CN107240718A - Solid state battery and preparation method thereof - Google Patents
Solid state battery and preparation method thereof Download PDFInfo
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- CN107240718A CN107240718A CN201710462747.2A CN201710462747A CN107240718A CN 107240718 A CN107240718 A CN 107240718A CN 201710462747 A CN201710462747 A CN 201710462747A CN 107240718 A CN107240718 A CN 107240718A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to solid state battery and preparation method thereof.A kind of method for preparing solid state battery may include：Stacking provisions are prepared, the stacking provisions at least include anode layer and the solid electrolyte layer being arranged in the anode layer, and the anode layer includes positive electrode active materials particle and solid electrolyte particle；Quick interface heating is carried out to the stacking provisions, to cause the interface of at least one of positive electrode active materials particle and solid electrolyte particle in the anode layer to melt, to generate interface fusion phase, so as to be directly connected to the positive electrode active materials particle and the solid electrolyte particle.
Description
Technical field
Present invention relates in general to new energy field, more specifically it relates to which one kind is simple, quick, it is solid to prepare on a large scale
The method of state battery and the solid state battery prepared by this method.
Background technology
In recent years, fast-developing electric automobile and energy storage industry are to using lithium ion battery, lead-acid battery as the two of representative
Energy density, cost, cycle characteristics and the security feature of primary cell propose higher requirement.By taking lithium ion battery as an example, often
The lithium ion battery of rule mainly uses graphite cathode, and the theoretical capacity of graphite cathode is 372mAh/g, at present domestic main stone
Black negative pole manufacturer, has been realized in 365mAh/g capacity, close to theoretical capacity such as the purple great mansion in Jiangxi, Shenzhen Bei Terui
The limit.In order to realize higher energy density and power density, people, which begin to focus on, disclosure satisfy that want higher to brand new cells
The novel anode material asked, such as lithium anode, but the electrolyte of lithium battery is generally flammable liquid at present, so if should
Battery is damaged, and may bring danger.Scientific research personnel wishes that replacing liquid electrolyte uses solid electrolyte, so as to prepare
More safe and reliable solid state battery.
Solid electrolyte in using or study at present is mainly oxide solid electrolyte, sulfide electrolyte, polymerization
Thing electrolyte and their compound type.Solid state battery company based on oxide is such as having Sakti3, typically using magnetic
The method of sputtering is controlled in metallic lithium surface sputtering sedimentation LiPON electrolyte and lithium cobaltate cathode material, but the making of this method
Cost is high, and LCO thickness of thin, the energy density of battery is low.The solid state battery company developed based on sulfide electrolyte is for example had
Toyota, Samsung, Hitachi's shipbuilding and Japanese fuji etc., it is general that solid state battery is prepared using condensation technique, but this technical conditions will
Ask height, cost of manufacture big.Solid state battery light weight based on polymer, good, the easy film forming of viscosity, chemical stability are good, energy is fine
Ground suppresses the growth of Li dendrite body, however, electrochemical window is less than 3.8V, therefore can not use high-voltage anode, so that
Battery system energy density is low, and such as Seeo polymerization cell energy density is only 100wh/kg.
In addition, compared with liquid electrolyte, solid electrolyte does not possess interface infiltration and mobility, and this causes solid state battery
Preparation is compared with liquid state batteries more difficult.The problem of in order to solve interface, it is solid to solve that researcher has attempted sintering process
Interracial contact between body electrolyte and solid electrolyte and between solid electrolyte and positive electrode, however sintering time compared with
Length easily causes interface resistance larger between positive pole and electrolyte.
Accordingly, it would be desirable to continuously be furtherd investigate to solid state battery, to overcome the above-mentioned problems in the prior art.
The content of the invention
In order to solve the above problems, the application proposes a kind of method for preparing solid state battery, and it can improve solid state battery
In particle between contact interface attribute, be conducive to transporting for lithium ion, so as to improve the performance and security of solid state battery.
This method can simply, be performed quickly, can be used to prepare solid state battery on a large scale.
According to an exemplary embodiment, a kind of method for preparing solid state battery may include：Prepare stacking provisions, the stacking
Structure at least includes anode layer and the solid electrolyte layer being arranged in the anode layer, and the anode layer includes positive-active material
Expect particle and solid electrolyte particle；Quick interface heating is carried out to the stacking provisions, to cause in the anode layer just
At least one of pole active material particle and solid electrolyte particle melt in interface, to generate interface fusion phase,
So as to be directly connected to the positive electrode active materials particle and the solid electrolyte particle.
In some instances, the quick interface heating includes microwave heating, high frequency heating, mechanical Wave heating, vibration
Frictionally heat, sound wave heating, ultrasonic Wave heating, infrasonic sound Wave heating, the one or more in the heating of electromagnetic field inducing electric current.High week
The frequency of Wave heating and electromagnetic induction heating is more than 20KHz, and mechanical Wave heating, vibration are frictionally heated, sound wave is heated, ultrasonic wave adds
Heat and the frequency range of infrasonic sound Wave heating are 20Hz to 1GHz, and the frequency range of microwave heating is 300MHz to 300GHz.Ripple
Form can be with sine wave, cosine wave, square wave, shear wave, compressional wave and their any combination.
In some instances, scope of the temperature of the quick interface heating at 300 DEG C to 1000 DEG C, preferably 400
DEG C to 800 DEG C of scope.Scope of the time of the quick interface heating at 0.01-1500 seconds, preferably at 0.5-900 seconds
Scope, more preferably in the scope of 1-600 seconds.
In some instances, methods described also includes：Before the quick interface heating is performed, by the stacking provisions
It is preheated to predetermined temperature, scope of the predetermined temperature at 25 DEG C to 800 DEG C, preferably in 100 DEG C to 500 DEG C of scope.
In some instances, methods described also includes：After the quick interface heating is performed, to the stacking provisions
Perform annealing, scope of the annealing temperature at 100 DEG C to 500 DEG C, preferably in 200 DEG C to 400 DEG C of scope, annealing time
In the scope of 0.5 minute to 120 minutes, preferably in the scope of 1 minute to 60 minutes.
In some instances, the stacking provisions also include the negative electrode layer being arranged on the solid electrolyte layer, described
Negative electrode layer includes negative active core-shell material particle.
In some instances, the negative electrode layer also includes solid electrolyte particle, and the quick interface is heated so that described
At least one of negative active core-shell material particle and solid electrolyte particle in negative electrode layer melt in interface, to generate
Interface fusion phase, so as to be directly connected to the negative active core-shell material particle and the solid electrolyte particle.
In some instances, methods described also includes：After the quick interface heating stepses, in the solid electrolytic
Polymer solid electrolyte layer and negative electrode layer are set gradually on matter layer, or negative electrode layer is directly set.
In some instances, the quick interface heating stepses only make positive electrode active materials particle in the anode layer and
In interface fusing occurs at least one of solid electrolyte particle to generate interface fusion phase, is lived without changing the positive pole
The internal structure of property material granule and the solid electrolyte particle.
According to an exemplary embodiment there is provided a kind of solid state battery, it is prepared from according to the above method.
In some instances, the interface fusion is mutually amorphous phase.
In some instances, in the positive electrode active materials particle and solid electrolyte particle in the anode layer it is described extremely
It is crystalline phase inside a kind of few particle.
In some instances, the solid state battery is alkali metal solid state battery.
The present invention to stacking provisions by carrying out quick interface heating so that contacts more preferable between particle, is more conducive to
Alkali metal ion such as lithium ion transport, while it is easy in heating process to also inhibits positive active material and electrolyte interface
The phase counterdiffusion of generation, the inert layer of generation chemical property difference.With handling interface by conventional long-time sintering method
The scheme of contact is compared, and is heated using quick interface, and interface transition layer is thin, between 0.1nm~100nm, and interface composition is generally
Melt the amorphous phase of phase.When heating treatment time longer power in interface is larger, the product meeting large area of fusing phase connects together,
Fine and close is more than 90%；And non-melt phase, then keep crystalline phase；When interface heating treatment time is shorter and during smaller power, if
Melt phase corner angle clearly demarcated, corner angle can disappear after being melted down, interface fusing mutually becomes the spheric granules of one one and ins succession one
Rise.If preparing stacking provisions, using binding agent, after quick interface heating, it is interface fusion and bonding to exist in stacking provisions
Agent bonded particulate coexisting state, if again using annealing, stacking provisions binding agent can have catabolite.The side of the present invention
Method is simple, and cost is low, can be used in the extensive manufacture of solid state battery.
The above and other feature and advantage of the present invention will become apparent from following to the description of exemplary embodiment.
Brief description of the drawings
Accompanying drawing diagrammatically illustrates the exemplary embodiment of the present invention.It should be understood that what accompanying drawing was not drawn to scale.
Fig. 1 shows the flow chart of the method for the manufacture solid state battery according to an exemplary embodiment of the invention
Fig. 2A shows the schematic diagram of the multilayer stacking provisions according to an exemplary embodiment of the invention.
Fig. 2 B show showing for the multilayer stacking provisions after being heated according to the quick interface of an exemplary embodiment of the invention
It is intended to.
Fig. 3 A show the schematic diagram of multiple multilayer stacking provisions according to an exemplary embodiment of the invention, and it has inside
Cascaded structure.
Fig. 3 B show the schematic diagram of multiple multilayer stacking provisions according to another exemplary embodiment of the present invention, and it has interior
Portion's parallel-connection structure.
Fig. 4 shows to utilize the SEM photograph of positive pole/electrolyte sheet prepared by sintering 3h at 850 DEG C of solid sintering technology.
Fig. 5 shows to utilize the SEM photograph of positive pole/electrolyte sheet prepared by sintering 5h at 850 DEG C of solid sintering technology.
Fig. 6 shows the SEM photograph of the positive pole/electrolyte sheet prepared according to another exemplary embodiment of the present invention.
Fig. 7 shows all charging and discharging curves of head of the battery of positive pole/electrolyte sheet assembling using Fig. 6.
Fig. 8 shows the SEM photograph of the positive pole/electrolyte sheet prepared according to another exemplary embodiment of the present invention.
Fig. 9 shows all charging and discharging curves of head of the battery of positive pole/electrolyte sheet assembling using Fig. 8.
Embodiment
The exemplary embodiment of the present invention is described below with reference to accompanying drawings.It should be understood that what accompanying drawing was not drawn to scale.
For the above mentioned problem of existing solid state battery, the present invention proposes a kind of method of quick interface heating, makes all solid state
The temperature of the interface of positive pole, negative pole in battery and the particle in solid electrolyte layer reaches the degree for melting interface,
So that between solid electrolyte and positive electrode particle, between solid electrolyte and solid electrolyte particle and solid electrolyte
Meromixis occurs for the interface between negative pole particle, so as in atomic scale, nanoscale or micro-meter scale, be melted by interface
That changes mutually forms being directly connected between solid electrolyte particle and positive and negative electrode particle, and then causes in all-solid-state battery, from
Son can be transmitted between positive pole, electrolyte, negative pole phase, and in all-solid-state battery charge and discharge process, interface connection is mutually
Will not be because positive and negative electrode particle volume changes and loses the connection with positive and negative electrode particle.After quick interface heating, interface
The phase of fusion can be amorphous phase or crystalline phase, can be positive pole, negative pole, solid electricity in all-solid-state battery
Solve the phase of matter or because the cenotype that quick interface is heated and produces.Due to being heated quick interface, positive and negative electrode
Original crystal structure and microstructure are maintained inside particle, is only melted and is connected in interface, and between particle
Diffuse into one another small so that cell interface impedance is small, and inhibit positive active material and electrolyte interface in heating process
The middle inert layer that chemical property difference is generated because of counterdiffusion.The method of the present invention is easily operated, suitable for large-scale production, has
Good application prospect.
Fig. 1 shows the flow chart of the method 100 for preparing solid state battery according to an exemplary embodiment of the invention.Such as Fig. 1
Shown, the method 100 for preparing solid state battery starts from step S110, prepares the stacking of sandwich construction.Fig. 2A shows multilayer stacking
The example of structure.As shown in Figure 2 A, multilayer stacking provisions include anode layer 10, dielectric substrate 20 and negative electrode layer 30.Anode layer 10
Including positive electrode active materials particle 11, dielectric substrate 20 includes electrolyte granular 21, and negative electrode layer 30 includes negative active core-shell material
Grain 31.It should be noted that also including electrolyte granular 21 during anode layer 10 and negative electrode layer 30 are each.In other words, anode layer 10 includes
The mixture of positive electrode active materials particle 11 and electrolyte granular 21, negative electrode layer 30 includes negative active core-shell material particle 31 and electrolysis
The mixture of matter particle 21.In further embodiments, negative electrode layer 30 can not also include electrolyte granular 21.Although not showing
Go out, but anode layer 10 and negative electrode layer 30 can also each include current collector layers.
Preparing the step S110 of the multilayer stacking provisions may include to prepare positive pole mixing material, electrolyte and negative pole material
Material, preparation method may include hand-ground, ball milling, vibration, tumble mixed etc..At least include positive-active in positive pole mixing material
Material and electrolyte, can also include conductive additive and binding agent etc..In electrolyte in addition to including electrolyte, also
Can be including binding agent etc..At least include negative active core-shell material in negative material, electrolyte, binding agent and conduction can also be included
Additive etc..Can be using these materials according to the stacking provisions that sequentially form shown in Fig. 2A, forming the method for stacking provisions has many
Kind, such as spraying, silk-screen printing, transfer coated, extrusion coated, nick version, electrostatic spinning or dry powder multilayer mixed pressure.This
A little methods have all been used in the prior art, are not detailed herein.
In certain embodiments, anode layer 10 may include solid electrolyte, positive active material, binding agent and conductive addition
Agent, their mass ratio may range from such as 20:80≤MPositive active material:MSolid electrolyte≤98:2；70:30≤
MPositive active material+solid electrolyte:MBinding agent≤100:0；82:20≤MPositive active material+solid electrolyte:MConductive additive≤100:0.Can be according to existing lithium
Ion battery stirring technique, anode sizing agent is prepared into by positive pole mixing material.In one example, for example, in positive pole mixing material
Material mass ratio can be positive active material:Solid electrolyte:Conductive agent:Binding agent=68:28:2:2.By these slurries
It is coated in by the way of transfer coating on plus plate current-collecting body, can be using one side coating or dual coating formation anode layer, positive pole
Thickness degree is at 2 μm -500 μm, and preferred thickness is 10 μm -200 μm, plus plate current-collecting body can be material can be aluminium, stainless steel,
One or more in nickel, carbon, existence form can be paper tinsel, hole, bar, net, and thickness is 1 μm~25 μm.
In certain embodiments, negative electrode layer 30 may include negative electrode active material, solid electrolyte, binding agent and conductive addition
Agent, their mass ratio may range from such as 40:60≤MNegative electrode active material:MSolid electrolyte≤98:2；80:20≤
MNegative electrode active material+solid electrolyte:MBinding agent≤100:0；80:20≤MNegative electrode active material+solid electrolyte:MConductive additive≤100:0.According to existing lithium-ion electric
Pond stirring technique, cathode size is prepared into by negative pole mixing material, and the material mass ratio wherein in negative pole mixing material can be
Negative electrode active material:Solid electrolyte:Conductive agent:Binding agent=66:30:2:2.By these slurries by the way of extrusion coated
Be coated on negative current collector, can using one side coating or dual coating formation negative electrode layer, the thickness of negative electrode layer can 2 μm-
500 μm, preferred thickness is 10 μm -120 μm.Negative current collector can be that material can be one kind in copper, stainless steel, nickel, carbon
Or it is a variety of.Existence form can be paper tinsel, hole, bar, net, and thickness is 1 μm~25 μm.
In certain embodiments, solid electrolyte layer 20 can include solid electrolyte and binding agent, wherein their matter
Amount ratio may range from such as 80:20≤MSolid electrolyte:MBinding agent≤100:0.It is also possible to according to existing lithium ion battery Beater operator
Skill, prepares electrolyte slurry, the wherein material mass ratio of dielectric substrate can be such as electrolyte:Binding agent=97:3.Can
So that electrolyte slurry transfer coated or nick method are coated on the surface of anode layer or negative electrode layer, the thickness of dielectric substrate can
So that in 1 μm -100 μm of scope, preferred thickness is 2 μm -50 μm.
In further embodiments, directly the powder of anode layer can also be tiled into grinding tool, gently pressurizeed；Then put down
The powder of electrolyte is spread, is gently pressurizeed；The powder of last tiling negative electrode layer, then pressurizes, to prepare the heap of three-decker again
Pile.In the method, powder can contain binding agent, can also not contain binding agent.
In various materials described above, positive active material may be selected from I2、S、O2、Me(NixCoyMnz)fO2g、Me
(FeaCobMncNid)f(PO4)g、M2e(FeaCobMncNid)f(SiO4)g、M2e(Fe2aCo2bMn2cNi2d)f(SO4)3g、Me
(FeaCobMncNid)f(BO3)g、M3eV2f(PO4)3g、MeCofO2g、FefS2g、MnfO2g、Me(NiaCobAlc)fO2、M2eMnfO3g、Me
(NixCoyMnz)fO2g、Me(NipMnq)2fO4gIn one or more, wherein M is alkali metal such as Li, Na, K, x+y+z=1,
And 0≤x≤1,0≤y≤1,0≤z≤1, a+b+c+d=1, and 0≤a≤1,0≤b≤1,0≤c≤1,0≤d≤1,0.5≤e
≤ 1.5,0.5≤f≤1.5,0.5≤g≤1.5, p+q=2 and 0≤p≤2,0≤q≤2.
In various materials described above, negative electrode active material may be selected from carbon material, silicon materials, tin material, alkali metal
Simple substance, alkali metal alloy compound MaX(1-a)In one or more, wherein carbon material includes graphite, hard carbon, soft carbon and its spreads out
Biology, silicon materials include nano-silicon, Si-C composite material, the sub- silicon of oxidation, the sub- silicon of oxidation and carbon composite, and tin material includes receiving
Rice tin, tin-carbon composite, tin oxide and its composite, alkali metal may include Li, Na, K, alkali metal alloy compound
MaX(1-a)In M may be selected from Li, Na, K, X may be selected from Sn, Si, Al, Ge, Sb, B, Mg, 0.1<a<1.
In various materials described above, solid electrolyte may include MgS, CaS, SrS, BaS, B2S3、Al2S3、
Ga2S3、In2S3、SiS2、GeS2、SnS2、CeS2、Nb2S5、Sc2S3、Y2S3、La2S3、TiS2、ZrS2、HfS2、ZnS、P2S5、As2S5、
MgO、CaO、SrO、BaO、B2O3、Al2O3、Ga2O3、In2O3、SiO2、GeO2、SnO2、Sc2O3、Y2O3、La2O3、TiO2、ZrO2、
HfO2、Nb2O5、ZnO、Na2O、K2O、Rb2O、Cs2O、CuO、M3One or more and M in N, MF, MCl, MBr, MI2S or
M2The compound of solid solution, compound, amorphous, amorphous and crystalline state that O is formed, wherein M is alkali metal Li, Na, K.
For example, the solid electrolyte for lithium ion solid state battery can include Li1+pAlpGe2-p(PO4)3、Li3qLa2/3- qTiO3、LiZr2-rTir(PO4)3、Li1+mAlmTi2-m(PO4)3、Li4-tGe1-tPtS4、Li7-2n-jAnLa3Zr2-jBjO12And Li7-2n- 2jAnLa3Zr2-jCjO12, Li7P3P11, Li3PS4, wherein, 0≤p≤2,0≤q≤2/3,0≤r≤2,0≤m≤2,0≤t≤1,0
≤ n≤3,0≤j≤2, A is Ge and/or Al, B are Nb and/or Ta, C are Te and/or W.
For example, the solid electrolyte for sodium ion solid state battery can include β-Al2O3、Na1+2x+yAxByCzP3O12, its
Middle A=Mg2+, B=Al3+、Cr3+、Ga3+、B3+, C=Ti4+、Ge4+、Si4+、Zr4+Deng 0≤x≤1,0≤y≤1,1≤z≤2.
For example, solid electrolyte can also be the solid electrolyte for sodium ion solid state battery, no longer enumerate here.
In some embodiments, binding agent may be selected from Vingon (PVDF), Vingon-hexafluoropropene (PVDF-
HFP), polytetrafluoroethylene (PTFE) (PTFE), polyethylene glycol oxide, polyester, polyethers, polyamide, polymethyl methacrylate, makrolon,
One or more in carboxymethyl cellulose, SB, polyacrylonitrile.
In certain embodiments, conductive additive may be selected from SP, acetylene black, KB, CNT, graphene, aluminium powder, copper
One or more in powder, nickel powder, magnesium powder, zinc powder, bronze, silver powder, the alloy of glass putty and above-mentioned material.Of conductive additive
Particle size can be such as 5nm-1 μm, preferably 10nm-500nm.
It should be understood that, although Fig. 2A shows electrolyte granular and dielectric substrate 20 in anode layer 10 and negative electrode layer 30
In electrolyte granular it is identical, but they can also be different, and the electrolyte in anode layer 10 can also and negative pole
Electrolyte granular (if any) in layer 30 is different.
In certain embodiments, wherein both positive and negative polarity surface of active material can also contain clad, mutual to suppress particle surface
Diffusion.The thickness of clad can be such as 0.5nm-500nm, and coating layer material can be oxide, sulfide and polymer
In one or more.
By above-mentioned steps, the multilayer stacking provisions shown in Fig. 2A are prepared for.Next, in the step s 120, can hold
Row quick interface heating process.Different from sintering process of the prior art, quick interface heating of the invention is aimed at
Fusion between grain interface, the especially interface fusion between positive electrode active materials particle 11 and electrolyte granular 21, but should
The counterdiffusion between particle caused by superheated is avoided, this counterdiffusion may generate the inert layer of chemical property difference,
So as to increase the interface impedance of battery, make the degradation of battery.
Therefore, in quick interface heating stepses S120, it should be noted that the temperature and time of control heating, to cause above-mentioned heap
The temperature at one or more granular boundaries in anode layer 10, negative electrode layer 30 and solid electrolyte layer 20 in pile structure reaches
To the degree for melting interface so that between solid electrolyte and positive electrode particle, solid electrolyte and solid electrolyte particle
Between and interface between solid electrolyte and negative pole particle occur meromixis, for example solid electrolyte particle 21 with
Interface fusion phase 12 is produced between positive electrode particle 11, boundary is produced between solid electrolyte particle 21 and solid electrolyte particle 21
Phase 22 is merged in face, and produces interface fusion phase 32 between solid electrolyte particle 21 and negative pole particle 31, as shown in Figure 2 B
As.These interface fusions can be mutually amorphous phase or crystalline phase；Can be in all-solid-state battery just
Pole, negative pole, the phase of solid electrolyte or the cenotype produced because of quick interface heating.So, can be in atom chi
Degree, nanoscale or micro-meter scale are mutually straight between solid electrolyte particle and positive and negative electrode particle to be formed by interface fusion
Connect, and then cause in all-solid-state battery in succession, ion can be transmitted between positive pole, electrolyte, negative pole, and all solid state
In battery charge and discharge process, interface connection mutually also will not be because positive and negative electrode particle volume changes and loses and positive and negative electrode particle
Connection.Because interparticle contact well forms entirety, battery will integrally have more preferable mechanical performance, while will possess higher electricity
Conductance.On the other hand, due to being heated quick interface, original crystal structure is maintained inside positive and negative electrode particle and microcosmic
Structure, is only melted and is connected in interface, and diffusing into one another between particle is small, so that cell interface impedance is small, and
Positive active material and electrolyte interface is inhibited to generate the inert layer of chemical property difference because of counterdiffusion in heating process.
Compared with the scheme by conventional long-time sintering method to handle interracial contact, heated using quick interface,
Interface transition layer is thin, between 0.1nm~100nm, and interface composition is generally the amorphous phase for melting phase.When interface heating treatment time
When longer power is larger, the product of fusing phase can large area connect together, fine and close is more than 90%；And non-melt phase, then keep
Crystalline phase；When interface heating treatment time is shorter and during smaller power, if fusing phase corner angle are clearly demarcated, corner angle can disappear after being melted down
Lose, interface fusing mutually becomes the spheric granules of one one and ined succession together.If preparing stacking provisions, using binding agent,
It is interface fusion and binding agent bonded particulate coexisting state to exist after quick interface heating, in stacking provisions, is moved back if using again
Fire processing, stacking provisions binding agent can have catabolite.
Step S120 quick interface heating process can be performed by various means, including but not limited to microwave adds
Heat, flash burning heating, high frequency heating, mechanical Wave heating, sound wave heating, ultrasonic Wave heating, infrasonic sound Wave heating, electromagnetic field inducing electricity
Stream heating and their any combination etc..As some examples, the frequency of high frequency heating and electromagnetic induction heating is general
More than 20KHz, mechanical Wave heating, vibration are frictionally heated, sound wave heating, ultrasonic Wave heating and infrasonic sound Wave heating frequency can be
20Hz to 1GHz scope, the frequency range of microwave heating can be 300MHz to 300GHz.The form of ripple can be with sine wave, remaining
String ripple, square wave, shear wave, compressional wave and their any combination etc..It is appreciated that using different mode of heatings, to not of the same race
Class, the stacked layers of thickness carry out interface and quickly heated, and will all influence time and the power of heating.In processing different-thickness
During stacked layers, the time quickly heat at interface is also different, for thicker stacked layers, the quick heat fusion in interface
Time is longer, and heating power also should be bigger.It should be noted that different from sintering process of the prior art, the present invention
Quick interface heating heat time be typically not to be exceeded 1800 seconds, to prevent serious mutual expansion between variable grain
Dissipate.The material of different electrolyte and both positive and negative polarity is carried out when interface is quickly heated also should using the different time and
Heating power.For the high granular materials of fusing point, the time of heating is longer, and the power of heating is bigger.Although as described above,
The acid extraction of quick interface heating is different because of material and stacking thickness, but in general, heating-up temperature can be 300
DEG C to 1000 DEG C of scope, preferably in 400 DEG C to 800 DEG C of scope, the heat time can be excellent in the scope of 0.01-1500 seconds
The scope of 0.5-900 seconds is selected in, more preferably in the scope of 1-600 seconds.Compared with conventional sintering process, heating of the invention
Time wants much shorter, and heating effect is concentrated mainly on interface, therefore can be described as " quick interface heating ".
In certain embodiments, for fusing point very high material, it can also quickly be carried out applying interface before heating
Pre-add is heat-treated, and pre-heating temperature must should be less than particle fusing point, to suppress to occur phase counterdiffusion between particle.Reach one in advance
Constant temperature degree can make material be easier to reach melting temperature when quick interface is heated, and make interface fusion more preferable.It is pre-heated
Temperature can be from 25 DEG C to 800 DEG C, preferably from 100 DEG C to 500 DEG C.
When performing quick interface heating, stacking provisions can also be pressurizeed, pressurization pressure can be such as 10kPa
To 10000kPa, it can also heat at ambient pressure.Heating can be carried out in atmosphere, can also be entered if necessary in particular atmosphere
Go to prevent undesirable chemical reaction.
Some embodiments of quick interface heating are described below.In certain embodiments, it is possible to use microwave adds
Heat performs quick interface heating stepses S120.When using microwave heating, stacking provisions can be made to be in 300 DEG C of left sides in advance
The right side, then performs microwave heating.Moreover, when microwave is heated, system can be pressurizeed, pressure 10kPa~10000kPa；Plus
The hot time can be 0.01~1800s, preferably 0.01~1000s.
In further embodiments, it is possible to use high frequency heats to perform quick interface heating stepses S120.Carrying out
When high frequency is heated, stacking provisions can be made to be in 25 DEG C in advance, and system is pressurizeed, pressure is, for example, 800kPa,
Heat time can be 50~200s, for example, 100s.
In further embodiments, it is possible to use mechanical Wave heating performs quick interface heating stepses S120.Mechanical wave
It is to produce heat to be heated by particle friction.When using mechanical Wave heating, system can be heated to 300 in advance~
500 DEG C, for example, it is preheated to 455 DEG C.System can be pressed, pressure is, for example, 800kPa, heated during mechanical Wave heating
Time can be 5~30s, such as 10s, 15s, 20s.
In further embodiments, it is possible to use electromagnetic induction heating performs quick interface heating stepses S120.Adopting
When using electromagnetic induction heating, system can be preheated to 300~500 DEG C, for example, be preheated to 455 DEG C.During mechanical Wave heating
System can be pressed, pressure is, for example, 800kPa, and the heat time can be 5~30s, such as 10s, 15s, 20s.
It is, of course, also possible to perform quick interface heating stepses S120 by other means, no longer enumerate here.
By above-mentioned quick interface heating stepses S120, the result shown in Fig. 2 B is obtained, wherein for example in solid electrolytic
Between matter particle 21 and positive electrode particle 11, between solid electrolyte particle 21 and solid electrolyte particle 21 and in solid
Interface fusion phase 12,22 and 32 is generated between electrolyte granular 21 and negative pole particle 31 respectively.The present inventor's experiment discovery,
After quick interface heat fusion, the alkali metal ion conductance of the interface fusion phase of formation is possible to relative to particle body phase
Material becomes higher or lower.In order to ensure the electrical conductivity of interface fusion phase is sufficiently high, it can also melt in quick interface heating
After conjunction, stacking provisions are further processed to increase the electrical conductivity of fusion phase, so as to improve battery performance.For example,
In some embodiments, the stacking result after being heated to quick interface makes annealing treatment, and annealing temperature can be at 100 DEG C extremely
500 DEG C of scope, preferably in 200 DEG C to 400 DEG C of scope, annealing time can be excellent in the scope of 0.5 minute to 120 minutes
Select the scope of 1 minute to 60 minutes.Annealing can equally be carried out in air or special atmosphere, for example can nitrogen, argon gas,
Carried out in the atmosphere of oxygen or their mixture.
It is then possible to perform step S130, solid state battery is assembled using the stacking provisions after step S120 processing, for example
Stacking provisions are encapsulated into battery container, and plus plate current-collecting body and negative current collector are being connected respectively to solid state battery just
Negative electrode etc..The packaging technology of solid state battery is known in the art, and description is not repeated herein, to avoid unnecessarily obscuring
The main points of the present invention.
In the embodiment described above in relation to Fig. 1,2A and 2B, stacked structure includes anode layer 10, the and of dielectric substrate 20
Negative electrode layer 30, i.e., with three-decker.In further embodiments, stacked structure can also only include two layers, i.e. anode layer 10
With dielectric substrate 20.Now, before number of assembling steps S130 is performed, then also need to set negative electrode layer on dielectric substrate 20.Now,
Polyelectrolyte floor first can also be set on the surface of dielectric substrate 20 directly against upper negative electrode layer, its thickness can be with
For such as 0.5 μm~50 μm, preferably 1 μm~20 μm.Then, then by negative electrode layer it is arranged on polyelectrolyte floor.At these
In embodiment, electrolyte granular can not be included in negative electrode layer.It is appreciated that similarly, being described above in relation to Fig. 2A and 2B
Embodiment in, negative electrode layer 30 can not also include electrolyte granular 21.Polymer dielectric can for dry polymeric electrolyte,
One or more in organosol polymeric electrolyte, porous organosol polymeric electrolyte and organic matter composite electrolyte.It is dry poly-
Polymer electrolyte can be composite of ethers polyeletrolyte, carbonates, polysiloxane group and alkali metal salt etc..It is conventional
Alkali metal salt include lithium salts, for example, lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), hexafluoroarsenate lithium
(LiAsF6), trifluoromethyl sulfonic acid lithium (CF3SO3Li), lithium perchlorate, lithium nitrate, double (trimethyl fluoride sulfonyl is sub-) amine lithiums
(LiTFSI), the one or more in double fluorine sulfimide lithiums (LiFSI) and di-oxalate lithium borate (LiBOB).
Fig. 3 A and 3B show the schematic diagram of multiple multilayer stacking provisions according to other exemplary embodiments of the invention, its
Multiple stacking provisions formation internal parallel structure in multiple stacking provisions formation internal series-connection structure in middle Fig. 3 A, Fig. 3 B.
By the serial or parallel connection of multiple stacking provisions, higher voltage, higher capacity etc. can be provided.Knot shown in Fig. 3 A and 3B
Structure can be by forming multiple stacking provisions prepared above are connected in series or in parallel.Alternatively, it can also make at the very start
Structure shown in standby Fig. 3 A and 3B, then performs quick interface described above and heats again.It is adjacent in internal series-connection battery
Both positive and negative polarity between stacking provisions can just share collector when stacked layers are prepared, and form positive pole and negative pole is serially connected
The structure of connection, can also be connected with each other between the both positive and negative polarity collection ear after preparing the single stacking provisions of completion by collector
Form cascaded structure.Internally in batteries in parallel connection, by the collection ear of collector between stacking provisions be interconnected to form positive pole and
The parallel-connection structure being connected with each other between positive pole, negative pole and negative pole, can also just use strip collector, most when prepared by stacking provisions
After be wound into battery.Finally, solid state battery can be made by aluminum plastic film sealing.
Some examples and comparative example according to the present invention will be described below.In these examples, used material is such as
Shown in following form.
The electrolyte of table 1
| Electrolyte | Composition |
| Electrolyte 1 | Li1+pAlpGe2-p(PO4)3 |
| Electrolyte 2 | Li3qLa2/3-qTiO3 |
| Electrolyte 3 | LiZr2-rTir(PO4)3 |
| Electrolyte 4 | Li1+mAlmTi2-m(PO4)3 |
| Electrolyte 5 | Li7-2n-jAnLa3Zr2-jBjO12 |
| Electrolyte 6 | Li7-2n-2jAnLa3Zr2-jCjO12 |
| Electrolyte 7 | Li2O-B2O3 |
| Electrolyte 8 | LiPON |
| Electrolyte 9 | β-Li3PS4 |
| Electrolyte 9 | Li7P3S11 |
| Electrolyte 10 | β-Al2O3 |
| Electrolyte 11 | Na3Zr2Si2PO12 |
Wherein, 0≤p≤2,0≤q≤2/3,0≤r≤2,0≤m≤2,0≤t≤1,0≤n≤3,0≤j≤2, A is Ge
And/or Al, B are Nb and/or Ta, C are Te and/or W.
The quick mode of heating in the interface of table 2
The binding agent of table 3
| Numbering | Composition |
| Binding agent 1 | Vingon (PVDF) |
| Binding agent 2 | PI |
| Binding agent 3 | Polytetrafluoroethylene (PTFE) (PTFE) |
| Binding agent 4 | Sodium carboxymethylcellulose (CMC) |
| Binding agent 5 | SBR |
| Binding agent 6 | Polyethylene glycol oxide |
| Binding agent 7 | Polyacrylic acid |
| Binding agent 8 | It is polycarbonate-based |
| Binding agent 9 | PVDF-HFP |
| Binding agent 10 | Polyacrylonitrile |
| Binding agent 11 | SB |
| Binding agent 12 | Polyamide |
The positive electrode of table 4
| Numbering | Composition |
| Positive electrode 1 | Particle diameter is 0.58nm LiNbO3The cobalt acid lithium of cladding |
| Positive electrode 2 | NCM622 |
| Positive electrode 3 | LiMn2O4 |
| Positive electrode 4 | LiNi0.5Mn1.5O4 |
| Positive electrode 5 | NCA |
| Positive electrode 6 | NCM811 |
| Positive electrode 7 | LiFePO4 |
| Positive electrode 8 | MnO2 |
| Positive electrode 9 | FeS2 |
| Positive electrode 10 | O2 |
| Positive electrode 11 | S |
| Positive electrode 12 | Cobalt acid lithium |
The negative material of table 5
| Negative pole is numbered | Composition |
| Negative pole 1 | Lithium metal |
| Negative pole 2 | Lithium-aluminium alloy (lithium mass fraction is 20 ± 1%) |
| Negative pole 3 | Lithium magnesium alloy (lithium mass fraction is 75 ± 1%) |
| Negative pole 4 | Lithium boron alloy (lithium mass fraction is 70 ± 1%) |
| Negative pole 5 | Lithium/graphite complex lithium (lithium mass fraction is 35 ± 1%) |
| Negative pole 6 | The sub- silicon of lithium/oxidation is compound (lithium mass fraction is 45 ± 1%) |
| Negative pole 7 | Lithium/nano-silicon is compound (lithium mass fraction is 30 ± 1%) |
| Negative pole 7 | Metallic sodium |
The conductive additive of table 6
| Conductive additive is numbered | Composition |
| Conductive additive 1 | SuperP |
| Conductive additive 2 | Acetylene black |
| Conductive additive 3 | Carbon black |
| Conductive additive 4 | Nanometer aluminium powder |
| Conductive additive 5 | Nano-silver powder |
| Conductive additive 6 | Nanometer glass putty |
| Conductive additive 7 | Copper nanoparticle |
Comparative example 1 is by traditional sintering process, by positive pole and electrolyte mixed sintering
Prepare respectively：Positive pole mixing material powder, including active material cobalt acid lithium, electrolyte LATP, conductive addition
In agent, uniform mixing, the mould for pouring into φ 10.By on the anode layer powder of electrolyte granular LAGP in a mold, by positive pole
Layer and dielectric substrate are pressed into disk together, and dielectric substrate thickness is 500 μm, and anode layer thickness is 400 μm.Will using traditional handicraft
Disk sinters potsherd into, and the 3h that anneals at 850 DEG C, obtains positive pole-electrolyte sheet, and its microstructure such as Fig. 4 SEM shines
Shown in piece.The 5h that annealed at 850 DEG C obtains positive pole-electrolyte sheet, and its microstructure is as shown in Fig. 5 SEM photograph.
It can be seen that there are obvious corner angle, interparticle contact between particle when heat treatment between high temperature, short time
It is a contact, contact area is small.When high temperature long time treatment, electrolyte granular melts, substantially without grain shape simultaneously
And connection is fine, but there is serious counterdiffusion between particle.
Positive pole-electrolyte sheet after annealing is sticked into lithium anode in electrolyte side, button cell is assembled into, and
Circulated under conditions of 55 DEG C, 1C,
After heat treatment, battery is because contact is poor or counterdiffusion seriously causes interface impedance to work greatly very much.There is no capacity
Release.
Example 1
By preparing respectively：Anode layer mixing material, wherein active material cobalt acid lithium, electrolyte LAGP, conductive carbon and viscous
The mass ratio for tying agent PVDF is 7:3:0.5:0.5, it is prepared into slurry by solvent of NMP；Dielectric substrate mixing material, wherein being electrolysed
Matter LAGP, binding agent PVDF mass ratio are 90:10, it is prepared into slurry by solvent of NMP.Anode sizing agent is coated on carrier Al
On, carrier Al thickness is 10 μm, and coating thickness is 100 μm.Electrolyte slurry is coated on support C u again, coating thickness is
150μm.Anode layer and dielectric substrate are overlapped to form into stacked layers, obtained stacked layers are subjected to mechanical wave heating, heating
Time 6s, pressurize 1MPa, obtains positive pole-electrolyte sheet.The microstructure of positive pole-electrolyte sheet as shown in Fig. 6 SEM photograph,
Because processing time is long, LAGP crystal morphologies have disappeared, and LAGP links together, and form a compacted zone, and fusing point is high
Cobalt acid lithium remain in that the pattern of crystal.Polymer dielectric film is sticked in electrolyte sheet side, polymer dielectric is
PEO, thickness is 50 μm.Lithium metal is sticked again and makees negative pole, is assembled into 2032 button cells.By the button cell of preparation 55 DEG C,
Circulated under conditions of 1C, circulating battery data are as shown in fig. 7, first week charging capacity is 91.3mAh/g, and discharge capacity is
52.3mAh/g, first week efficiency is 57.28%.
Example 2
Distinguish blended anode layer mixing material, dielectric substrate mixing material and negative electrode layer mixing by vibrating the method for mixing
Material.Wherein anode layer mixing material includes anode active material of phosphate iron lithium, electrolyte LATP, binding agent PVA, conductive addition
Agent super P；Dielectric substrate mixing material includes electrolyte LATP, binding agent PVA；Negative electrode layer mixing material includes negative electrode active
Material graphite, binding agent CMC.By three kinds of well mixed materials, large area is sprayed on collector Al in order respectively, finally
Along with Cu is used as negative current collector.The stacking provisions that spraying is obtained pass through ultrasonic Wave heating, heat time 0.1s, pressurization
1MPa, obtains battery unit.The microstructure of battery unit is as shown in Fig. 8 SEM photograph.Because processing time is shorter, particle
It is not completely melt, only interface between particles melts to form a small amount of amorphous phase.Originally sharp-featured electrolyte granular
Become globulate, and be connected together by amorphous.Obtain 10 monomers are connected in parallel by the lug formation of collector,
Finally encapsulated with aluminum plastic film, make soft-package battery.The soft-package battery of preparation is circulated at room temperature, under conditions of 1C, electricity
Pond loop-around data is as shown in figure 9, first week charging capacity is 118.9mAh/g, and discharge capacity is 94.8mAh/g, and first week efficiency is
79.73%.
Example 3-12
Following table 7 lists example 3-12 material composition and quick interface heating means, and gained battery electricity
Press scope and first all efficiency.
The example 3-12 of table 7
By the way that the result of comparative example 1 above is compared with embodiment according to the present invention 1-12 result it can be found that
Relative to solid state battery is prepared with long-time sintering method merely, the present invention is by using quick interface heating means, to particle
Between interface, including electrolyte granular, between electrolyte and positive electrode particle, it is high that the interface between negative pole and electrolyte granular carries out the short time
Temperature heating, can reach improvement interracial contact, while suppressing interdiffusion at interface and inert layer generation, to improve the mesh of interface performance
, and then the cycle performance of solid state battery is improved, also improve the security of solid state battery.
Above for all solid state some embodiments for describing the present invention of lithium, however, it is understood that the principle of the present invention also may be used
Sodium all-solid-state battery is applied to, it is similar in every respect to lithium battery.Now, positive active material, electrolyte, binding agent
It can be the material in corresponding sodium all-solid-state battery with negative electrode active material.In other words, it should be appreciated that through this specification,
When referring to lithium, the embodiment of sodium should be also covered by.
Some embodiments of the application are described above for lithium solid state battery, it should be understood that the original of the application
Reason also may be used on otheralkali metal solid state battery, such as sodium and potassium solid state battery.Now, it is only necessary to carry out replacing for associated materials
The adjustment with parameter is changed, under the teachings of the present invention, this is will be obvious to those skilled in the art that need not appoint
What performing creative labour.
Although describing the present invention above with reference to one exemplary embodiment, the invention is not restricted to this.Those skilled in the art
It is readily apparent that in the case where not departing from the scope of the present invention and thought, the various changes in form and details can be carried out
Change and change.The scope of the present invention is only defined by appended claims and its equivalent.
Claims (13)
1. a kind of method for preparing solid state battery, including：
Stacking provisions are prepared, the stacking provisions at least include anode layer and the solid electrolyte being arranged in the anode layer
Layer, the anode layer includes positive electrode active materials particle and solid electrolyte particle；
Quick interface heating is carried out to the stacking provisions, to cause positive electrode active materials particle and the solid in the anode layer
At least one of electrolyte granular melts in interface, to generate interface fusion phase, so as to be directly connected to the positive pole
Active material particle and the solid electrolyte particle.
2. according to the method described in claim 1, wherein, quick interface heating include microwave heating, high frequency heat, machine
Tool Wave heating, vibration are frictionally heated, sound wave is heated, ultrasonic Wave heating, infrasonic sound Wave heating, microwave are heated, electromagnetic field inducing electric current
One or more in heating.
Wherein, the frequency of high frequency heating and electromagnetic induction heating is more than 20KHz, and mechanical Wave heating, vibration are frictionally heated, sound wave
The frequency range of heating, ultrasonic Wave heating and infrasonic sound Wave heating is 20Hz to 1GHz, and the frequency range of microwave heating is 300MHz
To 300GHz, and
Wherein, the form of ripple can be with sine wave, cosine wave, square wave, shear wave, compressional wave and their any combination.
3. according to the method described in claim 1, wherein, the model of the temperature of quick interface heating at 300 DEG C to 1000 DEG C
Enclose, preferably in 400 DEG C to 800 DEG C of scope, and
Wherein, scope of the time of the quick interface heating at 0.01-1500 seconds, preferably in the scope of 0.5-900 seconds, more
Preferably in the scope of 1-600 seconds.
4. according to the method described in claim 1, in addition to：
Before the quick interface heating is performed, the stacking provisions are preheated to predetermined temperature, the predetermined temperature is 25
DEG C to 800 DEG C of scope, preferably in 100 DEG C to 500 DEG C of scope.
5. according to the method described in claim 1, in addition to：
After quick interface heating is performed, the stacking provisions are performed with annealing, annealing temperature at 100 DEG C extremely
500 DEG C of scope, preferably in 200 DEG C to 400 DEG C of scope, scope of the annealing time at 0.5 minute to 120 minutes, preferably
Scope of the ground at 1 minute to 60 minutes.
6. according to the method described in claim 1, wherein, the stacking provisions also include be arranged on the solid electrolyte layer
Negative electrode layer.
7. method according to claim 6, wherein, the negative electrode layer also includes solid electrolyte particle, the quick boundary
Face heating causes at least one of negative active core-shell material particle and solid electrolyte particle in the negative electrode layer in interface
Melt, to generate interface fusion phase, so as to be directly connected to the negative active core-shell material particle and the solid electrolyte
Grain.
8. according to the method described in claim 1, in addition to：
After the quick interface heating stepses, polymer solids are set gradually in the anode layer and solid electrolyte layer
Dielectric substrate and negative electrode layer, or negative electrode layer is directly set.
9. according to the method described in claim 1, wherein, the quick interface heating stepses only make the positive pole in the anode layer
In interface fusing occurs at least one of active material particle and solid electrolyte particle to generate interface fusion phase, without
Change the internal structure of the positive electrode active materials particle and the solid electrolyte particle.
10. a kind of solid state battery, its method according to any one of claim 1 to 9 is prepared from.
11. solid state battery as claimed in claim 10, wherein, the interface fusion is mutually amorphous phase.
12. solid state battery as claimed in claim 11, wherein, positive electrode active materials particle and solid electricity in the anode layer
It is crystalline phase to solve inside at least one particle in matter particle.
13. solid state battery as claimed in claim 10, wherein, the solid state battery is alkali metal solid state battery.
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| CN108878961A (en) * | 2018-07-11 | 2018-11-23 | 桑德集团有限公司 | Sulfide solid electrolyte and preparation method thereof and equipment |
| CN109004268A (en) * | 2018-07-06 | 2018-12-14 | 浙江大学 | The sodium-ion battery quasi-solid electrolyte and preparation method and application of hydrated glass base |
| CN109148818A (en) * | 2018-08-28 | 2019-01-04 | 江苏双登富朗特新能源有限公司 | Polyethylene oxide solutions filling technique for solid lithium battery |
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| CN109148818B (en) * | 2018-08-28 | 2021-04-13 | 江苏双登富朗特新能源有限公司 | Polyethylene oxide solution injection process for all-solid-state lithium battery |
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| CN110911725A (en) * | 2019-11-26 | 2020-03-24 | 徐建 | Melting type all-solid-state battery |
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