CN109698319A - Cathode of solid state battery and preparation method thereof and solid state electrode - Google Patents
Cathode of solid state battery and preparation method thereof and solid state electrode Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/052—Li-accumulators
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- 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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The present invention proposes cathode of solid state battery and preparation method thereof and solid state battery.The cathode includes: conductive material；Binder course, binder course are coated on the surface of the conductive material；Active material layer, active material layer are arranged on the surface of binder course；Electrolyte layer, electrolyte layer are coated on the surface of active material layer and binder course.Conductive material provides quick electron channel for cathode as a result, and the cathode that is set as of electrolyte layer provides continuous ion channel, to meet the job requirement of cathode；The setting of active material layer can provide high specific capacity for the battery using the cathode；The setting of binder course can be improved active material layer and uniformly be distributed in conductive material surface, avoid cathode in conductive material surface serious agglomeration；And electrolyte layer is arranged on the surface of active material layer, active material layer can be not only further avoided to fall off, and have certain inhibiting effect to the bulking effect of the active material in active material layer, the variation of cathode thickness or volume will not be caused in this way in battery charge and discharge process.
Description
Technical field
The present invention relates to battery technology fields, in particular to cathode and preparation method thereof and solid state electrode.
Background technique
With the development and progress of society, demand of the people to high-energy density lithium battery is more more and more intense.It is commercial at present
Lithium battery mostly uses greatly the liquid electrolyte containing combustible organic solvent, and there are volatile, inflammable, explosive risks, has very
Serious safety problem；Solid state battery is expected to fundamentally thoroughly solve as next-generation most potential electrochemical energy storage device
The certainly safety problem of battery.
The cathode of common solid state battery mainly has graphite, silicon (Si) cathode, lithium metal etc. at present, wherein graphite electrode by
In its lower specific capacity, seriously constrain the raising of battery energy density, but its with preferable high rate performance and
Cycle life；Silicium cathode have very high theoretical specific capacity (can reach 4200mAh/g), but its there is also very serious volumes
Expansion issues, and reversible capacity is lower for the first time；When lithium metal is as negative electrode material, Li dendrite is easily generated in cyclic process and is made
At battery short circuit, and unconfined volume expansion can occurs in it, and dusting is serious, while lithium metal is extremely active, easily with air
In moisture, oxygen etc. react, high production cost, production is difficult.Therefore, developing one kind has height ratio capacity, convenient for adding
It is extremely urgent for the negative electrode material of high energy density cells demand to can satisfy people for work.
Research accordingly, with respect to the cathode of solid state battery needs to be goed deep into.
Summary of the invention
In view of this, the present invention is directed to propose a kind of cathode of solid state battery, the negative electrode volume expansion is unobvious, Ke Yiti
Height uses specific capacity, high rate performance, cycle performance or the energy density of the cathode.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
An object of the present invention is to provide a kind of cathode of solid state battery.According to an embodiment of the invention, including: to lead
Electric material；Binder course, the binder course are coated on the surface of the conductive material；Active material layer, the active material layer
It is arranged in the part of the surface of the binder course；Electrolyte layer, the electrolyte layer are coated on the active material layer and described
On the surface of binder course.Conductive material provides quick electron channel for cathode as a result, and electrolyte layer is set as cathode offer
Continuous ion channel, to meet the job requirement of cathode；The setting of active material layer can be to be mentioned using the battery of the cathode
For high specific capacity；The binding force between conductive material and active material layer can be improved in the setting of binder course, guarantees active matter
Matter layer is uniformly distributed in conductive material surface；And electrolyte layer is arranged on the surface of active material layer, it not only can be into
One step avoids active material layer from falling off, and has certain inhibiting effect to the bulking effect of the active material in active material layer,
It will not cause the variation of cathode thickness or volume in this way in battery charge and discharge process.
According to an embodiment of the invention, the conductive material includes carbon paper, foam copper, nickel foam or foamed aluminium or class 3D more
Hole conductive material, the preferably described carbon paper, the carbon paper meet at least one the following conditions: with a thickness of 100~300 microns；It is formed
The carbon fiber diameter of the carbon paper is 2~10 microns.
According to an embodiment of the invention, the material for forming the binder course includes zinc oxide, aluminium oxide, silicon monoxide, two
At least one of silica, germanium dioxide, silicon, germanium, aluminium, nickel, magnesium and silver, preferably zinc oxide, the binder course with a thickness of
Nanoscale.
According to an embodiment of the invention, the active material includes active material, the active material layer includes silicon, an oxygen
At least one of SiClx, silica and Si-C composite material；The active material layer further includes binder, the binder
At least one in Kynoar, polytetrafluoroethylene (PTFE), carboxymethyl cellulose, SBR styrene butadiene rubbers and polyimides
Kind；The active material layer further includes conductive agent, and the conductive agent is selected from conductive black, acetylene black, electrically conductive graphite (KS-6, carbon
At least one of nanotube and graphene；Based on the gross mass of the cathode, the mass percentage of active material is 5~
50%.
According to an embodiment of the invention, the electrolyte layer includes at least one of organic matter, solid electrolyte, and
Lithium salts；The organic matter is selected from polyethylene glycol oxide, polypropylene oxide, polypropylene carbonate, poly- ethylene carbonate, succinonitrile, gathers
At least one of biasfluoroethylene-hexafluoropropylene；The lithium salts is selected from lithium perchlorate, double trifluoromethanesulfonimide lithiums, double fluorine
At least one of sulfimide lithium, biethyl diacid lithium borate and LiBF4；The solid electrolyte is selected from electrostrictive polymer
At least one of Xie Zhi, oxide electrolyte, sulfide electrolyte；Based on the gross mass of the cathode, the electrolyte layer
Mass percentage be 5%~60%；The porosity of the cathode is 5%~85%.
Another object of the present invention is to propose a kind of method of cathode for preparing solid state battery, this method is simple, easily grasps
Make, preparation cost is low or easy to industrialized production.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
According to an embodiment of the invention, the method for preparing the cathode of mentioned-above solid state battery includes: in conductive material
Surface on form binder course；Active material layer is formed on the surface of the binder course, and is carried out first and be dried, so as to
Active material layer is formed in the part of the surface of the binder course；The shape on the surface of the active material layer and the binder course
It at electrolyte solution layer or electrolyte melt liquid layer, and carries out second and is dried, so as in the active material layer and institute
It states and forms electrolyte layer on the surface of binder course.It is provided as a result, by the conductive material in the cathode of above method preparation for cathode
Quick electron channel, electrolyte layer provide continuous ion channel for cathode, to meet the job requirement of cathode；Active material
Layer provides high specific capacity for the battery using the cathode；The combination between conductive material and active material layer can be improved in binder course
Power guarantees that active material layer is uniformly distributed in conductive material surface；And electrolyte layer is formed in the surface of active material layer
On, it can not only further avoid active material layer and fall off, and have one to the bulking effect of the active material in active material layer
Fixed inhibiting effect will not cause the variation of cathode thickness or volume in this way in battery charge and discharge process；In addition, above-mentioned preparation
Method is simple, easy to operate, and preparation cost is low, easy to industrialized production.
According to an embodiment of the invention, forming the binder course on the surface of the conductive material is by the following method
One of obtain: method one: the conductive material is impregnated into certain time in the organic solution containing functional element；After immersion
The conductive material carry out high temperature sintering, to form the binder course on the surface of the conductive material, method two: it is logical
It crosses magnetron sputtering or pyrolytic coating and directly forms the binder course on the surface of the conductive material；It is described containing functional element
What organic solution was obtained through the following steps: functional element source, surfactant and organic solvent are mixed, so as to
To the organic solution containing functional element；The functional element source is two water zinc acetates, anhydrous zinc acetate, aluminum acetate, positive silicon
At least one of acetoacetic ester and germanium tetrachloride；The concentration of functional element is 0.5~2mol/L in the functional element source.
According to an embodiment of the invention, what the slurry for forming the active material layer was obtained through the following steps: by silicon,
At least one of silicon monoxide, silica and Si-C composite material, binder and solvent are uniformly mixed, described to obtain
Slurry.
According to an embodiment of the invention, the electrolyte solution for forming the electrolyte solution layer is obtained through the following steps
: at least one of organic matter and solid electrolyte, lithium salts and solvent are mixed；The solid content of the electrolyte solution is
2%~15%；What the electrolyte melt liquid was obtained through the following steps: by organic matter and solid electrolyte at least
A kind of and lithium salts mixed melting.
Another object of the present invention is to propose a kind of solid state battery.According to an embodiment of the invention, the solid state battery
Including mentioned-above cathode.The solid state battery cyclicity is good as a result, and circulation volume conservation rate is high, long service life.Ability
The feature and advantage that field technique personnel are appreciated that the solid state battery compared with the existing technology and have above-mentioned cathode all,
This is repeated no more.
Detailed description of the invention
Fig. 1 is the method flow diagram that the cathode of solid state battery is prepared in one embodiment of the invention；
Fig. 2 is the method flow diagram that the cathode of solid state battery is prepared in another embodiment of the present invention；
Fig. 3 is the method flow diagram that the cathode of solid state battery is prepared in another embodiment of the present invention
Fig. 4 is the scanning electron microscope (SEM) photograph of carbon paper used by the embodiment of the present invention 1；
Fig. 5 is the EDS figure of carbon paper employed in the embodiment of the present invention 1；
Fig. 6 is that the scanning electron microscope (SEM) photograph after zinc oxide film is formed in the embodiment of the present invention 1；
Fig. 7 is the EDS figure after forming zinc oxide film in the embodiment of the present invention 1；
Fig. 8 is that the surface sweeping electron microscope after active material layer is formed in the embodiment of the present invention 1；
Fig. 9 is that the surface sweeping electron microscope after electrolyte layer is formed in the embodiment of the present invention 1；
Figure 10 is the charging and discharging curve figure of solid state battery in the embodiment of the present invention 1.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art
It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer,
For can be with conventional products that are commercially available.
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.
An object of the present invention is to provide a kind of cathode of solid state battery.According to an embodiment of the invention, including: to lead
Electric material；Binder course, the binder course are coated on the surface of the conductive material；Active material layer, the active material layer
It is arranged in the part of the surface of the binder course；Electrolyte layer, the electrolyte layer are coated on the active material layer and described
On the surface of binder course.Conductive material provides quick electron channel for cathode as a result, and electrolyte layer is set as cathode offer
Continuous ion channel, to meet the job requirement of cathode；The setting of active material layer can be to be mentioned using the battery of the cathode
For high specific capacity, to improve the energy density of the battery using the cathode；The setting of binder course can be improved conductive material with
Binding force between active material layer guarantees that active material layer is uniformly distributed in conductive material surface；And electrolyte layer is set
It sets on the surface of active material layer, can not only further avoid active material layer and fall off, and to the work in active material layer
The bulking effect of property substance has certain inhibiting effect, and cathode thickness or volume will not be caused in this way in battery charge and discharge process
Variation；In addition, binder course is arranged while having the effect of close lithium, the presence of this layer can increase conductive material for metal
The compatibility of lithium facilitates deposition of the lithium metal on conductive material, is more conducive to conductive material and plays itself de- lithium/embedding
Lithium performance facilitates the performance of battery higher energy density.
According to an embodiment of the invention, active material layer is to exist in granular form, so active material layer can not be complete
Binder course is covered entirely, so electrolyte layer is not only coated on the surface of active material layer, is also coated on not by active material
On the surface of the binder course of layer covering, also further active material layer can be avoided to fall off in this way.
According to an embodiment of the invention, to improve the high rate performance and cycle life of cathode, conductive material includes carbon paper, bubble
The conductive material of foam copper, nickel foam or foamed aluminium or other classes 3D structure.Above-mentioned material can make cathode and use as a result,
The battery of the cathode has better high rate performance and cycle life；It is conductive and since carbon paper is made of more conductive fibers
The structure of fiber holistic conformation constitutes continuous conductive network, is evenly distributed in foam copper, nickel foam and foamed aluminium and largely connects
Logical or non-intercommunicating pore hole, so above-mentioned material is a kind of material of 3D structure, inside there is certain gap, the gap
Not only effective space can be provided for the injection of electrolyte inside pole piece, provide enough expansions for the expansion of active material layer
Space；In addition, the presence in above-mentioned gap makes the specific surface area of cathode larger, it can effectively mitigate the overall weight of the cathode, into
And help to improve the cathode i.e. energy density of battery entirety.In some embodiments of the invention, conductive material is carbon paper.By
This, service performance more preferably, can be better.
According to an embodiment of the invention, binder course is coated on the whole table for referring to conductive material on the surface of conductive material
Face, by taking carbon paper as an example, carbon paper includes many root carbon fibers, and binder course is coated on the surface of every carbon fiber；With foam
For copper, foam copper surface and its it is internal there is a large amount of gap, and binder course be covered on foam copper outer surface and its
On the inner surface of internal voids.
According to an embodiment of the invention, carbon paper meets at least one the following conditions to improve the performance of cathode: with a thickness of
100~300 microns, such as 100 microns, 120 microns, 140 microns, 160 microns, 180 microns, 200 microns, 220 microns, 240
Micron, 260 microns, 280 microns or 300 microns, the service performance of cathode is best as a result, so that being had using the cathode preferable
High rate performance and cycle life；If carbon paper thickness is less than 100 microns, carbon paper is easily broken, and makes the high rate performance of battery
It is relatively not good enough with cycle life；If carbon paper thickness is greater than 300 microns, cathode integral thickness is thicker, is unfavorable for battery entirety energy
The performance of metric density.The carbon fiber diameter for forming carbon paper is 2~10 microns, for example, 2 microns, 3 microns, 4 microns, 5 microns, it is 6 micro-
Rice, 7 microns, 8 microns, 9 microns or 10 microns, the conduction of carbon paper is preferable as a result, convenient for the transmission of electronics；If carbon fiber diameter
Less than 2 microns, then carbon fiber relative intensity reduces, and influences the integral strength of pole piece；If the diameter of carbon fiber is greater than 10 microns,
Specific surface area is opposite inside pole piece is reduced, and active material layer coats area reduction.
According to an embodiment of the invention, carbon paper can be touched with solvent, in order to prevent carbon paper knot due in preparation process
Structure changes, and is formed between more carbon fibers of carbon paper and is not provided with binder.Thus, it is possible to binder is avoided to be dissolved in solvent,
The phenomenon that causing carbon paper structure to change.
According to an embodiment of the invention, being formed to guarantee that active material layer is uniformly distributed on the surface of binder course
The material of binder course includes in zinc oxide, aluminium oxide, silicon monoxide, silica, germanium dioxide, silicon, germanium, aluminium, nickel, magnesium and silver
At least one.Thus, it is possible to greatly improve active material layer in the dispersion for combining layer surface, prevent active material in binder course
Surface occurs to reunite and accumulate, and the material will not influence the performance of conductive material and active material layer performance.Of the invention
In some embodiments, the material for forming binder course is zinc oxide, in this way, its service performance is best, is farthest improved conductive
The binding force of material and active material layer.
According to an embodiment of the invention, on the basis of improving the binding force of conductive material and active material layer, it is unobvious
Increase the integral thickness of cathode, binder course with a thickness of nanoscale, such as 10 nanometers, 20 nanometers, 40 nanometers, 50 nanometers, 60 receive
Rice, 80 nanometers or 100 nanometers.As a result, on the basis of improving the binding force of conductive material and active material layer, the knot of the thickness
The integral thickness and weight of cathode will not be significantly increased by closing layer, and then will not be had a negative impact to the performance of cathode；If thickness
It is excessive, not only can be with respect to the thickness and weight that obviously increase cathode, and then understand relative reduction cathode pole piece and use the cathode
Battery energy density.
According to an embodiment of the invention, active material layer includes active material, institute in order to guarantee battery higher specific capacity
Stating active material includes at least one of silicon, silicon monoxide, silica and Si-C composite material.Above-mentioned material can as a result,
To improve the specific capacity of the battery using the cathode, and material source is extensive, and material selectivity is also wide.
According to an embodiment of the invention, the thickness of the cathode in order not to make is partially thick, silicon, silicon monoxide, silica and silicon
The partial size of carbon composite is micron order and nanoscale.
According to an embodiment of the invention, in order to improve the binding force between active material layer and binder course, active material layer
It further include binder.In some embodiments of the invention, it is fine to be selected from Kynoar, polytetrafluoroethylene (PTFE), carboxymethyl for binder
At least one of dimension element, SBR styrene butadiene rubbers and polyimides.It not only can be very good to improve active material as a result,
Binding force between layer and binder course will not also generate adverse effect to the performance of cathode pole piece.
According to an embodiment of the invention, in order to improve the electric conductivity of active material layer, active material layer further includes conductive agent.
In some embodiments of the invention, conductive agent is received selected from conductive black (Surpe-P), acetylene black, electrically conductive graphite (KS-6), carbon
At least one of mitron (CNT) and graphene.Thus, it is possible to improve the electric conductivity of active material layer well, electronics is improved
Transmittability, and then improve the high rate performance and cycle life of the battery using the cathode.
According to an embodiment of the invention, the weight of the addition meeting relative increase cathode of conductive agent, and then relative reduction battery
Energy density, so those skilled in the art can choose whether according to actual needs be added conductive agent.
According to an embodiment of the invention, in order to preferably improve the specific capacity of cathode and the battery using the cathode, base
In the gross mass of cathode, the mass percentage of active material is 5~50%, such as 5%, 10%, 15%, 20%, 25%,
30%, 35%, 40%, 45% or 50%.Cathode specific capacity with higher as a result, and then improve the electricity for using the cathode
The whole specific capacity in pond；If activity substance content is lower than 5%, the specific capacity improvement of cathode and battery is unobvious；If active
Content of material is higher than 50%, then the opposite electric conductivity that will affect cathode, influences the high rate performance and cycle performance of battery, and opposite
The expansion of active material layer is more obvious, seriously affects the integral thickness of cathode and battery.
According to an embodiment of the invention, in order to provide continuous ion channel, electrolyte layer includes organic matter and consolidates
At least one of body electrolyte and lithium salts.Organic matter and/or solid electrolyte, lithium salts can provide as a result, for lithium ion
Continuous channel, to realize the middle electronics of battery and exchanging for ion.In some embodiments of the invention, organic matter is selected from poly-
Ethylene oxide (PEO), polypropylene oxide (PPO), polypropylene carbonate (PPC), poly- ethylene carbonate (PEC), succinonitrile (SN),
At least one of Kynoar-hexafluoropropene (PVdF-HFP), the as a result, binding force of above-mentioned organic matter and active material layer
Preferably, and preferable channel can be provided for lithium ion, improve the charge-discharge performance of battery.In some embodiments of the present invention
In, lithium salts is selected from lithium perchlorate (LiClO4), double trifluoromethanesulfonimide lithiums (LiTFSI), double fluorine sulfimide lithiums
(LiFSI), biethyl diacid lithium borate (LiBOB) and LiBF4 (LiBF4) at least one of, as a result, service performance compared with
It is good, improve the energy density of battery.In some embodiments of the invention, solid electrolyte is selected from organic matter electrolyte, oxidation
At least one of object electrolyte, sulfide electrolyte or other novel solid electrolyte (phosphoric acid salt, fast-ionic conductor,
Anti-perovskite etc.), as a result, with the good bonding strength of active material layer, and preferable channel can be provided for lithium ion, improve electricity
The charge-discharge performance in pond.
According to an embodiment of the invention, in order to enable electrolyte layer can uniformly coat active material layer and not active
The binder course of material layer covering, the gross mass based on cathode, the mass percentage of electrolyte layer are 5%~60%, such as
5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%50%, 55% or 60%.Electrolyte layer can be with as a result,
Uniformly active material layer and binder course are enveloped, guarantee the uniformity of ion channel distribution；If the quality hundred of electrolyte layer
Content is divided to be lower than 5%.Electrolyte layer cannot completely by active material layer and and by active material layer cover binder course it is complete
It envelopes, ion channel cannot be evenly distributed in entire cathode；If the mass percentage of electrolyte layer is greater than 60%,
Under the premise of conductive material is certain, the thickness of electrolyte layer can be thicker, can obviously increase the integral thickness of cathode and battery, shadow
Ion transmission is rung, and then influences the performance of battery.
According to an embodiment of the invention, in order to enable electrolyte layer preferably coats active material layer and binder course, electrolysis
Matter layer with a thickness of 1~30 micron, such as 1 micron, 5 microns, 10 microns, 15 microns, 20 microns, 25 microns or 30 microns.By
This, the electrolyte layer of the thickness both can be very good to envelope active material layer and binder course, will not make the entirety of cathode
Thickness is partially thick, influences the specific capacity of cathode and battery；If the thickness of electrolyte layer is too small, electrolyte layer point may result in
Cloth is uneven；If electrolyte layer thickness is bigger than normal, the adhesive force of electrolyte layer, the i.e. covered effect of electrolyte layer will affect not
It is good, it is easy to fall off, and also cathode integral thickness can be made partially thick, influences battery integral energy density.
According to an embodiment of the invention, in order to guarantee the expansion of active material in active material layer will not influence cathode and
The integral thickness of battery, the porosity of cathode is 5%~85%, such as 5%, 10%, 15%, 20%, 25%, 30%, 35%,
40%, 45%50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%.Thus, it is possible to provide one for active material layer
Fixed expansion space, i.e. active material layer can be expanded into gap, and then can reduce the increase of cathode and cell thickness；
If porosity is too low, the expansion of active material layer will significantly increase the integral thickness of cathode and battery；If porosity mistake
Greatly, then the intensity of cathode is weaker, the service life of meeting relative effect cathode.
Another object of the present invention is to propose a kind of method of cathode for preparing solid state battery.Implementation according to the present invention
Example, referring to Fig.1, the method for preparing the cathode of mentioned-above solid state battery includes:
S100: binder course is formed on the surface of conductive material.
According to an embodiment of the invention, forming the material of conductive material and binder course and mentioned-above consistent, herein not
It is repeated after more.
According to an embodiment of the invention, the preferable binder course of quality, binder course can pass through method one or side in order to obtain
Method two is prepared:
Method one: S110: the combination is directly formed on the surface of conductive material by magnetron sputtering or pyrolytic coating
Layer, i.e., directly by the sputtering of materials for forming binder course or the surface for being sprayed on conductive material, above-mentioned technical maturity, and can essence
The size of quasi- control binder course generally selects this method when the material of binder course is metal simple-substance.
Method two: S121: conductive material is impregnated into certain time in the organic solution containing functional element.
According to an embodiment of the invention, what the organic solution containing functional element was obtained through the following steps: by Functional Unit
Plain source, surfactant and organic solvent are mixed, to obtain the organic solution containing functional element.Method is simple as a result,
It is easy to operate.
According to an embodiment of the invention, the binder course of better performances, functional element source are two water zinc acetates, nothing in order to obtain
At least one of water zinc acetate, aluminum acetate, ethyl orthosilicate and germanium tetrachloride (wherein functional element is zinc, aluminium, silicon, germanium).
Thus, it is possible to obtain the binder course of better performances, and then improve the knot between conductive material and the active material layer being subsequently formed
With joint efforts.
According to an embodiment of the invention, there is no limit requirement, this fields for the specific type of surfactant and organic solvent
Technical staff can flexible choice according to actual needs, as long as not influencing the performance of conductive material.
According to an embodiment of the invention, in order to form the binder course being evenly distributed, functional element on the surface of conductive material
In source the concentration of functional element be 0.5~2mol/L, for example, 0.5mol/L, 0.7mol/L, 0.9mol/L, 1mol/L,
1.2mol/L, 1.5mol/L, 1.8mol/L or 2.0mol/L.Thus, it is possible to form binder course in homogeneous thickness in conductive material；
It is relatively uneven in the binder course that the surface of conductive material is formed if the concentration of functional element is too low, and then may result in
The active material layer being subsequently formed is unevenly distributed in partial region；If the excessive concentration of functional element, may cause to be formed
The thickness of binder course is thicker (being likely to be breached micron order), so then with respect to the weight that can obviously increase cathode, and then reduces cathode
And the energy density of the battery using the cathode.
According to an embodiment of the invention, what the organic solution containing functional element was obtained through the following steps: using two water
Zinc acetate, ethanol amine and normal propyl alcohol mix above-mentioned three kinds of raw materials respectively as functional element source, surfactant and organic solvent
It closes, and through magnetic stirring apparatus heating stirring, is clarified, is transparent, the uniform organic solution (Zn-sol) containing Zn-ef ficiency.
According to an embodiment of the invention, time for being impregnated in the organic solution containing functional element of conductive material there is no limit
It is required that this is not restricted requires as long as conductive material is sufficiently soaked.
S122: carrying out high temperature sintering to the conductive material after immersion, to form parent's activity on the surface of conductive material
Material layer.As a result, binder course more fully can be formed on the surfaces externally and internally of conductive material using method two.
According to an embodiment of the invention, the condition of high temperature sintering is there is no limit requirement, those skilled in the art can basis
Conductive material and the material of binder course to be formed flexibly set, this is not restricted requires.
According to an embodiment of the invention, for below using carbon paper as conductive material, the step of introducing high temperature sintering:
Carbon paper after immersion is taken out and be transferred in air dry oven at 50~200 DEG C dry 5~30 minutes it is extra to remove
Carbon paper after drying is then transferred in Muffle furnace by solvent, and is warming up to 500~550 DEG C with the rate of 5~10 DEG C/min,
10~30min is kept the temperature at such a temperature, thus can obtain binder course.
According to an embodiment of the invention, when conductive material is immersed in the organic solution containing functional element, the organic solution
It penetrates into inside conductive material, the outer surface of conductive material and inner surface are infiltrated by above-mentioned organic solution, so in high temperature
After sintering, binder course is on the outer surface and inner surface for be formed conductive material.Such as when conductive material is carbon paper, such as preceding institute
It states, carbon paper is made of the carbon fiber of many roots, and carbon paper is immersed in the organic solution containing functional element, organic solution infiltration
To inside carbon paper, the surface of every carbon fiber is infiltrated by the organic solution, so active material layer is to be formed after high temperature sintering
On the surface of every carbon fiber.
S200: forming active material slurry layer on the surface of binder course, and carries out first and be dried, to combine
Active material layer is formed on the surface of layer.
According to an embodiment of the invention, the slurry for forming active material slurry layer is obtained through the following steps: by silicon,
At least one of silicon monoxide, silica and Si-C composite material, binder and solvent are uniformly mixed, described to obtain
Slurry.Method is simple as a result, easy to operate, easy to industrialized production.
According to an embodiment of the invention, what the slurry for forming active material slurry layer can also be obtained by following steps: will
At least one of silicon, silicon monoxide, silica and Si-C composite material, binder, conductive agent and solvent are uniformly mixed, with
Just the slurry is obtained.Method is simple as a result, easy to operate, easy to industrialized production, and introduces conductive agent and active matter can be enhanced
The electric conductivity of matter layer.
According to an embodiment of the invention, the type of binder and conductive agent and mentioned-above consistent, no longer excessive herein
It repeats；According to an embodiment of the invention, the specific type of solvent is there is no limit requirement, those skilled in the art can be according to reality
Demand flexible choice, as long as side effect is not generated to material each in cathode, for example, solvent can be N- crassitude
At least one of ketone, acetonitrile, n,N-dimethylacetamide (DMAC), the medium organic solvent of acetone, solvent may be water.
According to an embodiment of the invention, also there is no limit requirement, art technologies for the method for formation active material slurry layer
Personnel can flexible choice according to actual needs, such as can for coating, impregnate or the methods of spraying.Method is simple as a result, easily
Operation, and active material slurry layer is evenly distributed, so that ultimately form equally distributed active material layer.
According to an embodiment of the invention, there is no limit requirements for the described first dry condition, as long as solvent is all removed
, there is no limit require herein.
According to some embodiments of the present invention (by taking carbon paper as an example), formed active material slurry layer after slurry penetration to walk
Rapid S100 obtains the inside of product, infiltrates the surface of the binder course formed on every fiber of carbon paper, then dry by first,
Active material layer is formed in the part of the surface of binder course.
S300: forming electrolyte solution layer or electrolyte melt liquid layer on the surface of active material layer and binder course,
And carry out second and be dried, to form electrolyte layer on the surface of active material layer and close binder course.
According to an embodiment of the invention, what the electrolyte solution for forming electrolyte solution layer was obtained through the following steps:
At least one of organic matter and solid electrolyte, lithium salts and solvent are mixed.Wherein, organic matter, solid electrolyte and lithium salts
Specific material and mentioned-above consistent, do not do excessively repeat herein；There is no limit requirements for the specific type of solvent, as long as right
Negative electrode material does not have negative effect, for example can be acetonitrile.
According to an embodiment of the invention, the preferable electrolyte layer of performance, the solid content of electrolyte solution are 2% in order to obtain
~15%, such as 2%, 7%, 9%, 11%, 13% or 15%.The electrolyte layer formed as a result, more even compact；Admittedly if containing
Amount is too low, then electrolyte layer is unevenly distributed, and the ion channel of cathode is caused to be unevenly distributed；If solid content is excessively high, it is electrolysed
The mobility of matter solution is relatively poor, is still unfavorable for being uniformly distributed for electrolyte layer.
What the electrolyte melt liquid of formation electrolyte melt liquid layer was obtained through the following steps: by organic matter and admittedly
At least one of body electrolyte and lithium salts mixed melting.In an embodiment of the present invention, directly above-mentioned solid feed can be mixed
Conjunction is melted, and can also first be dried above-mentioned solid feed after mixing with organic solvent, is prepared into homogeneous solid electrolytic
After matter, then with heating melting.Simple process as a result, it is easy to operate, can make electrolyte layer be evenly coated at active material layer and
On the surface for the binder course not covered by active material layer.
According to an embodiment of the invention, providing quick electricity by the conductive material in the cathode of above method preparation for cathode
Subchannel, electrolyte layer provide continuous ion channel for cathode, to meet the job requirement of cathode；Active material layer is cathode
High specific capacity is provided；The binding force between conductive material and active material layer can be improved in binder course, guarantees that active material layer is equal
It is even to be distributed in conductive material surface；And electrolyte layer is arranged on the surface of active material layer, to the work in active material layer
The bulking effect of property substance has certain inhibiting effect, and cathode thickness or volume will not be caused in this way in battery charge and discharge process
Variation；In addition, above-mentioned preparation method is simple, easy to operate, preparation cost is low, easy to industrialized production.
Another object of the present invention is to propose a kind of solid state battery.According to an embodiment of the invention, the solid state battery
Including mentioned-above cathode.The solid state battery cyclicity is good as a result, and circulation volume conservation rate is high, long service life.Ability
The feature and advantage that field technique personnel are appreciated that the solid state battery compared with the existing technology and have above-mentioned cathode all,
This is repeated no more.
It will be understood by those skilled in the art that the solid state battery further includes conventional solid battery in addition to above-mentioned cathode
Essential structure or component, for example further include the structures such as the solid electrolyte of anode and setting between a positive electrode and a negative electrode.
According to an embodiment of the invention, the electrolyte in solid state battery can be prepared by mentioned-above electrolyte solution
It arrives, i.e., the electrolyte solution is prepared into certain thickness dielectric film, the solid-state electricity by the dielectric film as the solid state battery
Xie Zhi.In an embodiment of the present invention, the solid electrolyte with a thickness of 10~200 microns, such as 10 microns, 50 microns, 80
Micron, 100 microns, 130 microns, 150 microns, 180 microns or 200 microns.Solid state battery better performances as a result,.
Embodiment
Embodiment 1
The step of preparing cathode:
Step 1: using two water zinc acetates as zinc source, and ethanol amine, will as solvent as surfactant, normal propyl alcohol
Above-mentioned three kinds of raw material mixing, after magnetic stirring apparatus heating stirring, is clarified, transparent uniform organic solution containing zinc
(Zn-sol), wherein the concentration of Zn-ef ficiency is 1mol/L in two water zinc acetates；
Step 2: by carbon paper, (its scanning electron microscope (SEM) photograph exists referring to Fig. 4, Energy dispersive x-ray spectrum (EDS) figure referring to Fig. 5)
After sufficiently soaking in Zn-sol organic solution, in air dry oven, dry 5~30min is extra to remove at 50~200 DEG C
Solvent be further warming up to 500~550 DEG C later with the rate of 5~10 DEG C/min, keep the temperature 10~30min, i.e., in carbon paper
In the surface of carbon fiber obtain zinc oxide film (binder course), the electron microscope for the product which obtains is referring to Fig. 6, EDS figure ginseng
According to (a) and (b) in Fig. 7, wherein (a) in Fig. 7 indicates the distribution of the product surface Zn-ef ficiency, and (b) in Fig. 7 is indicated should
The distribution of product surface oxygen element；
Step 3: using micron order Si material as active material, sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR) as
Binder, water are uniformly mixed as solvent, silicon slurry are made；
Step 4: the silicon slurry prepared being coated on the surface for the product that step 2 obtains, and it is dry to carry out first later
Dry processing forms active material layer (silicon layer) that is, on the surface of zinc oxide film, the electron microscope reference for the product which obtains
Fig. 8；
Step 5: by bis trifluoromethyl sulfimide lithium (LiTFSI), polyethylene glycol oxide (PEO), acetonitrile (ACN) as former
Expect and be uniformly mixed, prepares the electrolyte solution that solid content is 3.5%；
Step 6: the electrolyte solution prepared is coated on the surface for the product that step 4 obtains, carries out the later
Two are dried, i.e., are not formed electrolyte layer on the surface for the zinc oxide film that active material layer covers in active material layer and,
The electron microscope for the product that the step obtains is referring to Fig. 9.
The step of preparing solid state battery:
Above-mentioned steps five are utilized using lithium piece as anode using cathode prepared by above-mentioned steps as the cathode of solid state battery
The electrolyte solution of acquisition prepares the solid electrolyte of the solid state battery, and above-mentioned anode, solid electrolyte and cathode assembling are obtained
Obtain solid electrolyte.Charge-discharge test done to the solid electrolyte, test chart referring to Fig.1 0.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of cathode of solid state battery characterized by comprising
Conductive material；
Binder course, the binder course are coated on the surface of the conductive material；
Active material layer, the active material layer are arranged in the part of the surface of the binder course；
Electrolyte layer, the electrolyte layer are coated on the surface of the active material layer and the binder course.
2. cathode according to claim 1, which is characterized in that the conductive material include carbon paper, foam copper, nickel foam or
Foamed aluminium or class 3D porous conductive material, the preferably described carbon paper,
Optional, the carbon paper meets at least one the following conditions:
With a thickness of 100~300 microns；
The carbon fiber diameter for forming the carbon paper is 2~10 microns.
3. cathode according to claim 1, which is characterized in that the material for forming the binder course includes zinc oxide, oxidation
At least one of aluminium, silicon monoxide, silica, germanium dioxide, silicon, germanium, aluminium, nickel, magnesium and silver, preferably zinc oxide,
It is optional, the binder course with a thickness of nanoscale.
4. cathode according to claim 1, which is characterized in that the active material layer includes active material, the activity
Substance includes at least one of silicon, silicon monoxide, silica and Si-C composite material；
Optional, the active material layer further includes binder, and the binder is selected from Kynoar, polytetrafluoroethylene (PTFE), carboxylic
At least one of methylcellulose, SBR styrene butadiene rubbers and polyimides；
Optional, the active material layer further includes conductive agent, the conductive agent be selected from conductive black, acetylene black, electrically conductive graphite,
At least one of carbon nanotube and graphene；
Optional, based on the gross mass of the cathode, the mass percentage of the active material is 5~50%.
5. cathode according to claim 1, which is characterized in that the electrolyte layer includes in organic matter and solid electrolyte
At least one and lithium salts,
The organic matter is selected from polyethylene glycol oxide, polypropylene oxide, polypropylene carbonate, poly- ethylene carbonate, succinonitrile, gathers partially
At least one of vinyl fluoride-hexafluoropropene；
The lithium salts be selected from lithium perchlorate, double trifluoromethanesulfonimide lithiums, double fluorine sulfimide lithiums, biethyl diacid lithium borate and
At least one of LiBF4；
The solid electrolyte is selected from least one of polymer dielectric, oxide electrolyte, sulfide electrolyte,
Optional, based on the gross mass of the cathode, the mass percentage of the electrolyte layer is 5%~60%.
Optional, the porosity of the cathode is 5%~85%.
6. a kind of method for the cathode for preparing solid state battery according to any one of claims 1 to 5 characterized by comprising
Binder course is formed on the surface of conductive material；
Active material slurry layer is formed on the surface of the binder course, and carries out first and is dried, so as in the combination
Active material layer is formed in the part of the surface of layer；
Electrolyte solution layer or electrolyte melt liquid layer are formed on the surface of the active material layer and the binder course, and
It carries out second to be dried, to form electrolyte layer on the surface of the active material layer and the binder course.
7. according to the method described in claim 6, it is characterized in that, forming the binder course on the surface of the conductive material
It obtains one of by the following method:
Method one: the conductive material is impregnated into certain time in the organic solution containing functional element；
High temperature sintering is carried out to the conductive material after immersion, to form the combination on the surface of the conductive material
Layer,
Method two: the binder course is directly formed on the surface of the conductive material by magnetron sputtering or pyrolytic coating.
Optional, what the organic solution containing functional element was obtained through the following steps:
Functional element source, surfactant and organic solvent are mixed, it is described organic molten containing functional element to obtain
Liquid,
The functional element source be two water zinc acetates, anhydrous zinc acetate, aluminum acetate, ethyl orthosilicate and germanium tetrachloride at least
It is a kind of；
The concentration of functional element is 0.5~2mol/L in the functional element source.
8. according to the method described in claim 6, it is characterized in that, the slurry for forming the active material slurry layer be by with
What lower step obtained:
At least one of silicon, silicon monoxide, silica and Si-C composite material, binder and solvent are uniformly mixed, with
Just the slurry is obtained.
9. according to the method described in claim 6, it is characterized in that, the electrolyte solution for forming the electrolyte solution layer is logical
It crosses what following steps obtained: at least one of organic matter and solid electrolyte, lithium salts and solvent is mixed,
Optional, the solid content of the electrolyte solution is 2%~15%,
Alternatively, what the electrolyte melt liquid for forming the electrolyte melt liquid layer was obtained through the following steps: will be organic
At least one of object and solid electrolyte and lithium salts mixed melting.
10. a kind of solid state battery, which is characterized in that including cathode according to any one of claims 1 to 5.
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| CN110931730A (en) * | 2019-11-04 | 2020-03-27 | 浙江锋锂新能源科技有限公司 | Titanium niobate negative electrode material and preparation method and application thereof |
| CN112216874A (en) * | 2020-10-13 | 2021-01-12 | 深圳中科瑞能实业有限公司 | Preparation process of all-solid-state battery |
| CN112467106A (en) * | 2020-11-24 | 2021-03-09 | 王立勇 | Preparation method and application of graphene film/silicon composite material |
| CN113036131A (en) * | 2019-12-09 | 2021-06-25 | 财团法人工业技术研究院 | Positive electrode material, positive electrode containing same, and battery |
| CN114441408A (en) * | 2022-01-24 | 2022-05-06 | 蜂巢能源科技(无锡)有限公司 | Method for monitoring degree of fibrosis in dry film making process, dry film making method, and preparation method and application of dry electrode plate |
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| CN116904822A (en) * | 2023-09-14 | 2023-10-20 | 赣州市瑞富特科技有限公司 | Lamellar stacked silicon-germanium alloy material and preparation method and application thereof |
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| CN116904822A (en) * | 2023-09-14 | 2023-10-20 | 赣州市瑞富特科技有限公司 | Lamellar stacked silicon-germanium alloy material and preparation method and application thereof |
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