cyclohexylbenzene (CHB), Propane Sultone (PS), Propylene Sulfite (PRS), Ethylene Sulfite (ES), and the like, and modifications thereof may be added to the electrolyte. Of course, other electrolyte additives can be contained, preferably, the electrolyte contains methanesulfonic acid propyne and/or a sulfonic compound, and more preferably, the sulfonic compound is 2-butyne-1, 4-diol dimethane sulfonate. When the graphene is in a liquid form and is positioned in the electrolyte, the methanesulfonic acid propyne can inhibit the surface reduction reaction of the graphene and the electrolyte, and can prevent resistance components from being formed on the surfaces of the silicon active material and the graphene, so that the resistance of movement of electrons and holes between graphene layers is reduced, and the performance and the service life of the battery are further improved. If the liquid form is adopted, generally, a diaphragm is also arranged in the first electrode and the second electrode, so that the first electrode and the second electrode are not in physical contact, and the diaphragm can be used as a hole conduction component and has a porous structure.

The electrolyte may also take a solid form, for example, preferably, the electrolyte is an all-solid electrolyte; the all-solid electrolyte can be selected from Lix1POy1Nz1, LiNbO3, Li10GeP2S12, LiTaO3, Lix2La (1/3-x2) TaO3, Li3PO4, Lix3Tiy3(PO4)3, Lix4Aly4Tiz4(PO4)3, Li2SiO3, Li2O, Li2S, Li2S-P2S5, Li2S-SiS2-P2S5, Lix5Siy5Sz5, Lix6Py6Sz6, LiBO2, Li3.6Si0.6P0.4O4 or Li 3N; wherein x is more than 2 and less than 1 and less than 4, y is more than 3 and less than 1 and less than 5, and z is more than 0.1 and less than 1 and less than 0.9; 0 < x2 < 3; x3 is more than 0 and less than 2, and y3 is more than 0 and less than 3; x4 is more than 0 and less than 2, y4 is more than 0 and less than 1, and z4 is more than 0 and less than 3; x5 is more than 0 and less than 3, y5 is more than 0 and less than 2, and z5 is more than 0 and less than 4; x6 is more than 0 and less than 3, y6 is more than 0 and less than 3, and z6 is more than 0 and less than 7. Preferably, the electrolyte contains phosphorus and sulfur elements; further optimizing battery performance. And/or, preferably, the electrolyte is a perovskite structure layer, and further preferably, the perovskite structure layer contains lead and iodine elements. In this case, the separator may or may not be used between the first electrode and the second electrode, and in the case where the separator is not used, the electrolyte layer formed of the all-solid electrolyte may serve as both the ion conductive member and the hole conductive member so that the first electrode and the second electrode do not physically contact each other. It may be applied directly to the surface of the first electrode or the second electrode, or may be supported on the separator when the separator is used. When it is preferred that the electrolyte is a perovskite structure layer, and the ion conducting member and/or the hole conducting member contain a perovskite material, the cation conducting speed and the hole conducting speed can be accelerated by transmitting pressure generated by expansion of the silicon active material to the perovskite upon charging. The perovskite structure layer generally comprises perovskite type solid electrolyte and a binder, wherein the binder can be one or more of polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, sodium carboxymethylcellulose and styrene butadiene latex. In the perovskite structure layer, the content of perovskite type solid electrolyte is 65-99.5 wt%, and the content of binder is 0.5-35 wt%.

The hole conducting member may be in solid form or in gel form, e.g., forming a polymer battery in the gel state; the solid form may be a solid electrolyte layer as described above, such as a perovskite structure layer; the ceramic diaphragm can also be used, namely the ceramic diaphragm is also arranged between the first electrode and the second electrode. The ceramic separator is a porous film containing an inorganic substance, the inorganic substance may be filled in or attached to the porous substrate, and specifically, the porous film may contain an inorganic oxide, and preferably, the inorganic oxide is alumina (. alpha. -Al)_２Ｏ_３) The inorganic oxide is preferably alumina-mixed ZrO, and the holes move on the surface of the alumina_２－Ｐ_２Ｏ_５Or antimony, aluminum, magnesium and other metals and complexes thereof, and is easier for hole conduction. Of course,the porous film may contain ZrO_２－Ｐ_２Ｏ_５Or may be mixed with titanium oxide, silicon, or the like.

The hole conducting part is not easy to shrink and has low resistance, the porous matrix of the ceramic diaphragm can be non-woven fabric or porous polymer film, specifically can be polyolefin microporous film, polyethylene felt, glass fiber felt or superfine glass fiber paper, and the like, and shows voltage resistance, oxidation resistance and low resistance. The thickness of the hole-conducting member is not particularly limited, and is preferably set to 6 μm to 25 μm.

The first electrode, i.e., the positive electrode for a battery, includes a first current collector and a first active material layer attached to the first current collector, the first active material layer contains a first electrode active material, the first electrode active material may include a composite oxide containing an alkali metal or an alkaline earth metal, the alkali metal may be lithium and/or sodium, and the alkaline earth metal may be magnesium or the like.

Preferably, the first electrode active material contains a composite oxide, and the composite oxide contains a p-type composite oxide, i.e., a p-type semiconductor. The p-type composite oxide may be a composite oxide containing lithium and nickel doped with at least one of antimony, lead, phosphorus, boron, aluminum, gallium, and the like, and may be expressed as LixNiyMzO α, where 0 < x < 3, y + z ═ 1, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, 1 ≦ α < 4, and M is selected from one or more of antimony, lead, phosphorus, boron, aluminum, and gallium. When M is doped, the p-type composite oxide is structurally damaged to form a hole. Specifically, the first electrode active material may include lithium nickelate doped with a metal element, and further may be lithium nickelate doped with antimony.

Further, it is also desirable that the composite oxide is mixed from a plurality of kinds. For example, it is also desirable that the composite oxide contains a solid solution-like composite oxide which forms a p-type composite oxide and a solid solution. The solid solution is formed from a p-type composite oxide and a solid solution-like composite oxide. The solid solution-like composite oxide is apt to form a solid solution of nickel acid and layers, and the structure of the solid solution is apt to move holes. For example, the solid solution composite oxide is lithium manganate (Li)_２ＭｎＯ_３) In this case, the valence of lithium is 2.

Examples of the active material of the electrode 10 include composite oxides such as lithium nickelate, lithium manganese phosphate, lithium manganate, lithium nickel manganate, lithium manganese niobate, solid solutions thereof, and modifications thereof (co-crystals of metals such as antimony, aluminum, and magnesium), and materials thereof, which are chemically or physically synthesized.

In addition, the first electrode active material may further contain fluorine element. For example, the first electrode active material contains LiMnPO4F, and even if the electrolyte containing lithium hexafluorophosphate generates fluoric acid, the change in the characteristics of the first electrode active material can be suppressed.

First current collector the present invention is not limited, and may be a positive electrode current collector commonly used in the art, such as aluminum foil or nickel mesh, stainless steel, and the like. The first active material layer is generally adhered to the first current collector by a binder using a mixture of the first electrode active material and a binder, and may generally contain a conductive agent. In the present invention, the first electrode may be prepared by slip-coating a slurry containing the first electrode active material for the first current collector. The slurry is uniformly mixed by using a first electrode active material, a binder and a suitable solvent in a certain proportion, the binder and the solvent are not particularly limited, generally known binders and solvents used for preparing a positive electrode of a lithium ion battery are used, generally a rubber-like high polymer material is selected, preferably, a high molecular weight is mixed with a low molecular weight rubber-like high polymer material, and the high polymer materials with different molecular weights are mixed, so that the slurry is more resistant to hydrofluoric acid and inhibits the interference of hole transport. Polyacrylic acid containing acrylic acid groups (SX 9172, Zeon Co., Ltd., Japan) is preferably used as the positive electrode binder, and the electrode active material is not easy to peel off during battery preparation, so that the yield is improved. In addition, by using the above-mentioned acryl-based positive electrode binder, internal resistance is reduced, and it is possible to improve charge and discharge efficiency of the battery while suppressing the factor of inhibiting p-type semiconductor properties of the first electrode. With this binder, the acryl-based resin can coat the first electrode active material, and also can suppress the reaction of the first electrode active material with the electrolyte and suppress the generation of gas.

Preferably, the acryl-based positive electrode binder further contains graphene, ion conductive glass, phosphorus, or the like, and is difficult to trap electrons, so that heat generation of the first electrode can be suppressed, dissociation reaction and diffusion of lithium can be promoted, and the battery potential is reduced, so that the oxidation potential of the first electrode active material is lowered, and movement of lithium ions is not interfered. In addition, the acryl-based resin is excellent in voltage resistance, can form an ion conduction structure of high capacity and high power at a high voltage in the first electrode, has an increased diffusion rate and a reduced resistance, can suppress a temperature rise at a high power, and can improve the life and safety of a battery. The conductive agent can be one or more of acetylene black, ketjen black, graphite, graphene, carbon nano-tubes and carbon nano-fibers.

The first electrode, the second electrode and the electrolyte between the first electrode and the second electrode are generally made into a pole core, the semiconductor nano battery generally further comprises a shell, a cover plate for sealing the shell and the like, the preparation method of the battery of the invention is well known to those skilled in the art, and generally, the preparation method of the battery comprises the steps of putting the pole core into a battery shell and packaging to obtain the battery. The packaging includes placing the battery pole core into the battery case, welding the cover plate and the battery case, injecting electrolyte into the battery case, forming and sealing the battery, and the forming and sealing techniques are various techniques known to those skilled in the art, and the present invention is not particularly limited.

The technical scheme of the invention is described in detail in the following with reference to the accompanying drawings,

referring to fig. 1, which is a schematic view illustrating the structure of a secondary battery 100 according to an embodiment of the present invention, the secondary battery 100 includes first and

second electrodes

10 and 20 having opposite polarities, and an ion-conducting member 30 and a hole-transporting member 40 disposed between the first and

second electrodes

10 and 20. The first electrode 10 and the second electrode 20 are not in physical contact. In this embodiment, the first electrode 10 is a positive electrode, and the second electrode 20 is a negative electrode. During battery discharge, the first electrode 10 has a higher potential than the second electrode 20, and current flows from the first electrode 10 to the second electrode 20 through an external load (not shown). When the battery is charged, a high potential end of an external power source (not shown) is connected to the first electrode 10, and a low potential end of the external power source (not shown) is connected to the second electrode 20. The first electrode 10 generally includes a first current collector 110 and a first active material layer on the first current collector 110; the second electrode 20 generally includes a second current collector 120 and a second active material layer on the second current collector 120.

The ion-conducting member 30 is used for conducting ions between the first electrode 10 and the second electrode 20, in this embodiment, as shown in fig. 1, the ion-conducting member 30 may be located in the pores of the porous hole-conducting member 40, but is not limited thereto, and the ion-conducting member 30 may also be located at a position far away from the hole-conducting member 40, such as the surface of the first electrode 10 or the second electrode 20; or in a non-porous ion-conducting membrane such as sodium super ion conductor (NASICON, Li)_1+x+yAlx(Ti,Ge)_2-xSi_yP_3-yO₁₂) In the membrane, the ionically conductive member 30 may be a liquid, such as an electrolyte, or may be a solid or gel. Upon discharge of the battery, the second electrode 20 releases cations, which move to the first electrode 10 through the ionically conductive member 30. Upon charging of the battery, the first electrode 10 releases cations that move through the ionically conductive member 30 to the second electrode 20. The cations move from the first electrode 10 to the second electrode 20, and the structure of the electrode active material of the first electrode 10 and the second electrode 20 can be changed while the potential of the first electrode 10 is higher than that of the second electrode 20. During charging, when electrons are inserted into the second electrode 20, holes are generated and moved to the second electrode 20 due to excess cations in the first electrode 10, and the holes generated in the ion-conducting member 30 and the first electrode 10 in the hole-conducting member 40 collide with each other, are deviated from the material capable of becoming multivalent cations contained in the hole-conducting member 40 or the portion containing the ion-conducting member, and transport multivalent cations, and collide with multivalent cations in the second electrode 20, thereby generating holes. While holes in the second electrode 20 proceed in a direction perpendicular to the direction of the electric field of the first electrode 10, electrons and holes are accumulated in opposite directions. The inventors of the present invention speculate that the above phenomenon is caused by the second electrode 20 of the present invention containing graphene and a specific silicon active material. Typically, the first electrode 10 comprises a p-type semiconductor materialIn this embodiment, it is preferable that the first electrode 10 contains a doped p-type semiconductor material, and the second electrode 20 of the present invention contains a silicon active material, which is an n-type semiconductor material, so as to realize rapid charging; when the battery is discharged, a dielectric polarization reaction occurs, electrons in the electron storage layer in the second electrode 20 are rapidly released from the inside of the electrode to the outside, and holes in the second electrode 20 move to the first electrode 10, so that the battery has high power performance. The above-mentioned phenomenon between the first electrode 10 and the second electrode 20, such as the presence of a bipolar power source of two batteries, allows the batteries to have high safety, long life, high power, and high capacity performance. The secondary battery 100 according to the embodiment of the present invention has both characteristics of a chemical battery in which cations are transferred through the ion conductive member 30 and a semiconductor battery in which holes are conducted from the p-type semiconductor first electrode 10 through the hole conductive member 40. Secondary battery 100 may be a hybrid battery of a chemical battery and a physical battery (semiconductor battery), or may be a semiconductor battery in which a portion of second electrode 20 is a semiconductor battery and a portion of first electrode 10 is a wake-up semiconductor battery. In the secondary battery 100 according to the embodiment of the present invention, cations discharged from the first electrode 10 or the second electrode 20 move between the first electrode 10 and the second electrode 20 through the ion-conducting member 30, thereby securing a high capacity of the battery. Meanwhile, in the secondary battery 100 according to the embodiment of the present invention, the holes move between the first electrode 10 and the second electrode 20 through the hole-conducting member 40, and the holes are smaller than the ions and have a higher moving speed, thereby securing high power of the battery. Meanwhile, in the hole conducting member 40 and the ion conducting member 30, there is also a substitution effect of cations and holes, which can ensure high safety, long life, and high power of the battery. As can be seen from table 1, the secondary battery of the present invention can greatly improve the capacity performance characteristics of the battery. In the secondary battery 100 of the present invention, if the electrolyte is used as the ion transport member 30, the amount of use can be reduced, the safety of the battery can be further improved, and even if the first electrode 10 and the second electrode 20 are in contact with each other to cause an internal short circuit, the temperature rise of the secondary battery 100 can be suppressed, thereby preventing occurrence of a safety accident such as ignition of the battery. Also, practice of the inventionThe secondary battery 100 of the example has high capacity retention rate after multiple rapid charge and discharge, and the cycle performance of the battery is excellent.

The cation may be an alkali metal or alkaline earth metal ion. For example, the first electrode 10 may contain an alkali metal or alkaline earth metal-based compound, and the second electrode 20 may absorb and discharge alkali metal or alkaline earth metal-based ions. When the secondary battery 100 is discharged, the alkali metal or alkaline earth metal ions are released from the second electrode 20 and move toward the first electrode 10 through the ion conductive member 30. When the secondary battery 100 is charged, alkali metal or alkaline earth metal ions are released from the first electrode 10 and move toward the second electrode 20 through the ion-conducting member 30, and are absorbed by the second electrode 20. The ion-conducting component 30 may also contain alkali metal and alkaline earth metal ions.

In an embodiment of the present invention, the first electrode 10 generally comprises a p-type semiconductor material. The holes move through the first electrode 10 when the battery is charged and discharged. The hole conducting member 40 is in contact with the first electrode 10 and the second electrode 20. During discharge of the battery, the holes of the first electrode 10 are moved to the second electrode 20 by an external load (not shown), and the holes are received by the first electrode 10 through the hole-conducting member 40. During charging of the battery, holes in the first electrode 10 move to the second electrode 20 through the hole-conducting member 40, and the first electrode 10 receives holes from an external power source (not shown).

In the secondary battery 100 of the present embodiment, both cations and holes move during charge and discharge. Specifically, when the battery is discharged, the second electrode 20 releases cations and moves to the first electrode 10 via the ion transport member 30, and holes are also circulated in the order of the first electrode 10, an external load (not shown), the second electrode 20, and the hole transport member 40 by a potential difference between the first electrode 10 and the second electrode 20. During charging of the battery, positive ions released from the first electrode 10 move to the second electrode 20 via the ion transport member 30, and positive holes are also circulated in the order of the first electrode 10, the hole transport member 40, the second electrode 20, and an external power source (not shown). Due to the second electrode active material of the present invention, upon discharge of the battery, electrons present in the second electrode 20 are released by the external circuit, and the present holes and substances reaching the hole conducting member 40 collide with multivalent cations of the ion conducting member. The presence of multivalent cations returns to the respective metal content. The holes in the first electrode 10 move along the hole-conducting member, so that the electrons in the first electrode 10 and the quanta in the electrode can be equalized. As described above, according to the present invention, the bipolar power supply structure having the first electrode 10 as the operation starting function can be obtained due to the high power and capacity of the electron storage in the second electrode 20. The second electrode active material of the second electrode 20 of the present invention contains graphene and silicon active materials, and can increase hole and electron storage.

In the present invention, it is preferable that the ion conducting member and/or the hole conducting member contain a perovskite material, and particularly, as shown in fig. 1, a perovskite structure layer 50 is attached to the surface of the second electrode 20, and the pressure generated by the expansion of the silicon active material during charging is transmitted to the perovskite structure layer, so that the cation conducting speed and the hole conducting speed can be increased.

Whether the first electrode 10 and the second electrode 20 of the present invention are a p-type semiconductor and an n-type semiconductor, respectively, can be judged by measuring a hall effect (hall effect). According to the hall effect, when a magnetic field is applied while a current flows, a voltage is generated in a direction perpendicular to the flow direction of the current and the application direction of the magnetic field. From the direction of the voltage, it is possible to determine whether the semiconductor is a p-type semiconductor or an n-type semiconductor. During charging and discharging of the battery, cations and holes are transferred through the ion transfer member 30 and the hole transfer member 40, respectively, and during one of the charging and discharging operations, cations and holes may be transferred through one of the ion transfer member 30 and the hole transfer member 40. For example, only holes may be transferred through the hole transfer member 40 without using the ion transfer member 30 (e.g., an electrolyte solution) at the time of battery discharge. Alternatively, only positive ions may be transferred from the first electrode 10 to the second electrode 20 via the ion transfer member 30 without using the hole transfer member 40 during charging of the battery. The hole transport member 40 may be formed integrally with the ion transport member 30, that is, the hole transport member 40 and the ion transport member 30 may be the same material that can transport both positive ions and positive holes.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

Example 1

Lithium nickelate (JFE minor co., ltd.) to which 0.4 wt% of antimony (sb) (manufactured by high purity scientific research, ltd.) was added was mixed with Graphene (Graphene type R, manufactured by XG science co., ltd.) as a conductive agent and a polyacrylic acid binder (SX 9172, manufactured by Zeon co., ltd., japan) containing an acryl group at a solid content weight ratio of 92:3:5, and was stirred and dispersed with N-methylpyrrolidone (NMP) in a thin film rotary high speed stirrer (filmix), manufactured by primix co., ltd., to prepare a positive electrode slurry.

The positive electrode slurry was applied to SUS foil (manufactured by Nissian iron-clad materials Co., Ltd.) having a thickness of 13 μm, dried, and then rolled to give an areal density of 26.7 mg/cm^２Then, the sheet is cut into a predetermined size to obtain a first electrode, i.e., a positive electrode. The positive electrode was confirmed to be a P-type semiconductor by measuring the hall effect of the positive electrode.

Graphite (manufactured by Shanghai fir Co., Ltd.) having a major axis particle diameter of 1 to 10 μm and silicon (spherical particle diameter of 30 to 200 nm) were mixed in NOB-130 (nobilta) manufactured by Mikan corporation at a speed of 800rpm for 3 minutes at a weight ratio of 1: 1. The mixture was stirred in a two-arm mixer for a certain period of time with a graphene material (XG Science, xgnprapene Nanoplatelets H type manufactured by Inc), a solution in which 1.4 wt% of CMC (MAC 350HC manufactured by japan paper-making co., ltd) was dissolved in water, and a binder (BM 451B manufactured by japan zeon co., ltd.) consisting of polyacrylic acid latex in a formulation ratio of 90.8%, 4.32%, 1.96%, and 2.92% by weight, and then phosphorus pentoxide (manufactured by high purity Science research, ltd.) was added to the stirred mixture in a weight ratio of 1:0.005 to prepare a negative electrode slurry in a filemix (manufactured by primix ltd.). Wherein, the amount of the graphite, the graphene and the silicon is in the range of 3 times to 20 times of the weight of the graphite and 4 times to 30 times of the weight of the graphene.

The negative electrode slurry was applied to SUS foil (manufactured by Nippon iron and Steel materials Co., Ltd.) having a thickness of 13 μm, dried, and then rolled to give an areal density of 5.2 mg/cm^２Then, the second electrode, that is, the negative electrode is manufactured by slicing the electrode into pieces having a predetermined size.

A ceramic material-supported thin film (CPORE manufactured by Utsu corporation) having a thickness of 25 μm was placed between the positive electrode and the negative electrode to prepare a laminate structure. The laminate structure is cut to a specific size and placed into a battery container.

Then, 1M LiPF was dissolved in a solvent in which EC (ethylene carbonate), DMC (dimethyl carbonate) and PC (propylene carbonate) were mixed in a volume ratio of 1:1:1_６Then, 1.5 wt% of Vinylene carbonate (Vinylene carbonate), 2.0 wt% of fluoroethylene carbonate (fluoroethylene carbonate), 0.5 wt% of propyne methanesulfonate (propylmethane sulfonate), 1 wt% of propane sultone, and 0.7 wt% of 2-butyne-1, 4-diol dimethanesulfonate as a sulfonate compound were added to prepare an electrolyte solution. And penetrating the electrolyte into the ceramic material-loaded film under a dry environment. After that, the battery container was placed in a dry air atmosphere for a certain period of time, and then pre-charged with a current corresponding to 0.1C for about 20 minutes, and then sealed and placed in a normal temperature atmosphere for a certain period of time to be aged, thereby producing a secondary battery.

Comparative example 1

BC-618 of lithium nickel manganese cobalt from Sumitomo 3M Co., Ltd, PVDF # 1320 from Wuyu Co., Ltd (N-methylpyrrolidone (NMP) solution of 12 parts by weight of solid content), and acetylene black were mixed in a weight ratio of 3: 1: 0.09, and further with N-methylpyrrolidone (NMP) in a double arm mixer to prepare a positive electrode slurry. The positive electrode slurry was applied to an aluminum foil having a thickness of 13.3 μm, dried, and then rolled to obtain a total thickness of 155 μm, and then cut into pieces having a specific size to prepare a positive electrode.

Artificial graphite, a styrene-butadiene copolymer rubber particle binder BM-400B (solid content 40 parts by weight) manufactured by japan regon corporation, and carboxymethyl cellulose (carboxymethyl cellulose: CMC) were mixed in a weight ratio of 100: 2.5: stirring the mixture 1 and a proper amount of water in a double-arm type stirring manner to prepare cathode slurry. The negative electrode slurry was applied to a copper foil having a thickness of 10 μm, dried, rolled to a total thickness of 180 μm, and then cut into pieces having a predetermined size to obtain a negative electrode.

The polypropylene microporous membrane with the thickness of 20um is used as a diaphragm and placed between a positive electrode and a negative electrode to be made into a laminated structure, and the laminated structure is cut into a set size and inserted into an electric tank. 1M LiPF was dissolved in a solvent prepared by mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate (MEC)_６The electrolyte solution of (2) was injected in a dry air atmosphere and left to stand for a certain period of time, and then pre-charged for 20 minutes with a current corresponding to 0.1C, followed by sealing, to prepare a laminated lithium ion secondary battery. And then, the mixture is placed in a normal temperature environment for aging for a certain time.

Comparative example 2

Lithium nickelate (manufactured by Sumitomo Metal mining Co., Ltd.) doped with 0.7 wt% of antimony (Sb), Li1.2MnPO4 (Lithotated Metal Phosphate II manufactured by Dow Chemicals Company) and Li2MnO3(ZHENHUA E-Chem co., ZHHFL-01 manufactured by ltd) were mixed in a weight ratio of 54.7 wt%, 18.2 wt% and 18.2 wt%, and treated in AMS-LAB (mechanical fusion machine) manufactured by Mikrang, Mikroo corporation at a rotation speed of 1500rpm for three minutes to obtain a first electrode active material. Then, the first electrode active material, acetylene black as a conductive agent, and a polyacrylic acid binder having an acryl group (SX 9172 manufactured by japan regen corporation) were mixed in such a manner that the solid content weight ratio of the first electrode active material to the polyacrylic acid binder was 92:3:5 was stirred together with N-methylpyrrolidone (NMP) by a double arm mixer to prepare a positive electrode slurry.

The positive electrode slurry was coated on SUS foil (manufactured by Nissian iron-on-gold materials Co.) having a thickness of 13 μm, dried, and then rolled to obtain an areal density of 26.7 mg/cm^２Then, the resultant was cut into pieces of a predetermined size to prepare positive electrodes. By measuringThe positive electrode was confirmed to be a p-type semiconductor by the hall effect of the positive electrode.

Mixing the following components in a weight ratio of 56.4: 37.6A second electrode active material was prepared by mixing a graphene material (XG graphene nanoplates H type manufactured by XG Sciences, Inc.) and silicon oxide SiOx (SiOx manufactured by Shanghai fir Co., Ltd.) and treating the mixture in NOB-130 (Nobilta) manufactured by Mikland, Chikawa at a rotation speed of 800rpm for three minutes. Next, the second electrode active material and a polyacrylic acid binder having an acryl group (SX 9172 manufactured by japan regen corporation) were mixed in a solid content weight ratio of 95: 5, stirring the mixture with N-methylpyrrolidone (NMP) in a double-arm stirrer to prepare a negative electrode slurry.

The negative electrode slurry was coated on SUS foil (manufactured by Nissian iron-on-gold) having a thickness of 13 μm, dried, and then rolled to obtain an areal density of 5.2 mg/cm^２Then, the resultant was cut into pieces of a predetermined size to prepare a negative electrode.

A sheet (Nano X manufactured by mitsubishi paper corporation) obtained by loading alpha alumina on a nonwoven fabric having a thickness of 20 μm was placed between a positive electrode and a negative electrode as a separator, and was cut into a predetermined size to be inserted into a battery container. The nonwoven fabric containing α -alumina was subjected to impregnation treatment using Novolyte technologies "Novolyte EEL-003" (vinylene carbonate: VC) and lithium bis (oxalato) borate (lithium bis (oxalato) borate: LiBOB) added in an amount of 2 wt% and 1 wt%, respectively).

1M LiPF is dissolved in a solvent formed by mixing EC (ethylene carbonate), DMC (dimethyl carbonate) and PC (propylene carbonate) according to a volume ratio of 1:1:1_６An electrolyte is prepared. Then, after an electrolyte is injected into the battery container in a dry air atmosphere and left to stand for a certain period of time, a preliminary charging is performed at a current equivalent to 0.1C for about 20 minutes, and then the battery container is sealed, and left to stand for a certain period of time in a normal temperature atmosphere to age the battery container, thereby obtaining a secondary batteryA battery.

Comparative example 3

A battery was fabricated by the same procedure as in example 1, except that silicon was used which had a particle size larger than 200nm in example 1, a particle size of 210 to 500nm in silicon, and an average particle size of 227 nm.

Comparative example 4

A battery was prepared using the same method steps as in example 1, except that the graphite weight/graphene weight was 2.9.

Comparative example 5

A battery was prepared using the same method steps as in example 1, except that the graphite weight/graphene weight was 21.

Comparative example 6

A cell was prepared using the same method steps as in example 1, except that the silicon/graphene weight ratio was 3.9.

Comparative example 7

A cell was prepared using the same method steps as in example 1, except that the weight ratio of silicon/graphene was 31.

Example 2

A battery was fabricated by the same procedure as in example 1, except that PbI was used_２Was applied and dried on the surface of the negative electrode of example 1 by an optical coater, and then, CH was added thereto so that the concentration of the N, N-dimethylformamide solution of (2) was 40%_３ＮＨ_３I was dissolved in 2-propanol at a concentration of 45%, and then applied to the surface of the negative electrode dried above, followed by drying. Then, the cells were stored in a vacuum drying environment of-100 kPa and 105 ℃ for 72 hours to be charged. Confirmation of CH formation on the surface of the produced negative electrode by TOF-SIMS or the like_３ＮＨ_３ＰｂＩ_３The thickness of the perovskite structure layer can reach 4-6 mu m, and electrolyte is not injected into the battery.

Performance testing

The battery capacities of example 1, example 2 and comparative examples 1 to 7 were compared, assuming that the 1C discharge capacity in the standard potential range of 2V to 4.3V of comparative example 1 was 100. The battery was shaped as a prismatic battery can and was a laminated battery, and the capacity was evaluated in a potential range of 2V to 4.6V. Meanwhile, the discharge capacity ratio of 10C/1C is measured, the output power performance is evaluated, the charge capacity ratio of 10C/1C is measured, and the input power performance and the quick charge performance are evaluated.

Nail penetration test

A fully charged secondary battery was penetrated with a round iron nail having a diameter of 2.7 mm at a speed of 5 mm/sec in a normal temperature environment, and the heat generation state and appearance at the time of penetrating the secondary battery were observed. As a result, as shown in table 1, the battery was represented as "OK" without the change in the battery temperature and appearance, and "NG" with the change in the battery temperature and appearance.

Overcharge test

The current was maintained at a charging rate of 200% for 15 minutes or longer, and it was judged whether or not the appearance was changed. As a result, in Table 1, the case where no abnormality was caused was represented as "OK", and the case where a change (swelling or cracking) was caused was represented as "NG".

Life characteristic at normal temperature

In the standard potential range of 2V-4.3V, after the batteries of examples 1 and 2 and comparative examples 1-7 were charged at 25 ℃ and 1C/4.3V, 1C/2V discharge was performed for 3000 and 1 ten thousand cycles, and the capacity was compared with the first capacity.

TABLE 1

As can be seen from the above table, while the conventional lithium ion secondary battery as shown in comparative example 1 was significantly overheated after 1 second in the nail penetration test, the secondary battery of example 1 of the present invention hardly had a temperature rise after nail penetration, and overheating was greatly suppressed. The secondary battery of comparative example 1 was analyzed by decomposition, and the separator was extensively melted, whereas in the secondary battery of example 1 of the present invention, the ceramic-containing thin film remained as it was, and the structure of the ceramic-containing thin film was not destroyed even by heat generation due to short-circuit after nail-piercing, so that enlargement of the short-circuit portion was suppressed, and significant overheating was prevented.

The battery operation occurred by pulling out the nail after the battery nail penetration test of example 1, whereas the battery operation did not occur in comparative example 1, indicating that the battery of the present invention is not an ion battery, but a semiconductor battery utilizing hole movement. Even if a part of the battery is broken, the battery can operate by forming a semiconductor structure, and has good impact resistance which is not possessed by the conventional ion battery.

In the semiconductor nano-battery of example 2, it was observed that the battery including the lead and iodine layer formed in the perovskite structure layer this time had the highest power performance, and had high performance, and the power performance of the battery was improved. This is because the expansion of silicon during charging of the battery applies pressure to the perovskite structure layer, which causes more holes to be generated and enables faster charging. When the battery is discharged, silicon shrinks to weaken the internal pressure of the perovskite structure layer, so that holes are accelerated and moved in the opposite direction to the charging direction, and high output is obtained.

Meanwhile, the ratio of graphite to graphene and the ratio of silicon to graphene have special requirements, and the performance of the battery is improved in combination. For example, if the amount of graphite shown in comparative example 4 is less than 3 times the amount of graphene, both the quick charging performance and the lifetime are reduced. The amount of graphite shown in comparative example 5, if more than 20 times the amount of graphene, would result in performance approaching that of the existing semiconductor nano-battery. This means that the semiconductor function of the invention becomes increasingly difficult to find. In the case where the content of silicon is less than 4 times the amount of graphene as shown in comparative example 6, the rate performance is also reduced while the capacity performance is significantly reduced. From this, it can be seen that the graphene host is difficult to store charges. In comparative example 7, when the amount of silicon is more than 30 times the amount of graphene, the capacity performance is good, but the lifetime performance is remarkably reduced. In addition, it can be seen that high power and fast charging are not favored due to the degradation of rate performance. Meanwhile, the particle diameter of the silicon particles of the present invention is 30nm or more, and if the silicon particles are made to be 30nm or less, the manufacturing cost is at least two times or more, and therefore, the present invention further reduces the cost.

In example 1, when charged at 4.6V, electrons in the negative electrode were distributed in a disk shape on each block. Evaluation was performed by current and resistance measurement, and it was found that the electric field was biased to be distributed in one direction perpendicular to the electric field. At the same time, holes were also measured, and it was found that the electron distribution was biased in a direction opposite to the electron distribution and almost perpendicular to the electric field direction. From this, a phenomenon that electrons and holes move in the negative electrode in the reverse direction to each other and in the direction almost perpendicular to the electric field can be found. It can then also be found that the electron reservoir is arranged within the negative electrode when charged.

The secondary battery of the present invention can realize high power, rapid charging, high capacity, and is suitable for use as a large-sized storage battery or the like. For example, the secondary battery of the present invention is suitable as a battery for a power generation mechanism in which the power generation force is unstable, such as geothermal power generation, wind power generation, solar power generation, hydraulic power generation, and wave power generation. Further, the secondary battery of the present invention is also suitably applied to a mobile tool such as an electric vehicle. Further, since it has high security performance, it is widely used from batteries for bank cards to mobile terminals such as cellular phones.

Claims

1. A semiconductor nano-battery comprising a first electrode, a second electrode and an electrolyte disposed between the first electrode and the second electrode, the second electrode comprising a current collector and an active material layer attached to the current collector, the active material layer comprising an electrode active material, the electrode active material comprising: silicon active material, graphene and graphite; the particle size of the silicon active material is 30-200 nm; the amount of the silicon active material, the graphene and the graphite is more than or equal to 20/3, and more than or equal to 30/4;

the electrolyte is an all-solid-state electrolyte, the electrolyte is a perovskite structure layer, and the perovskite structure layer contains lead and iodine elements;

will PbI_２The concentration of N, N-dimethylformamide solution of (2) is 40%, coating and drying are carried out on the surface of the second electrode, and CH is added_３ＮＨ_３I is dissolved in 2-propanol with the concentration of 45 percent and then coated on the surface of the dried second electrode, and after drying, the second electrode is stored for 72 hours in a vacuum drying environment with the pressure of-100 kPa and 105 degrees to be made into a battery, and the perovskite structure layer with the thickness of 4-6 mu m is formed on the surface of the second electrode.

2. The semiconductor nano-battery of claim 1, wherein the silicon active material is selected from one or more of silicon, an oxide of silicon, an alloy of silicon; the graphene is of a multilayer structure, and preferably contains less than 10 layers of nano-scale layer graphene.

3. The semiconductor nano-battery of claim 1, wherein the graphene comprises lithium-doped graphene;

and/or, the silicon active material comprises a lithium doped silicon active material;

and/or, the graphite comprises lithium doped graphite;

and/or the electrode active material is doped with a halogen.

4. The semiconductor nano-battery according to claim 1, wherein lithium metal is further attached to the surface of the active material layer;

and/or the active material layer is also doped with phosphorus oxide and/or sulfur oxide;

and/or a perovskite structure layer is further attached to the surface of the active material layer, preferably, the perovskite structure layer is CH_３ＮＨ_３ＰｂＩ_３And (3) a layer.

5. The semiconductor nano-battery of claim 1, wherein the electrolyte contains phosphorus and sulfur elements.

6. The semiconductor nano-battery according to claim 1, wherein the electrolyte contains propyne mesylate and/or a sulfonate compound, preferably wherein the sulfonate compound is 2-butyne-1, 4-diol dimethane sulfonate.

7. The semiconductor nano-battery of claim 1, further comprising a ceramic separator between the first and second electrodes.

8. The semiconductor nano-battery according to claim 1, wherein the first electrode comprises a first current collector and a first active material layer attached to the first current collector, the first active material layer contains a first electrode active material, and the first electrode active material contains a p-type semiconductor material; preferably, the first electrode active material contains lithium and nickel elements; preferably, the first electrode active material contains LixNiyMzO alpha, wherein, 0 < x < 3, y + z ═ 1, 1 < alpha < 4, M is selected from one or more of antimony, lead, phosphorus, boron, aluminum and gallium;

preferably, the first active material layer further contains a binder, and the binder further contains graphene, ion-conductive glass, or phosphorus.