CN112331906A - Active material ball layer structure - Google Patents
Active material ball layer structure Download PDFInfo
- Publication number
- CN112331906A CN112331906A CN201910716537.0A CN201910716537A CN112331906A CN 112331906 A CN112331906 A CN 112331906A CN 201910716537 A CN201910716537 A CN 201910716537A CN 112331906 A CN112331906 A CN 112331906A
- Authority
- CN
- China
- Prior art keywords
- active material
- electrolyte
- layer structure
- mixed
- material ball
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, 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 present invention teaches an active material ball layer structure, which mainly comprises a plurality of active material balls composed of active material particles, a first mixed electrolyte located inside the active material balls, and a second mixed electrolyte located outside the active material balls. The first mixed electrolyte is mainly composed of electrolyte with larger deformation, and the second mixed electrolyte is mainly composed of electrolyte with smaller deformation. The invention utilizes the first mixed electrolyte to effectively control the position of active material particles in the active material ball and reduce the derived problems, and then the first mixed electrolyte and the second mixed electrolyte are arranged inside and outside the active material ball in a different way to reduce the charge transfer resistance and provide the resistance of volume expansion of the active material ball.
Description
Technical Field
The present invention relates to a pole layer structure, and more particularly to an active material ball pole layer structure.
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 liquid electrolytes is also a great safety concern for battery users.
Furthermore, one of the reasons for the unstable performance of the current lithium battery is that the surface activity of the electrode is relatively high (negative electrode) and the voltage is relatively high (positive electrode), which leads to the unstable interface between the electrode and the electrolyte, and further generates a so-called exothermic reaction to form an inactive protective film on the contact interface between the electrode and the electrolyte, and the reaction consumes the liquid electrolyte and the lithium ions and also generates heat. Once local short circuit occurs, the local temperature rises rapidly, and at the moment, the passive protective film becomes unstable and releases heat; this exothermic reaction is cumulative, and the temperature of the entire battery continues to rise. 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, having ionic conductivity similar to that of liquid electrolytes, but without 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 the effective transmission of lithium ions, and thus it is still difficult to completely replace liquid electrolytes.
Furthermore, on the lithium ion battery negative electrode material, because the theoretical specific capacity of the traditional graphite carbon negative electrode material is only 372mAh/g, the improvement of the energy density of the lithium ion battery is limited, and because silicon has the theoretical specific capacity as high as 4200mAh/g, the silicon becomes the focus of the current research. However, when the elemental silicon is used as a negative electrode, a large volume change (up to 300%) is generated in the charge and discharge process, which easily causes a depletion interface to be formed between the electrolyte and the elemental silicon, and the performance of the electrode is continuously reduced.
How to effectively apply a large amount of solid electrolyte and improve the electrical capacity of the electrode layer is an urgent problem in the art.
Disclosure of Invention
In view of the above, the present invention is directed to an active material ball electrode layer structure, which utilizes a dual-type electrolyte inside and outside an active material ball constructed by a concentration difference or a property difference for the combination of the active material ball to solve the problems of high charge transfer resistance and low contact area caused by the direct contact between the solid electrolyte and the active material, and to reduce the amount of organic solvents as much as possible to improve the safety of the battery.
Another objective of the present invention is to provide an active material ball layer structure, in which the internal electrolyte can solve the problem of depletion region generated by the drastic change of active material volume by the electrolyte configuration with different concentrations and properties inside and outside the active material ball, and the external electrolyte can provide resistance to the active material volume expansion.
In order to achieve the above object, the present invention provides an active material ball layer structure, which comprises a plurality of active material balls and a second mixed electrolyte, wherein the active material ball comprises a plurality of active material particles, a first conductive material, a first adhesive and a first mixed electrolyte, and the first mixed electrolyte in the active material ball can solve the problem of a depletion region caused by the violent change of the volume of the active material particles by the distribution of the active material ball and the first mixed electrolyte and the second mixed electrolyte with different properties, and the second mixed electrolyte outside the active material sphere can provide resistance to volume expansion of the active material sphere, meanwhile, 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 an optimal ion conduction mode can be achieved while considering safety.
The purpose, technical content, features and effects of the present invention will be more readily understood by the following detailed description of the embodiments.
Drawings
Fig. 1 is a schematic structural view of an active material sphere of the present invention.
Fig. 2 is a schematic diagram of an active material ball layer structure according to an embodiment of the invention.
Fig. 3 is a schematic diagram of another embodiment of an active material ball layer structure according to an embodiment of the invention.
Fig. 4 is a schematic view of another embodiment of the active material sphere of the present invention.
[ description of reference ]
10 active material sphere
11 active material particles
12 first conductive material
14 first mixed electrolyte
20 active material ball layer structure
21 active material particles
22 second conductive material
24 second mixed electrolyte
31 third active material particles
Detailed Description
First, refer to fig. 1, which is a schematic structural view of an active material sphere of the present invention. As shown, the active material sphere 10 is a pre-formed sphere mainly composed of a plurality of first active material particles 11, a first conductive material 12, and a first mixed electrolyte 14, and the median particle diameter (D50) of the active material particles 11 is not more than 60% of the diameter of the active material sphere. The variation in volume of the first active material particles 11 during the ion intercalation/deintercalation reaction ranges from 15% to 400%.
Please refer to FIG. 2. Fig. 2 is a schematic diagram of an active material ball layer structure according to an embodiment of the invention. The active material ball electrode layer structure 20 disclosed by the invention mainly comprises a plurality of preformed active material balls 10, wherein a first mixed electrolyte 14 is arranged in each active material ball 10, a second mixed electrolyte 24 is arranged outside each active material ball 10, the first mixed electrolyte 14 mainly comprises an electrolyte with a larger deformation amount, and the second mixed electrolyte 24 mainly comprises an electrolyte with a smaller deformation amount. The particle size of the active material spheres is not more than 70% of the thickness of the polar layer of the active material spheres. The electrolyte of larger deformation amount may be selected from liquid/colloidal electrolyte, liquid ion, or soft solid electrolyte selected from sulfur-based, boron hydride-based, halide, or polymer solid electrolyte including polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), and polyvinylidene chloride (PVC) -based polymer solid electrolyte.
Wherein the sulfur-based solid electrolyte can be Thio-lithium ion (Li)xM1_x005FyM0yS4(wherein M is Si or Ge, M0 is P, Al, Zn, Ga or Sb), Li4-x005FxGe1-x005FxPxS4、Li4GeS4、Li3.9Zn0.05GeS4、Li4.275Ge0.61Ga0.25S4、Li3.25Ge0.25P0.75S4、Li3.4Si0.4P0.6S4、Li2.2Zn0.1Zr0.9S3、Li7P3S11、Li4SnS4、Li10GeP2S12、Li10Ge0.95Si0.05P2S12、Li9.54Si1.74P1.44S11.7Cl0.3Or is Li10GeP2S12、Li10MP2S12(M is Si4+, Sn4+), Li10+dM1+dP2-x005FdS12(M is Si4+, Sn4+), Li10Ge1-x005FxSnxP2S12isoLGPS family, or Li6PS5X (X is Cl, Br, I), 67(0.75 Li)2S·0.25P2S5)·33LiBH4An orthorhombic (Argyrodite) crystal system, or Li4PS4I、Li7P2S8I phosphorus sulfur amino (thiophosphates) series material, or Li3x[LixSn1-x005FxS2]、Li2Sn2S5、Li2SnS3、Li0.6[Li0.2Sn0.8S2]And the like. The borohydride can be, for example, LiBH4-LiI(-LiNH2；-P2I4；-P2S5)。
Besides the above components, the polymer solid electrolyte can also be PEO-LiX(X is ClO)4、PF6、BF4、N(SO2CF3)2Etc.), PEO-LiCF3SO3、PEO–LiTFSI、PEO–LiTFSI–Al2O3Composite solid polymer (Composite solid polymer), PEO-LiTFSI-10% TiO2Composite solid polymer, PEO-LiTFSI-10% HNT composite solid polymer, PEO-LiTFSI-10% MMT composite solid polymer, PEO-LiTFSI-1% LGPS composite solid polymer, PEO-LiClO4LAGP, or poly (ethylene glycol) diacrylate (PEGDA), poly (ethylene glycol) dimethacrylate (PEGDMA), poly (ethylene glycol) monomethylether (PEGME), poly (ethylene glycol) dimethacrylate (PEGDME), poly [ ethylene oxide-co-2- (2-methoxyethoxy) ethyl glycidyl ether (PEGDME), poly (ethylene oxide-co-2- (2-methoxyethoxy) ethyl glycidyl ether (PEGDME)](poly[ethylene oxide-co-2-(2-methoxyethoxy)ethyl glycidyl ether]PEO/MEEGE), polyethyl methacrylate (Poly (ethylene methacrylate, PEMA), Poly (oxyethylene) (Poly (oxylene)), polycyanoacrylate (Poly (cyanoacrylate), PCA), Polyethylene glycol (Polyethylene glycol, PEG), Polyvinyl alcohol (Poly (vinyl alcohol), PVA), Polyvinyl butyral resin (PVB), Polyvinyl chloride (Poly (vinyl chloride), PVC-PEMA, PEO-PMMA, Poly (acrylonitrile-co-methyl methacrylate) (Poly (acrylonitrile-co-methyl methacrylate), P (AN-co-MMA)), PVA-PVdF, PAN-PVA, PVC-PEMA; hyperbranched polymers, e.g. poly [ bis (triethylene glycol) benzoic acid](poly[bis(triethylene glycol)benzoate]) (ii) a Polycarbonates (polycarbonates) series, for example poly (ethylene oxide-Poly (ethylene oxide-co-ethylene carbonate), PEOEC, Polyhedral oligomeric silsesquioxane (POSS), poly (ethylene carbonate, PEC), poly (propylene carbonate), PPC), poly (ethyl glycidyl ether carbonate), P (Et-GEC), poly (t-butyl glycidyl ether carbonate), P (tBu-GEC); cyclic carbonates, such as poly (trimethylene carbonate), PTMC; polysiloxane-based, e.g., Polydimethylsiloxane (PDMS), Poly (dimethylsiloxane-co-polyethylene oxide), P (DMS-co-EO), Poly (siloxane-g-ethylene oxide); plastic Crystal Electrolytes (PCEs) series, for example, Succinonitrile (SN), PEO/SN, ETPTA// SN, PAN/PVA-CN/SN; polyesters (Polyesters) series, such as ethylene glycol adipate, diethyl succinate, ethylene malonate. Polynitriles (Polynitriles) series, such as Polyacrylonitrile (PAN), polymethacrylonitrile (Poly (methacrylonitrile), PMAN), Poly (N-2-cyanoethyl) ethyleneamine) (Poly (N-2-cyanoethyl) ethyleneamine), PCEEI, Poly (vinylidenedifluorideenefluoropropylene) (PvdF-HFP), polyvinylidene fluoride (Poly (vinylidenedifluorideene), PvdF), Poly epsilon-caprolactone (Poly (epsilon-caprolactone), PCL).
The electrolyte of lesser deformation may be selected from hard-textured solid electrolytes, such as oxygen-based solid electrolytes, e.g., Lithium Aluminum Titanium Phosphate (LATP) solid electrolyte, Lithium Lanthanum Zirconium Oxide (LLZO) solid electrolyte, or other derivatives. Of course, the description of the electrolyte material with larger deformation amount or smaller deformation amount in this section is only illustrative, and is not intended to limit the present invention to only the electrolyte with larger deformation amount or smaller deformation amount. The larger and smaller deformation amounts defined above refer to the amount of deformation that the electrolyte can undergo with recovery. For example, if fracture occurs it is referred to as non-recoverable, it is not within the scope of the larger and smaller deformations defined herein.
When the first mixed electrolyte 14 is selected from liquid/colloidal electrolytes or liquid ions, the active material particles 11 are expanded due to the charge and discharge processes to squeeze the first mixed electrolyte 14, so that the first mixed electrolyte 14 is slightly squeezed out of the active material balls 10. When the active material particles 11 shrink in volume, the first mixed-electrolyte 14 is drawn into the active material spheres 10, and therefore, the depletion region and the associated depletion derived therefrom do not occur in the overall process. When the first mixed-state electrolyte 14 is a soft solid-state electrolyte, the squeezed first mixed-state electrolyte 14 forms a buffer zone that is deformed under pressure because of the elasticity of the soft solid-state electrolyte. Meanwhile, when the ratio of the soft solid electrolyte in the first mixed electrolyte 14 is high, a certain level of confinement effect can be exerted on the active material particles 11.
The second mixed electrolyte 24 is disposed outside the active material ball 10, fills the adjacent gap of the active material ball 10, and abuts on the outer surface of the active material ball 10, and the resistance to volume expansion of the active material ball 10 can be formed by the second mixed electrolyte 24 mainly composed of electrolyte with small deformation. In this regard, the second mixed electrolyte 24 may intersect or partially intrude into the boundary of the active material ball 10 when disposed, the active material ball 10 is shown only for illustration and not for limitation, the boundary and the second mixed electrolyte 24 are maintained in such a state, and the second mixed electrolyte 24 is also shown only for illustration and not for limitation, position, size, distribution, etc.
Furthermore, the first mixed-mode electrolyte 14 may also contain a smaller amount of electrolyte and the second mixed-mode electrolyte 24 may also contain a larger amount of electrolyte, but in different volume percentages. For example, in the first hybrid electrolyte 14, the volume percentage of the deformable electrolyte is greater than 50%, preferably even greater than 90%, of the total amount of the first hybrid electrolyte 14; in the second mixed-mode electrolyte 24, the volume percentage of the electrolyte with a smaller deformation amount is more than 50%, preferably even more than 90%, of the total amount of the second mixed-mode electrolyte 24. Therefore, by disposing the electrolyte inside and outside the active material ball 10 with different concentrations and properties, the resistance to volume expansion of the active material ball 10 can be effectively provided, and simultaneously, the contact area and state between the electrolyte and the active material particles can be maintained in the optimal state, and the problem of depletion region caused by drastic change of the volume of the active material particles can be eliminated.
In order to make the foregoing active material ball 10 more clear, only possible processes thereof will be illustrated below. When the first mixed electrolyte 14 is in a liquid state, the active material particles 11, the first conductive material 12, and a first adhesive (not shown) are mixed with a solvent according to the above ratio, and then coated on a temporary substrate, followed by drying and removing the solvent, and then the temporary substrate is removed, and then crushed and ball-milled to obtain the active material balls 10. At this time, when the solvent is removed, voids, which are approximately irregular in shape, are generated in the active material sphere 10, and the first mixed electrolyte 14 may be filled.
Since the pores need to be filled with the electrolyte, the first mixed electrolyte 14 is made of the electrolyte with a large deformation amount to be filled conveniently, and the shape of the first mixed electrolyte 14 can be changed according to the shape of the pores by using the characteristics of softness and compressibility of the first mixed electrolyte, so that the first mixed electrolyte 14 can be filled into the pores more reliably to ensure the contact state of the active material particles 11 with the first mixed electrolyte 14. On the other hand, when the composition of the first mixed-type electrolyte 14 is mainly composed of the soft solid-state electrolyte in the electrolyte having a large deformation amount, the soft solid-state electrolyte may also be directly mixed and molded with the active material particles 11, the first conductive material 12, and the first adhesive.
The active material particles 11 may be selected from lithium metal, carbon material or silicon group material, such as silicon and/or silicon oxide, which generate volume variation in electrochemical reaction, and the first adhesive is selected, adjusted or modified to fix the relative position thereof or match the characteristics of different active materials, so as to solve the problems derived therefrom, for example, in the case of silicon and/or silicon oxide, in order to control the volume expansion during charging and discharging, the first adhesive mainly comprises a cross-linked polymer (cross-linked polymer), and the volume percentage of the cross-linked polymer in the first adhesive is greater than 70%, and at the same time, by means of a higher proportion of the first conductive material 12 and the first adhesive, a sufficiently high expansion binding force and electron conductivity can be provided. It is generally known that in a layer (in the case of silicon and/or silicon oxide (Si/SiOx) mixed directly with graphite), the conductive material is about 5% by volume, the adhesive is about 7% by volume, and the active material (including silicon and/or silicon oxide (Si/SiOx) and graphite) is about 88% by volume; in this embodiment of the present invention, in the active material ball 10, the first conductive material 12 accounts for 7-10% by volume, and the first adhesive accounts for 10-15% by volume. Therefore, the expansion binding force can be greatly improved by using a higher amount of the first adhesive and combining with the hard adhesive of which the main component is the cross-linked polymer, and the huge volume change of the silicon material caused by the charging and discharging process can be effectively controlled.
The first conductive material 12 may include artificial graphite (artificial graphite), carbon black (carbon black), acetylene black (acetylene black), graphene (graphene), carbon nanotubes (nanotubes), Vapor Grown Carbon Fibers (VGCF), glass fibers, or a mixture thereof, wherein the carbon nanotubes and the vapor grown carbon fibers may also have the ability to absorb the electrolyte and elastically deform in addition to serving as the conductive material. The first adhesive is mainly composed of a crosslinked polymer with strong physical or chemical adhesion, and has less elasticity, such as a good electron donor (donor) having Acid groups, including Polyimide (PI), Acrylic Acid (Acrylic Acid), Epoxy resin (Epoxy), polyacrylic Acid (PAA), and the like. In combination with the adoption of a large amount of adhesive, the first adhesive with strong rigidity can be used for forming a limiting effect on the active material particles, and the expansion scale generated after the active material particles are charged and discharged is controlled, so that the depletion region which cannot be recovered is controlled or eliminated.
Although the bending ability is reduced by the first adhesive with higher rigidity and the first conductive material 12, and the ratio of the remaining active material is reduced by the compression, which in turn reduces the specific capacity, the active material ball 10 of the present invention is only used as part of the active material in the pole layer structure, so that these concerns are not present, i.e. these defects do not affect the pole layer structure, which will be described in detail later.
Referring back to fig. 2, the preformed active material ball 10 is mixed with a second adhesive to form an active material ball layer structure 20, wherein the second adhesive is different from the first adhesive, for example, when the first adhesive is based on a strong rigid adhesive to control the volume change of the active material ball 10, because the second adhesive lacks elasticity, the second adhesive can be based on an adhesive with higher elasticity, in other words, the elasticity of the second adhesive is higher than that of the first adhesive, and mainly consists of a linear polymer with better elasticity, which may include Polyvinylidene fluoride (PVDF), Polyvinylidene fluoride-co-trichloroethylene (PVDF-HFP), styrene-butadiene rubber (styrene-butadiene rubber; SBR), and sodium carboxymethyl cellulose (CMC); while maintaining the flexible nature of the overall active material ball layer structure 20; among them, PVDF-HFP, SBR have a sponge-like structure and have a high capacity of absorbing an electrolyte.
The space between the active material balls 10 or the outside of the active material balls 10 is mainly formed by mixing the second adhesive, the second conductive material and the second mixed electrolyte 24. This portion is far from the active material particles 11 relative to the first mixed electrolyte 24 in the active material sphere 10, and under the electrolyte requirement conditions, the requirement of this portion (far from the active material particles 11) on the effective contact area with the active material particles 11 is smaller than that of the surface of the active material particles 11 emphasizing a large contact area to obtain high charge transfer, so that the second mixed electrolyte 24 mainly consists of the electrolyte with a small deformation amount, which can greatly reduce the amount of the organic solvent (colloidal/liquid electrolyte) in the whole structure, thereby having better thermal stability and heat dissipation performance, and maintaining safety, and at the same time, a certain limit effect can be generated on the active material sphere 10 by the electrolyte with a small deformation amount. The stopper effect is to restrict or prevent the internal distribution deterioration state of the active material balls due to the expansion of the internal active material particles, particularly, the volume shrinkage and expansion under the charge-discharge cycle, by using an electrolyte having a small amount of external deformation, for example, a hard solid electrolyte. Since the requirement for the effective contact area is not so large, it is possible to perform ion conduction using solid electrolyte particles with a small deformation amount and to allow lithium ions to be transported (bulk transport) between the dots at a high speed. The compositions of the electrolyte with smaller deformation and the electrolyte with larger deformation can be the same as the above, and the filling or forming process is the same, and will not be repeated herein.
In addition, referring to fig. 3, a plurality of second active material particles 21 and a second conductive material 22 may be further included between the active material balls 10 of the active material ball layer structure 20, wherein the second conductive material 22 may also be artificial graphite (artificial graphite), carbon black (carbon black), acetylene black (acetylene black), graphene (graphene), carbon nanotubes (nanotubes), Vapor Grown Carbon Fibers (VGCF), or a mixture thereof, which may be the same as or different from the first conductive material 12, and the second active material particles 21 are selected according to the properties of the active material balls 10.
Further, the active material balls 10 may also have third active material particles 31 mixed therein, as shown in fig. 4. The second active material particles 21 and the third active material particles 31 may be selected from the same or different materials.
In summary, the active material ball layer structure provided by the present invention is formed by the pre-formed active material ball, the second mixed electrolyte located outside the active material ball, the conductive material and the adhesive. The active material sphere includes a first mixed electrolyte therein, which is mainly composed of an electrolyte having a large deformation amount. The second mixed electrolyte is mainly composed of an electrolyte with a small deformation amount. The structure of the invention forms the external part (active material ball) with high transmission speed and the internal part (active material ball) with more directional transmission on ion transmission, thereby achieving the best ion transmission mode and greatly reducing the quantity of organic solvent (colloidal state/liquid state electrolyte) to maintain the continuous safety of the battery system. Meanwhile, the inside of the active material ball can be formed by using the first adhesive and limited aiming at the active material, so that huge volume change of the silicon material caused by the charging and discharging process can be effectively controlled on the premise of maintaining the proportion of the conductive material and the adhesive, or various defects of other active materials are overcome, the problems of depletion regions and derivation caused by the silicon material are solved, the flexibility characteristic of the pole layer can be maintained, and the specific capacity, the electronic conductivity and the ion conductivity can be improved.
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 changes and modifications that come within the spirit and scope of the invention are desired to be protected by the following claims.
Claims (12)
1. An active material ball layer structure, comprising:
a plurality of active material balls formed by a plurality of first active material particles, a first conductive material, a first adhesive and a first mixed electrolyte; and
the second mixed electrolyte is configured outside the active material ball, is filled in the adjacent gap of the active material ball and abuts against the outer surface of the active material ball so as to form resistance to volume expansion of the active material ball;
wherein the first mixed-mode electrolyte consists essentially of a larger amount of deformation of electrolyte and the second mixed-mode electrolyte consists essentially of a smaller amount of deformation of electrolyte.
2. The active material ball layer structure of claim 1 wherein the greater amount of deformation of electrolyte in the first mixed electrolyte is selected from liquid/colloidal electrolyte, liquid ionic or sulfur-based, borohydride-based, halide or polymer solid electrolyte.
3. The active material ball layer structure according to claim 2, wherein the polymer solid electrolyte includes polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, and polyvinylidene chloride-based polymer solid electrolyte.
4. The active material ball layer structure of claim 1, wherein the second mixed electrolyte comprises primarily a less strained electrolyte, and the less strained electrolyte has a volume content greater than 50% of the total volume content of the second electrolyte.
5. The active material ball layer structure of claim 4, wherein the volume content of the lesser deformation amount of electrolyte is greater than 90% of the total volume amount of the second electrolyte.
6. The active material ball layer structure according to claim 4, wherein the electrolyte of a smaller deformation amount is selected from oxygen-based solid electrolytes.
7. The active material ball layer structure of claim 6, wherein the oxygen-based solid electrolyte is a lithium lanthanum zirconium oxygen solid electrolyte or a lithium titanium aluminum phosphate solid electrolyte.
8. The active material ball layer structure of claim 1, wherein the active material particles are selected from metals, carbon materials, silicon and/or silicon oxide.
9. The active material sphere layer structure of claim 1, wherein the active material spheres have a median particle diameter D50 of 70% of the layer thickness and the active material particles have a median particle diameter D50 of 60% of the active material sphere diameter.
10. The active material sphere layer structure of claim 1, further comprising a plurality of second active material particles having different material characteristics from the first active material particles, the second active material particles being located between the active material spheres.
11. The active material sphere layer structure according to claim 1, wherein the active material sphere further has a plurality of third active material particles therein, the third active material particles having a material property different from that of the first active material particles.
12. The active material ball layer structure of claim 1, wherein the volume variation of the first active material particles during ion intercalation/deintercalation reaction ranges from 15% to 400%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910716537.0A CN112331906B (en) | 2019-08-05 | 2019-08-05 | Active material ball layer structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910716537.0A CN112331906B (en) | 2019-08-05 | 2019-08-05 | Active material ball layer structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112331906A true CN112331906A (en) | 2021-02-05 |
| CN112331906B CN112331906B (en) | 2022-08-05 |
Family
ID=74319664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910716537.0A Active CN112331906B (en) | 2019-08-05 | 2019-08-05 | Active material ball layer structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112331906B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022264161A1 (en) * | 2021-06-16 | 2022-12-22 | Tvs Motor Company Limited | Solid-state electrode for ion conducting battery and method of fabricating thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2268346A1 (en) * | 1999-04-07 | 2000-10-07 | Hydro-Quebec | Lipo3 commutation electrode |
| JP2009224239A (en) * | 2008-03-18 | 2009-10-01 | Nissan Motor Co Ltd | Electrode for battery |
| US20110136017A1 (en) * | 2008-08-01 | 2011-06-09 | Seeo, Inc | High capacity anodes |
| CN102324317A (en) * | 2011-09-14 | 2012-01-18 | 中国第一汽车股份有限公司 | Electrode for flexible solid super capacitor and preparation method thereof |
| CN103534847A (en) * | 2011-05-17 | 2014-01-22 | 丰田自动车株式会社 | Positive-electrode active material particle for all-solid battery and method for production thereof |
| CN104756287A (en) * | 2012-08-24 | 2015-07-01 | 斯拉纳米技术有限公司 | Scaffolding matrix with internal nanoparticles |
| CN105280892A (en) * | 2014-07-16 | 2016-01-27 | 辉能科技股份有限公司 | Active material |
| CN107078287A (en) * | 2014-10-14 | 2017-08-18 | 新罗纳米技术有限公司 | Nano-complex battery electrode particle with variation characteristic |
| CN107534138A (en) * | 2015-04-29 | 2018-01-02 | 株式会社Lg 化学 | Negative active core-shell material and the negative pole for including it |
| US20180097235A1 (en) * | 2016-09-30 | 2018-04-05 | Samsung Electronics Co., Ltd. | Negative electrode for lithium secondary battery and lithium secondary battery including the same |
| WO2019065030A1 (en) * | 2017-09-29 | 2019-04-04 | 日本ゼオン株式会社 | All-solid secondary battery electrode composite particles, method of manufacturing same, all-solid secondary battery electrode, and all-solid secondary battery |
| KR20190044397A (en) * | 2017-10-20 | 2019-04-30 | 주식회사 엘지화학 | An anode for all-solid type batteries including solid electrolyte |
| CN110034275A (en) * | 2019-04-25 | 2019-07-19 | 上海空间电源研究所 | A kind of sulfide solid state battery buffer layer and preparation method thereof and solid state battery |
-
2019
- 2019-08-05 CN CN201910716537.0A patent/CN112331906B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2268346A1 (en) * | 1999-04-07 | 2000-10-07 | Hydro-Quebec | Lipo3 commutation electrode |
| JP2009224239A (en) * | 2008-03-18 | 2009-10-01 | Nissan Motor Co Ltd | Electrode for battery |
| US20110136017A1 (en) * | 2008-08-01 | 2011-06-09 | Seeo, Inc | High capacity anodes |
| CN103534847A (en) * | 2011-05-17 | 2014-01-22 | 丰田自动车株式会社 | Positive-electrode active material particle for all-solid battery and method for production thereof |
| CN102324317A (en) * | 2011-09-14 | 2012-01-18 | 中国第一汽车股份有限公司 | Electrode for flexible solid super capacitor and preparation method thereof |
| CN104756287A (en) * | 2012-08-24 | 2015-07-01 | 斯拉纳米技术有限公司 | Scaffolding matrix with internal nanoparticles |
| CN105280892A (en) * | 2014-07-16 | 2016-01-27 | 辉能科技股份有限公司 | Active material |
| CN107078287A (en) * | 2014-10-14 | 2017-08-18 | 新罗纳米技术有限公司 | Nano-complex battery electrode particle with variation characteristic |
| CN107534138A (en) * | 2015-04-29 | 2018-01-02 | 株式会社Lg 化学 | Negative active core-shell material and the negative pole for including it |
| US20180097235A1 (en) * | 2016-09-30 | 2018-04-05 | Samsung Electronics Co., Ltd. | Negative electrode for lithium secondary battery and lithium secondary battery including the same |
| WO2019065030A1 (en) * | 2017-09-29 | 2019-04-04 | 日本ゼオン株式会社 | All-solid secondary battery electrode composite particles, method of manufacturing same, all-solid secondary battery electrode, and all-solid secondary battery |
| KR20190044397A (en) * | 2017-10-20 | 2019-04-30 | 주식회사 엘지화학 | An anode for all-solid type batteries including solid electrolyte |
| CN110034275A (en) * | 2019-04-25 | 2019-07-19 | 上海空间电源研究所 | A kind of sulfide solid state battery buffer layer and preparation method thereof and solid state battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022264161A1 (en) * | 2021-06-16 | 2022-12-22 | Tvs Motor Company Limited | Solid-state electrode for ion conducting battery and method of fabricating thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112331906B (en) | 2022-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8974966B2 (en) | Negative electrode for lithium rechargeable battery and lithium rechargeable battery adopting the same | |
| US20190067685A1 (en) | Negative electrode slurry, negative electrode plate and electrochemical energy storage device | |
| KR102590173B1 (en) | Passivation Layer for Lithium Electrode, Lithium Electrode and Lithium Secondary Battery Comprising the Same | |
| CN103165840B (en) | Electrode assembly of lithium secondary battery | |
| CN113594408B (en) | Negative plate and battery | |
| JP2000164254A (en) | Gel electrolyte and gel electrolyte battery | |
| CN102368562B (en) | A kind of lithium ion battery | |
| US20210296704A1 (en) | All solid state battery and method for manufacturing the same | |
| CN112331906B (en) | Active material ball layer structure | |
| KR102473509B1 (en) | Active material ball electrode layer structure | |
| CN108023051A (en) | A kind of isolation film and the lithium ion battery containing the isolation film | |
| JP2010118216A (en) | Electrode body for power storage element, and non-aqueous lithium type power storage element including the same | |
| US20230352666A1 (en) | Active material ball composite layer | |
| KR20190085874A (en) | Slurry composition for forming cathode, cathode manufactured thereby, and battery comprising the same | |
| JP5114857B2 (en) | Electrode plate for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery | |
| CN115050960A (en) | Material for accelerating mass transfer and improving expansion of negative electrode and application | |
| JP2003223931A (en) | Polymer electrolyte base material, polymer electrolyte, polymer electrolyte sheet, and electrochemical element using them | |
| KR101438696B1 (en) | Electrode Assembly and Secondary Battery having the Same | |
| CN112448022A (en) | Asymmetric electrolyte battery and preparation method thereof | |
| KR102002404B1 (en) | Electrode and method for manufacturing of the same | |
| CN110649224A (en) | Electrode for battery cell, battery cell comprising same and use thereof | |
| JPH0935705A (en) | Polymer electrolyte-lithium battery and manufacture of its electrode | |
| CN112331820B (en) | Active material ball composite layer | |
| KR102649623B1 (en) | Zinc negative electrode with gel coating layer for aqueous zinc ion battery and manufacturing method thereof and aqueous zinc ion battery including the same | |
| JPH11204098A (en) | Lithium secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |