CN110165221A - Pole layer composite material - Google Patents

Pole layer composite material Download PDF

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Publication number
CN110165221A
CN110165221A CN201810151689.6A CN201810151689A CN110165221A CN 110165221 A CN110165221 A CN 110165221A CN 201810151689 A CN201810151689 A CN 201810151689A CN 110165221 A CN110165221 A CN 110165221A
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electrolyte
layer
solid electrolyte
composite material
layer composite
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CN110165221B (en
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杨思枬
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HUINENG TECHNOLOGY CO LTD
Prologium Holding Inc
Prologium Technology Co Ltd
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HUINENG TECHNOLOGY CO LTD
Prologium Holding Inc
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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

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention discloses a kind of pole layer composite material.Pole layer composite material of the invention includes at least one active material, the surface of active material is provided with one layer of artificial passive film (APF), effectively to obstruct contact of the electrolyte with active material, unnecessary lithium ion is avoided to consume, middle layer and outer layer are formed outside artificial passive film simultaneously, middle layer and outer layer all have colloidal state/liquid electrolyte and solid electrolyte, but colloidal state/liquid electrolyte and solid electrolyte be not identical as the ratio of outer layer in middle level, by reduce charge transfer resistance and reduce organic solvent amount purpose under reach in a manner of optimal ionic conduction.

Description

Pole layer composite material
Technical field
The present invention relates to a kind of pole layer composite material, especially a kind of pole layer applied to lithium ion secondary battery system is multiple Condensation material.
Background technique
Existing lithium ion secondary battery mainly passes through liquid electrolyte as lithium ion transport medium, however liquid is electric The volatile characteristic for solving matter, can all cause adverse effect to human body and environment；Meanwhile the inflammability of liquid electrolyte is for battery For user and great security risk.
Furthermore it is larger (cathode) to be primarily due to electrode active surface for unstable one of the reason of lithium battery performance at present It is higher (anode) with voltage, it will lead to interface between the two under directly contact of electrode and electrolyte and generate unstable, and then production Raw so-called exothermic reaction forms passivity protective film on the two contact interface, these reactions can consume liquid electrolyte and lithium Ion, while can also generate heat.Once partial short-circuit occurs, local temperature is quickly increased, and passivity protective film will become not at this time Stablize, while heat can be released；And the exothermic reaction can be accumulated, so that the constant temperature of battery entirety rises.One Denier battery temperature increase to thermal runaway reaction (thermal runaway) initial temperature (or induce temperature (trigger Temp)), then the phenomenon that causing thermal runaway, in turn results in the breakoff phenomenon of battery, such as explosion or on fire, in use Cause sizable safety concerns.
In recent years, solid electrolyte becomes another research focal point, and there is ion similar with liquid electrolyte to lead Electric rate, but the not property for being easy to evaporate with burn of liquid electrolyte, meanwhile, it is opposite with the interface of surface of active material steady Fixed (either chemically or electrochemical properties).However solid electrolyte is different from liquid electrolyte, with active material Contact surface is small and contact surface is bad, charge transfer reaction constant is lower, therefore there is the active materials with positive and negative anodes in the layer of pole The larger problem of charge transfer interface resistance value, be unfavorable for lithium ion and effectively transmit, therefore be still difficult to replace liquid completely at present Electrolyte.
To solve the above problems, the present invention proposes a kind of novel pole layer composite material.
Summary of the invention
In view of this, above-mentioned known technology can be solved the main purpose of the present invention is to provide a kind of pole layer composite material Defect, using artificial passive film (APF) effectively contact of the barrier electrolyte with active material, and avoid unnecessary lithium ion The decaying of consumption and the lithium battery caused by it.
Another object of the present invention is to provide a kind of pole layer composite materials, construct colloidal state/liquid using concentration difference The middle layer of electrolyte and solid electrolyte different distributions and outer layer are directly contacted solving solid electrolyte with active material and are produced Raw high charge transfer resistance and low contact area, and the amount of organic solvent is reduced as far as possible, improve the safety in utilization of battery.
In order to achieve the above objectives, the present invention provides a kind of pole layer composite material, it includes active material, artificial passive film, Middle layer and outer layer, the artificial passive film form and are coated on surface of active material, and then middle layer and outer layer sequentially wrap again It is overlying on outside it, and middle layer and outer layer all have colloidal state/liquid electrolyte and solid electrolyte, wherein the colloidal state/liquid in the middle layer The content of state electrolyte is greater than the content of solid electrolyte, and the content of the solid electrolyte of the outer layer is greater than colloidal state/liquid electricity The content of matter is solved, the method that artificial passive film is directly coated by surface of active material is used and is greatly reduced or avoids colloidal state/liquid State electrolyte is directly contacted with active material, and can reduce declining for lithium battery caused by unnecessary lithium ion consumption Subtract, while being formed by middle layer and outer layer using concentration difference, in addition to liquid/colloidal electrolyte usage amount can be greatly reduced Outside, can more solve solid electrolyte directly contacted with active material caused by high charge transfer resistance spread out with low contact area Raw problem, thus optimal ionic conduction mode can be reached in the case where compromise between security.
Hereafter by specific embodiment elaborate, make it easier to understand the purpose of the present invention, technology contents, feature and Its effect reached.
Detailed description of the invention
Fig. 1 is the schematic diagram of the structure of the layer composite material of pole provided by the embodiment of the present invention.
Fig. 2 is the partial enlargement diagram of pole layer composite material of the invention.
Fig. 3 is another partial enlargement diagram of pole layer composite material of the invention.
Fig. 4 is the embodiment schematic diagram that pole layer composite material of the invention is applied to lithium battery.
Fig. 5 is that the layer composite material of pole provided by the embodiment of the present invention is applied to the another of lithium battery system
Embodiment schematic diagram.
Specific embodiment
The present invention provides a kind of pole layer composite material, and consideration liquid/colloidal electrolyte and solid electrolyte first respectively has it Advantage and disadvantage, for currently known technology, solid electrolyte is difficult to replace liquid/colloidal electrolyte completely, therefore mixes liquid/ Colloidal electrolyte method appropriate compared with solid electrolyte will be one is configured, Lai Fahui by the distribution of concentration difference The advantages of two kinds of electrolyte, while (or reduction) its defect is solved, to reach optimal ionic conduction situation.Meanwhile considering to live Property material and liquid/colloidal electrolyte will form the defect of passivity protective film, then by way of artificial passive film is arranged, to subtract Less or the excessive contact of liquid/colloidal electrolyte and active material is avoided, it is compound with regard to the active material structure and its pole layer below The part of the structure of material cooperates attached drawing to be explained.
First also referring to Fig. 1, Fig. 2 and Fig. 3, it is followed successively by the layer composite material of pole provided by the embodiment of the present invention Another the implementing of schematic diagram, the partial enlargement diagram of pole layer composite material of the invention and pole layer composite material of the invention The partial enlargement diagram of mode.Pole provided by the present invention layer composite material 10 mainly comprising multiple active materials 11 and in Layer 12, outer layer 13.11 surface of active material is formed with artificial passive film (Artificial passive film；APF) 101, people 101 main purpose of work passive film is that the excessive contact of liquid/colloidal electrolyte Yu active material 11 is reduced or avoided.This place The artificial passive film 101 referred to can be considered internal layer, and mainly can be according to ion transport whether, and divide into non-solid electrolyte system Column and solid electrolyte series.The thickness of artificial passive film 101 is probably less than 100 nanometers in fact.Non-solid electrolyte series It can be conductive material, the mixture without the ceramic material of lithium ion or both materials.Ceramic material without lithium It can be selected from zirconium oxide, silica, aluminium oxide, titanium oxide or gallium oxide etc..Further, for example when artificial passive film 101 It is to select the ceramic material without lithium come when constituting, which can be used mechanical deposit mode, physical/chemical Sedimentation or aforesaid way mixing are to be made.It can be in mechanical deposit mode and adopt ball mill or fluidized bed (Fluidized Bed mechanical deposit mode) is formed, and at this time the thickness of artificial passive film 101 is less than 100 nanometers.It is deposited in physical/chemical Membrane structure made of atomic level storehouse can be obtained in method, the thickness of artificial passive film 101 may be selected to receive less than 20 at this time Rice.And the artificial passive film 101 of conductive material series can equally adopt above-mentioned mechanical deposit mode, physical/chemical sedimentation or Aforesaid way mixes to be made, and repeats no more in this.
In this non-solid electrolyte series in ion transport, when with certain thickness, electrolyte conduct need to be relied on The medium of ion transport.If class membrane structure made of thinner thickness, such as atomic level storehouse, then ion can be without relying on Electrolyte directly transmits.
When artificial passive film 101 is solid electrolyte series, oxygen system, sulphur system or lithium-aluminium alloy or nitrogen can be selected from Change lithium (LiN3), form can be crystalline state or glassy state.When the material of artificial passive film 101 is selected from conductive material, It can be carbonaceous material, such as graphite or graphene or conducting polymer.With regard to implementing for above, the structure institute energy of Fig. 2 The effect reached is better than the structure of Fig. 3, and when carrying out the structure of Fig. 2, artificial passive film 101 is best with solid electrolyte.
Therefore, ion as mentioned earlier itself could be perforated through under the considerations of artificial passive film 101 factor, artificial blunt Property film 101 and active material 11 modular construction design can be and completely be coated on the mode on 11 surface of active material to each other, or Person is the form for having hole for electrolyte flow and touching 11 surface of active material, further can also be in the form of above two Mixing.
For example, as shown in Fig. 2, artificial passive film 101 is substantially completely coated on 11 surface of active material, to avoid The contact area of liquid/colloidal electrolyte and active material 11.Or as shown in figure 3, artificial passive film 101 is can with hole The form on 11 surface of active material is moved and touched to electrolysis liquid stream, such as the non-solid electrolyte of powder shaped storehouse, utilizes heap The mutual gap of stack powder is as hole, to reduce the contact area of liquid/colloidal electrolyte Yu active material 11.In addition, Under the configuration state of Fig. 3, the powder of stack states can give the SEI layer structural support for being formed in 11 surface of active material, increase The stability for adding chemistry, electrochemistry and heat, avoids SEI layers of duration from crumbling and live again, and then reduces the consumption of lithium ion.It is above-mentioned The thickness of artificial passive film 101 described in Fig. 2 and Fig. 3 is about several to tens nanometers.
Then, to be located at artificial 101 outside of passivity film layer middle layer 12 be located at 12 outside of middle layer outer layer 13 into Row illustrates.Middle layer 12 includes the first colloidal state/liquid electrolyte 121 and the first solid electrolyte 122.Outer layer 13 includes second Colloidal state/liquid electrolyte 131 and the second solid electrolyte 132.For convenient for substantially understanding, by the preparation method of pole layer composite material To illustrate.It is, in general, that pole layer composite material is mainly by active material, conductive material, adhesion promoter (binder) and liquid/colloidal state Electrolyte (including organic solvent, lithium salts) is mixed to be formed.Pole layer composite material 10 of the invention is to be prepared via a method which : after 11 surface of active material is first formed artificial passive film 101, then by the active material with artificial passive film 101, conduction Material, adhesion promoter (binder) are mixed with liquid/colloidal electrolyte (including organic solvent, lithium salts), by liquid after mixing Electrolyte is extracted out, and obtains the overall accumulated amount M of first time liquid/colloidal electrolyte1.Active material 11 and conductive material, After adhesion promoter mixing, the reason of because of its material particle size and material property, hole not of uniform size is formed, in general Accumulated between slurry solvent drying process and active material 11 and formed larger hole (about diameter be greater than 500nm, and/or Farther out (approximately more than 500nm) from artificial passive film 101), area more mixed by active material 11 and conductive material, adhesion promoter Domain, will form lesser hole, (about diameter is less than 500nm, and/or relatively close (from artificial passive film apart from active material 11 To 500nm)) other than 101.In general, the total volume of small hole can be less than the total volume of larger hole.Preferred mode Under, the total volume of small hole can be much smaller than the total volume of larger hole.
Then in aforementioned biggish hole or from inserting volume or higher concentration in the farther away hole of active material Second solid electrolyte 132, then in aforementioned lesser hole or from the closer hole of active material insert small amount or Be low concentration the first solid electrolyte 122 after, then according to distance apart from the active material 11 insert first and second liquid State/colloidal electrolyte 121,131, hereon referred to as second of liquid/colloidal electrolyte total volume M2.It therefore, can be in artificial passivity About it is less than the part of 500nm other than film 101 to the region of 500nm and/or hole about diameter, filling is mixed with the first solid state electrolysis Matter 122 and the first liquid/colloidal electrolyte 121 and form middle layer 12, and away from artificial passive film 101 be approximately more than 500nm area Domain and/or hole diameter are greater than about the part of 500nm, and filling the second solid electrolyte 132 of mixing and the second liquid/colloidal state are electrolysed Matter 131 and form outer layer 13.Certainly, active material 11 and correlation distribution are only to illustrate in attached drawing, are not limited to it The mode of distribution.At this point, because the former filling liquid/colloidal electrolyte hole in part has changed by first and second solid state electrolysis Matter 122,132 is inserted, so M1≧M2, liquid/colloidal electrolyte usage amount will can so be greatly reduced.Above-mentioned first glue State/liquid electrolyte 121 is selected from identical material or different materials with the second colloidal state/liquid electrolyte 122.First solid-state electricity Solution matter 122 is selected from identical material or different materials with the second solid electrolyte 132.
Therefore, for its component ratio, liquid/colloidal electrolyte in middle layer 12 can be made according to aforementioned filling mode Content is higher than solid electrolyte and the solid electrolyte content in outer layer 13 is higher than liquid/colloidal electrolyte.Furthermore middle layer 12 Conductive material and adhesion promoter when being all blended with pole layer with outer layer 13, this is unquestionable.Usually, with regard to middle layer 12 It says, the volume content of the first colloidal state/liquid electrolyte 121 is greater than the first colloidal state/liquid electrolyte 121 and the first solid electrolyte The 50% of 122 overall accumulated amount is preferably even greater than 90%.In the same manner, for outer layer 13, the second solid electrolyte 132 Volume content is greater than the 50% of the overall accumulated amount of the second colloidal state/liquid electrolyte 131 and the second solid electrolyte 132, preferably very To more than 90%.So compromise between security (reducing liquid/colloidal electrolyte usage amount) and ion are mainly wanted in design (contact surface for solving solid electrolyte and active material is small and contact surface is bad, reaction constant is more low asks for conductibility optimization Topic).
It is directed to the part in middle layer 12 again, because the layer is directly directly to connect with active material 11 (or artificial passive film 101) Touching is to conduct ion, if it is as the main component with solid electrolyte, then can derive with known identical problem, that is, connect The problems such as contacting surface is small and bad, reaction constant is lower, therefore, design middle layer 12 are as the main component with colloidal state/liquid electrolyte, It is exactly the content that colloidal state/liquid electrolyte content is greater than solid electrolyte, liquid/colloidal electrolyte content is greater than total amount 50%, preferably even it is greater than 90%, and can provide ion non-directional optimal transmission mode, while liquid/colloidal electrolyte With the contact surface state of active material 11 (or artificial passive film 101), can also be greatly improved compared to solid electrolyte, and can drop Low charge transfer resistance.Middle layer 12 is about apart from artificial passive film 101 about less than 500nm or hole diameter less than 500 nanometers.
And outer layer 13 then for further away from and the biggish regional scope of area, be about to be about apart from artificial passive film 101 Greater than except 500nm or hole diameter is greater than 500 nanometers of region, therefore, it is as the main component with solid electrolyte to design this layer, Namely the content of solid electrolyte is greater than colloidal state/liquid electrolyte content, and solid electrolyte content is greater than the 50% of total amount, Preferably even be greater than 90%, and the amount of integrally-built organic solvent (colloidal state/liquid electrolyte) can be greatly reduced, and can have compared with Good hotlist is existing, and sustainable maintenance safety.Therefore, outer layer 13 can be by determining whether the contact of solid electrolyte particle Ionic conduction direction, and it is defined as the ion transmission mode for relatively having certain party tropism, and lithium ion high speed and a large amount of biographies can be allowed Defeated (bulk transport).
The material of middle layer 12 and the solid electrolyte of outer layer 13 can consolidating as described in previous artificial passive film 101 with form State electrolyte.
Furthermore further material illustration is carried out for above-mentioned solid electrolyte.The choosing of sulphur system solid electrolyte From the Li of glassy state2S-P2S5, crystalline state Lix’My’PSzOr the Li of glass ceramics state2S-P2S5One of or it is a variety of, wherein M is one of Si, Ge, Sn or a variety of, x '+4y '+5=2Z ', 0≤y '≤1；It is further preferred that the glassy state Li2S-P2S570Li selected from glassy state2S-30P2S5、75Li2S-25P2S5、80Li2S-20P2S5One of or it is a variety of；It is described The Li of glass ceramics state2S-P2S570Li selected from glass ceramics state2S-30P2S5、75Li2S-25P2S5、80Li2S-20P2S5In It is one or more；The Li of 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 of Cl or a variety of.
Oxide system solid electrolyte one kind can be the solid oxide electrolyte of fluorite structure, such as mix molar fraction The zirconium oxide (yttria stabilized zirconia, YSZ) of 3-10% yttria；Another kind of is perovskite structure (ABO3) solid oxide electrolyte, such as doping LaGaO3(lanthanum gallate).Or various oxide systems solid electrolyte, it lifts Li for example1+x+y(Al,Ga)x(Ti,Ge)2-xSiyP3-yO12Crystallization, wherein 0≤x≤1 and 0≤y≤1.Oxide system solid-state electricity Solving matter can be such as 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。
Certainly, it is possible to use the various solid electrolytes of remaining above-mentioned non-exhaustive list, this part solid electrolyte are said It is bright be only it is schematically illustrate, be not intended to limit the invention and be only capable of using solid electrolyte above-mentioned.
It is applied in battery system, can be in monopole using layer composite material 10 in pole provided by the present invention, citing comes It says and is set as anode, cooperate known pole layer 30 and 42, two current collection layers 41,43 of separation layer to constitute battery system, such as Fig. 4 institute Show；It certainly, can also be by two pole layers (positive and negative electrode) all using pole layer composite material 10 of the invention (see Fig. 5).
In summary, pole provided by the present invention layer composite material (or is subtracted using artificial passive film (APF) effectively barrier It is few) contact of the liquid/colloidal electrolyte with active material, avoid unnecessary lithium ion consumption and its caused lithium battery Decaying.Furthermore the middle layer established using liquid/colloidal electrolyte concentration difference opposite with solid electrolyte and outer layer, shape At make on lithium ion transport can be by the outer layer of high transmission speed, and the internal layer transmitted compared with polytropism can be carried out, to reach most Good ion transmission mode, while the amount of organic solvent (colloidal state/liquid electrolyte) can be greatly reduced again, maintain battery system Continue safety.Furthermore two-electrolyte system (liquid/colloidal electrolyte and solid electrolyte) of the invention can effectively increase The ability of ion conducting can possess its high chemical stabilization especially when solid electrolyte is using oxide series Property, and its ionic conductance and electrode compatibility can be increased by two-electrolyte system.
The foregoing is only a preferred embodiment of the present invention, is not used to limit the scope of implementation of the present invention.Therefore All equivalent changes or modification made according to feature described in the present patent application range and spirit, should all include in Shen of the invention It please be in the scope of the patents.
[description of symbols]
10 poles layer composite material
101 artificial passive films
11 active materials
12 middle layers
121 first liquid/colloidal electrolyte
122 first solid electrolytes
13 outer layers
131 second liquid/colloidal electrolyte
132 second solid electrolytes

Claims (14)

1. a kind of pole layer composite material, it includes:
Active material；
Artificial passive film is coated on the surface of active material；
Middle layer, coats the artificial passive film, and the middle layer includes the first solid electrolyte and the first colloidal state/liquid electrolyte Matter, and first colloidal state/liquid electrolyte content is greater than the content of first solid electrolyte；And
Outer layer, coats the middle layer, and the outer layer includes the second solid electrolyte and the second colloidal state/liquid electrolyte, and institute The content for stating the second solid electrolyte is greater than second colloidal state/liquid electrolyte content.
2. layer composite material in pole according to claim 1, wherein the thickness of the artificial passive film is less than 100 nanometers.
3. layer composite material in pole according to claim 1, wherein the artificial passive film is coated on institute to be substantially complete State the solid electrolyte of surface of active material.
4. layer composite material in pole according to claim 1, wherein the artificial passive film is non-solid electrolyte.
5. layer composite material in pole according to claim 4, wherein the artificial passive film is selected from conductive material, is free of lithium Ceramic material or both mixture, wherein the conductive material is selected from carbonaceous material or conducting polymer, described to be free of The ceramic material of lithium is selected from zirconium oxide, silica, aluminium oxide, titanium oxide or gallium oxide.
6. layer composite material in pole according to claim 1, wherein first solid electrolyte and the outer layer in the middle layer The second solid electrolyte form be crystalline state or glassy state.
7. pole according to claim 1 layer composite material, wherein the middle layer at a distance from the artificial passive film≤ 500 nanometers.
8. layer composite material in pole according to claim 1, wherein the outer layer is greater than at a distance from the artificial passive film 500 nanometers.
9. layer composite material in pole according to claim 1, wherein first colloidal state in the middle layer/liquid electrolyte body Product content is greater than the 50% of the first colloidal state/liquid electrolyte in the middle layer and the overall accumulated amount of the first solid electrolyte.
10. layer composite material in pole according to claim 9, wherein first colloidal state in the middle layer/liquid electrolyte body Product content is greater than the 90% of the first colloidal state/liquid electrolyte in the middle layer and the overall accumulated amount of the first solid electrolyte.
11. layer composite material in pole according to claim 1, wherein the volume of the second solid electrolyte of the outer layer contains Amount is greater than the 50% of the second colloidal state/liquid electrolyte of the outer layer and the overall accumulated amount of the second solid electrolyte.
12. layer composite material in pole according to claim 11, wherein the volume of the second solid electrolyte of the outer layer contains Amount is greater than the 90% of the second colloidal state/liquid electrolyte of the outer layer and the overall accumulated amount of the second solid electrolyte.
13. layer composite material in pole according to claim 1, anode and/or cathode as lithium battery.
14. pole according to claim 1 layer composite material, wherein first colloidal state in the middle layer/liquid electrolyte and the One solid electrolyte is filling hole of the diameter less than 500 nanometers, and the second colloidal state/liquid electrolyte of the outer layer and second are consolidated State electrolyte is the hole inserted diameter and be greater than 500 nanometers.
CN201810151689.6A 2018-02-14 2018-02-14 Electrode layer composite material Active CN110165221B (en)

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CN112701346A (en) * 2019-10-22 2021-04-23 辉能科技股份有限公司 Solid electrolyte contact surface conditioning material and mixed electrolyte system thereof
CN113140730A (en) * 2021-03-26 2021-07-20 万向一二三股份公司 High-nickel ternary lithium ion battery

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