CN110165221B - Electrode layer composite material - Google Patents

Electrode layer composite material Download PDF

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Publication number
CN110165221B
CN110165221B CN201810151689.6A CN201810151689A CN110165221B CN 110165221 B CN110165221 B CN 110165221B CN 201810151689 A CN201810151689 A CN 201810151689A CN 110165221 B CN110165221 B CN 110165221B
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electrolyte
colloidal
solid electrolyte
lithium ion
secondary battery
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CN110165221A (en
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杨思枬
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Prologium Holding Inc
Prologium Technology Co Ltd
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Prologium Holding Inc
Prologium Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses an electrode layer composite material. The electrode layer composite material comprises at least one active material, wherein the surface of the active material is provided with an Artificial Passive Film (APF) to effectively prevent the contact of electrolyte and the active material and avoid unnecessary lithium ion consumption, and simultaneously, a middle layer and an outer layer are formed outside the artificial passive film, and both the middle layer and the outer layer are provided with colloidal/liquid electrolyte and solid electrolyte, but the proportions of the colloidal/liquid electrolyte and the solid electrolyte in the middle layer and the outer layer are different, so that the optimal ion conduction mode is achieved under the aims of reducing charge transfer resistance and reducing the amount of organic solvents.

Description

Electrode layer composite material
Technical Field
The present invention relates to a pole layer composite material, and more particularly to a pole layer composite material for a lithium ion secondary battery system.
Background
The existing lithium ion secondary battery mainly uses liquid electrolyte as a lithium ion transmission medium, but the volatile property of the liquid electrolyte can cause adverse effects on human bodies and the environment; meanwhile, the flammability of the liquid electrolyte is also a great safety hazard for battery users.
Furthermore, one of the reasons for the unstable performance of the current lithium battery is mainly due to the large surface activity of the electrode (negative electrode) and the high voltage (positive electrode), which results in the instability of the interface between the electrode and the electrolyte under the direct contact therebetween, and further generates so-called exothermic reactions that consume the liquid electrolyte and lithium ions and also generate heat, thereby forming an inactive protective film on the contact interface therebetween. Once local short circuit occurs, the local temperature rises rapidly, and at the moment, the passive protective film becomes unstable and releases heat; the exothermic reaction is cumulative, and the temperature of the entire battery is continuously increased. Once the temperature of the battery is increased to the initial temperature (or trigger temperature) of the thermal runaway reaction (thermal runaway), a thermal runaway phenomenon is caused, which may cause damage to the battery, such as explosion or fire, and cause considerable safety concerns in use.
In recent years, solid electrolytes have become another focus of research, which have similar ionic conductivity to liquid electrolytes, but do not have the easy evaporation and combustion properties of liquid electrolytes, while the interface with the active material surface is relatively stable (whether chemical or electrochemical). However, unlike liquid electrolytes, solid electrolytes have a small contact surface with active materials, a poor contact surface, and a low charge transfer reaction constant, so that the resistance of the charge transfer interface with the active materials of the positive and negative electrodes in the electrode layer is large, which is not conducive to effective transmission of lithium ions, and thus it is still difficult to completely replace liquid electrolytes.
In order to solve the above problems, the present invention provides a novel electrode layer composite material.
Disclosure of Invention
Accordingly, the present invention is directed to a pole layer composite material, which solves the above-mentioned drawbacks of the prior art, effectively blocks the contact between the electrolyte and the active material by using an Artificial Passive Film (APF), and prevents unnecessary consumption of lithium ions and the degradation of the lithium battery caused thereby.
Another objective of the present invention is to provide an electrode layer composite material, which utilizes concentration difference to construct a middle layer and an outer layer of colloidal/liquid electrolyte and solid electrolyte with different distributions, so as to solve the problems of high charge transfer resistance and low contact area caused by direct contact between the solid electrolyte and the active material, reduce the amount of organic solvent as much as possible, and improve the safety of the battery.
In order to achieve the above objects, the present invention provides an electrode layer composite material, which comprises an active material, an artificial passive film, a middle layer and an outer layer, wherein the artificial passive film is formed and coated on the surface of the active material, then the middle layer and the outer layer are sequentially coated on the active material, and both the middle layer and the outer layer have a colloidal/liquid electrolyte and a solid electrolyte, wherein the colloidal/liquid electrolyte content of the middle layer is greater than the solid electrolyte content, and the solid electrolyte content of the outer layer is greater than the colloidal/liquid electrolyte content, and the direct contact between the colloidal/liquid electrolyte and the active material is greatly reduced or avoided by a method of directly coating the artificial passive film on the surface of the active material, so that the attenuation of a lithium battery caused by unnecessary lithium ion consumption can be reduced, and the middle layer and the outer layer formed by the concentration difference are utilized, in addition to greatly reducing the usage amount of the liquid/colloidal electrolyte, the problems derived from high charge transfer resistance and low contact area generated by direct contact between the solid electrolyte and the active material can be solved, so that the optimal ion conduction mode can be achieved while considering safety.
The purpose, technical content, features and effects of the present invention will be more easily understood through the detailed description of the specific embodiments.
Drawings
Fig. 1 is a schematic diagram of a structure of a pole layer composite according to an embodiment of the present invention.
Fig. 2 is a partially enlarged schematic view of the electrode layer composite of the present invention.
Fig. 3 is another enlarged partial view of the electrode layer composite of the present invention.
Fig. 4 is a schematic view of an embodiment in which the electrode layer composite of the present invention is applied to a lithium battery.
Fig. 5 is a schematic diagram of another embodiment of the electrode layer composite material applied to a lithium battery system according to an embodiment of the present invention.
Detailed Description
The present invention provides an electrode layer composite material, which firstly considers the advantages and disadvantages of the liquid/colloidal electrolyte and the solid electrolyte, and the solid electrolyte is difficult to completely replace the liquid/colloidal electrolyte in the prior art, so that the mixing of the liquid/colloidal electrolyte and the solid electrolyte is a relatively good method, and the advantages of the two electrolytes can be exerted through the distribution configuration of concentration difference, and the defects can be simultaneously solved (or reduced) to achieve the best ion conduction condition. Meanwhile, considering the defect that the active material and the liquid/colloidal electrolyte may form an inactive protective film, the active material structure and the electrode layer composite structure thereof will be partially described with reference to the accompanying drawings by providing an artificial inactive film to reduce or avoid the excessive contact between the liquid/colloidal electrolyte and the active material.
First, referring to fig. 1, fig. 2 and fig. 3, a schematic diagram of a pole layer composite material according to an embodiment of the present invention, a partially enlarged schematic diagram of a pole layer composite material according to the present invention, and a partially enlarged schematic diagram of another embodiment of a pole layer composite material according to the present invention are sequentially shown. The electrode layer composite material 10 provided by the invention mainly comprises a plurality of active materials 11, a middle layer 12 and an outer layer 13. An Artificial Passive Film (APF) 101 is formed on the surface of the active material 11, and the main purpose of the Artificial passive film 101 is to reduce or prevent the excessive contact of the liquid/colloidal electrolyte with the active material 11. The artificial passive film 101 may be considered as an inner layer, and may be classified into a non-solid electrolyte series and a solid electrolyte series according to whether it is ion-transmissive or not. The thickness of the artificial passive film 101 is roughly less than 100 nm. The series of non-solid electrolytes may be a conductive material, a ceramic material without lithium ions, or a mixture of the two materials. The lithium-free ceramic material may be selected from zirconia, silica, alumina, titania, gallium oxide, or the like. Further, for example, when the artificial passivation film 101 is formed by using a ceramic material containing no lithium, the artificial passivation film 101 can be formed by using a mechanical deposition method, a physical/chemical deposition method, or a mixture thereof. The mechanical deposition method may be a ball mill or a Fluidized bed (Fluidized bed) mechanical deposition method, and the thickness of the artificial passive film 101 is less than 100 nm. An atomic-scale stacked film structure can be obtained by physical/chemical deposition, and the thickness of the artificial passive film 101 can be selected to be less than 20 nm. The artificial passive film 101 of the conductive material series can be manufactured by the above mechanical deposition method, physical/chemical deposition method, or a mixture thereof, which will not be described herein.
In this non-solid electrolyte family, the electrolyte is relied upon to mediate ion transfer when it has a certain thickness. If the thickness is thin, such as a film-like structure stacked on an atomic scale, ions can be directly transferred without relying on an electrolyte.
When the artificial passive film 101 is a solid electrolyte, it may be selected from oxygen-based, sulfur-based, or lithium aluminum alloy, or lithium nitride, and its form may be crystalline or glassy. When the material of the artificial passive film 101 is selected from conductive materials, it may be a carbonaceous material, such as graphite or graphene, or a conductive polymer. In practice, the structure of fig. 2 achieves better results than the structure of fig. 3, and the artificial passive film 101 is optimized for solid electrolyte when the structure of fig. 2 is implemented.
Therefore, as mentioned above, considering whether the ions can penetrate through the artificial passive film 101, the structural design of the assembly between the artificial passive film 101 and the active material 11 may be a complete coating on the surface of the active material 11, or a configuration having pores for the electrolyte to flow and touch the surface of the active material 11, or a mixture of the two configurations.
For example, as shown in fig. 2, the artificial passive film 101 is substantially completely coated on the surface of the active material 11 to avoid the contact area between the liquid/colloidal electrolyte and the active material 11. Alternatively, as shown in fig. 3, the artificial passivation film 101 has a form of a porous structure for the electrolyte to flow and touch the surface of the active material 11, such as a powder-like stacked non-solid electrolyte material, and the contact area between the liquid/colloidal electrolyte and the active material 11 is reduced by using the gaps between the stacked powder as pores. In addition, in the structural state of fig. 3, the powder in the stacked state can provide structural support to the SEI layer formed on the surface of the active material 11, thereby increasing chemical, electrochemical and thermal stability, preventing the SEI layer from being continuously broken down and regenerated, and further reducing the consumption of lithium ions. The thickness of the artificial passive film 101 described above with reference to fig. 2 and 3 is about several to several tens of nanometers.
Next, the middle layer 12 located around the outer periphery of the artificial passivation film layer 101 and the outer layer 13 located around the outer periphery of the middle layer 12 will be explained. The middle layer 12 includes a first colloidal/liquid electrolyte 121 and a first solid electrolyte 122. The outer layer 13 comprises a second glueA liquid/liquid electrolyte 131 and a second solid electrolyte 132. For the sake of general understanding, the method of preparing the electrode layer composite will be described. Generally, the electrode layer composite is mainly formed by mixing an active material, a conductive material, an adhesion promoter (binder) and a liquid/colloidal electrolyte (containing an organic solvent, lithium salt). The electrode layer composite 10 of the present invention is prepared by the following method: firstly, forming an artificial passive film 101 on the surface of an active material 11, then mixing the active material with the artificial passive film 101, a conductive material and an adhesion promoter (binder) with a liquid/colloidal electrolyte (comprising an organic solvent and a lithium salt), extracting the liquid electrolyte after mixing, and obtaining the total volume M of the first liquid/colloidal electrolyte1. When the active material 11 is mixed with the conductive material and the adhesion promoter, pores with different sizes are formed due to the particle size and material characteristics of the active material, and generally, a larger pore (about more than 500nm in diameter and/or farther from the artificial passive film 101 (about more than 500nm)) is formed by the accumulation of the slurry solvent drying process and the active material 11, while a smaller pore (about less than 500nm in diameter and/or closer to the active material 11 (from the outside of the artificial passive film 101 to 500nm)) is formed in a region where the active material 11 is mixed with the conductive material and the adhesion promoter. Generally, the total volume of smaller holes will be less than the total volume of larger holes. Preferably, the total volume of the smaller holes is much smaller than the total volume of the larger holes.
Then, a large amount or a high concentration of the second solid electrolyte 132 is filled in the larger pores or the pores far from the active material, and then a small amount or a low concentration of the first solid electrolyte 122 is filled in the smaller pores or the pores near to the active material, and then the first and second liquid/ colloidal electrolytes 121, 131 are filled according to the distance from the active material 11, which is referred to as the total volume M of the second liquid/colloidal electrolyte2. Therefore, the middle layer 12 is formed by filling the first solid electrolyte 122 and the first liquid/colloidal electrolyte 121 in a region of about 500nm and/or a portion of the hole having a diameter of less than about 500nm outside the artificial passivation film 101, and in a region of about 500nm or more from the artificial passivation film 101And/or the portion with pores larger than about 500nm in diameter, is filled with a mixture of the second solid electrolyte 132 and the second liquid/colloidal electrolyte 131 to form the outer layer 13. Of course, the active material 11 and the associated distribution in the drawings are merely illustrative and are not intended to limit the manner in which it is distributed. At this time, since the pores partially filled with the liquid/colloidal electrolyte have been filled with the first and second solid electrolytes 122 and 132, M1≧M2This will allow a substantial reduction in the amount of liquid/colloidal electrolyte used. The first colloidal/liquid electrolyte 121 and the second colloidal/liquid electrolyte 122 are selected from the same material or different materials. The first solid electrolyte 122 and the second solid electrolyte 132 are selected from the same material or different materials.
Therefore, the filling method can make the content of the liquid/colloidal electrolyte in the middle layer 12 higher than that of the solid electrolyte and the content of the solid electrolyte in the outer layer 13 higher than that of the liquid/colloidal electrolyte. Furthermore, it is needless to say that the middle layer 12 and the outer layer 13 both have a conductive material and an adhesion promoter when the electrode layers are mixed. Generally, for the middle layer 12, the volume content of the first colloidal/liquid electrolyte 121 is more than 50%, preferably even more than 90%, of the total volume content of the first colloidal/liquid electrolyte 121 and the first solid electrolyte 122. Similarly, in the case of the outer layer 13, the volume content of the second solid-state electrolyte 132 is more than 50%, preferably even more than 90%, of the total volume amount of the second colloidal/liquid-state electrolyte 131 and the second solid-state electrolyte 132. Such design is mainly to take into account safety (reduction of the amount of liquid/colloidal electrolyte used) and optimization of ion conductivity (solving the problems of small contact area, poor contact area, low reaction constant, etc. of the solid electrolyte and the active material).
Further, regarding the portion of the middle layer 12, since the layer is directly contacted with the active material 11 (or the artificial passive film 101) to conduct ions, if the layer is mainly composed of a solid electrolyte, the same problem as the known one is derived, i.e. the contact area is small and bad, the reaction constant is low, and the like, therefore, the middle layer 12 is designed to be mainly composed of a colloidal/liquid electrolyte, i.e. the content of the colloidal/liquid electrolyte is greater than the content of the solid electrolyte, the content of the liquid/colloidal electrolyte is greater than 50%, preferably even greater than 90%, of the total amount, so as to provide the best transmission mode without directionality of ions, and simultaneously, the contact area state between the liquid/colloidal electrolyte and the active material 11 (or the artificial passive film 101) can be greatly improved compared with the solid electrolyte, and the charge transfer resistance can be reduced. The middle layer 12 is approximately less than 500nm away from the artificial passive film 101 or the diameter of the holes is less than 500 nm.
The outer layer 13 is a region with a larger area, which is more than about 500nm away from the artificial passivation film 101 or has a pore diameter more than 500nm, so that the layer is designed to have a solid electrolyte as a main component, i.e. the solid electrolyte content is greater than the colloidal/liquid electrolyte content, which is greater than 50% of the total amount, preferably even greater than 90%, so as to greatly reduce the amount of organic solvent (colloidal/liquid electrolyte) in the whole structure, thereby achieving better thermal performance and maintaining the safety. Therefore, the outer layer 13 can determine the ion conduction direction by the contact or non-contact of the solid electrolyte particles, and is defined as an ion transport manner having a more specific orientation, and can allow high-speed and mass transport (bulk transport) of lithium ions.
The material and form of the solid electrolyte of the middle layer 12 and the outer layer 13 may be the same as those of the solid electrolyte described in the prior art for the artificial passive film 101.
Further, the above solid electrolyte is exemplified by further materials. The sulfur-based solid electrolyte is selected from Li in a glassy state2S-P2S5Crystalline form of Lix’My’PSzOr Li in the form of glass-ceramics2S-P2S5Wherein M is one or more of Si, Ge and Sn, and x '+ 4 y' +5 is 2Z ', 0 is less than or equal to y' ≦ 1; further preferably, the glassy Li2S-P2S5Selected from glassy 70Li2S-30P2S5、75Li2S-25P2S5、80Li2S-20P2S5One or more of; li in the glass-ceramic state2S-P2S570Li in a state selected from glass-ceramics2S-30P2S5、75Li2S-25P2S5、80Li2S-20P2S5One or more of; li in the crystalline statex’My’PSz’Selected from Li3PS4、Li4SnS4、Li4GeS4、Li10SnP2S12、Li10GeP4S12、Li10SiP2S12、Li10GeP2S12、Li7P3S11、L9.54Si1.74P1.44S11.7Cl0.3、β-Li3PS4、Li7P2SI、Li7P3S11、0.4LiI-0.6Li4SnS4、Li6PS5One or more of Cl.
Oxide-based solid electrolyte one type may be a fluorite-structured solid oxide electrolyte such as zirconia (YSZ) doped with 3 to 10 mole percent yttria; the other is perovskite structure (ABO)3) Solid oxide electrolytes, e.g. doped LaGaO3(lanthanum gallate). Or various oxide-based solid electrolytes, e.g. Li1+x+y(Al,Ga)x(Ti,Ge)2-xSiyP3-yO12And (3) crystallization, wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1. The oxide-based solid electrolyte may be, for example, Li2O-Al2O3-SiO2-P2O5-TiO2、Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2、Na3.3Zr1.7La0.3Si3PO12、Li3.5Si0.5P0.5O4、Li3xLa2/3xTiO3、Li7La3Zr2O12、Li0.38La0.56Ti0.99Al0.01O3、Li0.34LaTiO2.94。
Of course, other solid-state electrolytes not listed in detail above may also be used, and the description of this portion of the solid-state electrolyte is merely illustrative and not intended to limit the present invention to the use of the foregoing solid-state electrolyte.
In practical application to a battery system, the electrode layer composite material 10 provided by the present invention can be used in a single electrode, for example, as a positive electrode, and the known electrode layer 30, the isolation layer 42, and the two current collecting layers 41 and 43 are combined to form a battery system, as shown in fig. 4; of course, it is also possible to use the inventive pole layer composite 10 for both pole layers (positive and negative) as well (see fig. 5).
In summary, the electrode layer composite provided by the present invention effectively blocks (or reduces) the contact between the liquid/colloidal electrolyte and the active material by using an Artificial Passive Film (APF), thereby preventing unnecessary consumption of lithium ions and the resulting degradation of the lithium battery. Furthermore, the intermediate layer and the outer layer, which are established by the relative concentration difference between the liquid/colloidal electrolyte and the solid electrolyte, form the outer layer which can realize high transmission speed in lithium ion transmission and the inner layer which can realize more directional transmission, so as to achieve the best ion transmission mode, and simultaneously, the amount of the organic solvent (colloidal/liquid electrolyte) can be greatly reduced, and the continuous safety of the battery system can be maintained. Furthermore, the dual electrolyte system (liquid/colloidal electrolyte and solid electrolyte) of the present invention can effectively increase the ion conduction capability, especially when the solid electrolyte is an oxide series, it can maintain its high chemical stability, and can increase its ionic conductivity and electrode compatibility through the dual electrolyte system.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Therefore, all equivalent changes or modifications made according to the features and the spirit of the invention described in the claims should be included in the claims of the invention.
[ description of reference ]
10-pole layer composite material
101 Artificial blunt Membrane
11 active material
12 middle layer
121 first liquid/colloidal electrolyte
122 first solid electrolyte
13 outer layer
131 second liquid/colloidal electrolyte
132 second solid electrolyte

Claims (14)

1. A lithium ion secondary battery electrode comprising:
an active material;
an artificial passive film coated on the surface of the active material;
a middle layer covering the artificial passive film, wherein the middle layer comprises a first solid electrolyte and a first colloidal/liquid electrolyte, and the volume content of the first colloidal/liquid electrolyte is greater than that of the first solid electrolyte; and
an outer layer covering the middle layer, wherein the outer layer comprises a second solid electrolyte and a second colloidal/liquid electrolyte, and the volume content of the second solid electrolyte is greater than that of the second colloidal/liquid electrolyte.
2. The lithium ion secondary battery electrode of claim 1, wherein the thickness of the artificial passive film is less than 100 nanometers.
3. The lithium ion secondary battery electrode of claim 1, wherein the artificial passive film is a solid electrolyte substantially completely coated on the surface of the active material.
4. The lithium ion secondary battery electrode according to claim 1, wherein the artificial passive film is a non-solid electrolyte.
5. The lithium ion secondary battery electrode according to claim 4, wherein the artificial passive film is selected from a conductive material selected from a carbonaceous material or a conductive polymer, a non-lithium containing ceramic material selected from zirconia, silica, alumina, titania, or gallium oxide, or a mixture thereof.
6. The lithium ion secondary battery electrode according to claim 1, wherein the first solid electrolyte of the middle layer and the second solid electrolyte of the outer layer are in a crystalline or glassy state.
7. The lithium ion secondary battery electrode according to claim 1, wherein the distance between the middle layer and the artificial passive film is 500nm or less.
8. The lithium ion secondary battery electrode of claim 1, wherein the distance of the outer layer from the artificial passive membrane is greater than 500 nanometers.
9. The lithium ion secondary battery electrode of claim 1, wherein the volume content of the first colloidal/liquid electrolyte of the middle layer is greater than 50% of the total volume amount of the first colloidal/liquid electrolyte and the first solid electrolyte of the middle layer.
10. The lithium ion secondary battery electrode of claim 9, wherein the volume content of the first colloidal/liquid electrolyte of the middle layer is greater than 90% of the total volume content of the first colloidal/liquid electrolyte and the first solid electrolyte of the middle layer.
11. The lithium ion secondary battery electrode of claim 1, wherein the volume content of the second solid state electrolyte of the outer layer is greater than 50% of the total volume amount of the second colloidal/liquid electrolyte and the second solid state electrolyte of the outer layer.
12. The lithium ion secondary battery electrode of claim 11, wherein the volume content of the second solid state electrolyte of the outer layer is greater than 90% of the total volume amount of the second colloidal/liquid electrolyte and the second solid state electrolyte of the outer layer.
13. The lithium ion secondary battery electrode according to claim 1, which is used as a positive electrode and/or a negative electrode of a lithium battery.
14. The lithium ion secondary battery electrode of claim 1, wherein the first colloidal/liquid electrolyte and the first solid electrolyte of the middle layer are filled with pores having a diameter of less than 500nm, and the second colloidal/liquid electrolyte and the second solid electrolyte of the outer layer are filled with pores having a diameter of more than 500 nm.
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CN111883759A (en) * 2020-07-29 2020-11-03 黄杰 Nano-silicon composite material with core-shell structure and preparation method thereof
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