CN109461887A - A kind of all-solid-state battery and preparation method thereof - Google Patents
A kind of all-solid-state battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of all-solid-state batteries and preparation method thereof.The preparation method of all-solid-state battery disclosed by the invention, comprising: step S1: the anode sizing agent containing poly- carbonic acid alkenyl esters is coated on plus plate current-collecting body；Step S2: after the solid electrolyte membrane stacking containing poly- carbonic acid alkenyl esters is placed in the plus plate current-collecting body coated with anode sizing agent, drying；Step S3: solid electrolyte film surface after the drying carries out magnetron sputtering, forms silicon layer；Step S4: magnetron sputtering is carried out in silicon surface, forms nickel layer or layers of copper.The all-solid-state battery that method produced according to the present invention obtains, without additional pressurizer, it can operate normally, the opposite all-solid-state battery for needing additional pressurizer improves energy density.
Description
Technical field
The present invention relates to battery technology fields more particularly to a kind of all-solid-state battery and preparation method thereof.
Background technique
Commercial li-ion battery contains low ignition point liquid state organic electrolyte, is easy to appear leakage, inflammable and explosive etc. and asks safely
Topic, largely limits the application field of liquid lithium ionic cell.And it is stored up as electric car and smart grid etc. are large-scale
Energy device is gradually popularized, and more stringent requirements are proposed for the energy density and security performance to battery.
Compared with commercial li-ion battery, all-solid-state battery replaces liquid state organic electrolyte using inorganic solid electrolyte,
The safety problem of lithium ion battery can preferably be solved.Inorganic solid electrolyte can be good at inhibiting the generation and life of Li dendrite
It is long, to improve the cycle life and security performance of lithium metal battery.In addition, inorganic solid electrolyte electrochemical stability window reaches
It to 5V or more, can be matched with high-voltage anode material, and simplify safety device, mitigate battery weight, be greatly improved
The energy density of battery.All-solid-state battery can also unit superposition series connection, simplify battery case, so that it is close to obtain higher energy
Degree.
Wherein, sulfide solid electrolyte due to ionic conductivity is high, composition variation range is wide, cost of material is less expensive by
The extensive concern of the solid electrolyte as all-solid-state battery is arrived.But in the preparation method of existing all-solid-state battery, sulfide
Do not have enough bonding forces between the powder of solid electrolyte, anode does not have between sulfide solid electrolyte film layer, cathode
Firm binding force, it is therefore desirable to there is pressurizer just and can make solid state battery to keep good ionic conductivity and good
Capacity retention ratio, but due to the presence of pressurizer, the energy density of solid state battery monomer can be made to reduce.
Summary of the invention
(1) technical problems to be solved
It can not achieve the technical issues of controlling oneself pressure to solve the all-solid-state battery of the prior art, the present invention provides a kind of complete
Solid state battery and preparation method thereof realizes the self-holding pressure of all-solid-state battery.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
According to an aspect of the invention, there is provided a kind of preparation method of all-solid-state battery, comprising:
Step S1: the anode sizing agent containing poly- carbonic acid alkenyl esters is coated on plus plate current-collecting body；
Step S2: the solid electrolyte membrane stacking containing poly- carbonic acid alkenyl esters is placed in coated with the anode sizing agent just
After the collector of pole, drying；
Step S3: the solid electrolyte surface after the drying carries out magnetron sputtering, forms silicon layer；
Step S4: magnetron sputtering is carried out in the silicon surface, forms nickel layer or layers of copper.
A kind of embodiment of method produced according to the present invention, the poly- carbonic acid alkenyl esters include at least one in following
Kind: poly- ethylene carbonate, polypropylene carbonate, poly- butylene, polycyclohexene.
A kind of embodiment of method produced according to the present invention, in step sl, the anode sizing agent includes positive electrode
And solvent, the poly- carbonic acid alkenyl esters account for 2~6% by percentage to the quality of the positive electrode.
A kind of embodiment of method produced according to the present invention, in step s 2, the poly- carbonic acid alkenyl esters account for solid-state electricity
Solve the 4~6% of plasma membrane layer.
A kind of embodiment of method produced according to the present invention, the poly- carbonic acid alkenyl esters are polypropylene carbonate, described
The molecular weight of polypropylene carbonate is 150000~500000；
It include the positive electrode active materials of sulfur-bearing in the positive electrode；
The solid electrolyte film layer includes sulfide solid electrolyte.
A kind of embodiment of method produced according to the present invention, the drying temperature are 220~250 DEG C, and drying time is
30~60min.
A kind of embodiment of method produced according to the present invention is in step s3, stable being formed in magnetron sputtering
Under conditions of plasma arc, vacuum degree is 2~80 millitorrs, and the time is 0.1~2 hour.
A kind of embodiment of method produced according to the present invention, the solid electrolyte film layer with a thickness of 2~300 μm.
A kind of embodiment of method produced according to the present invention, the layers of copper or nickel layer with a thickness of 1 μm~10 μm.
According to another aspect of the present invention, a kind of all-solid-state battery that method produced according to the present invention obtains is provided.
Beneficial effects of the present invention:
The preparation method of all-solid-state battery according to the present invention, in a first aspect, in anode sizing agent, containing poly- carbon in step S1
Sour alkenyl esters, preferably comprise polypropylene carbonate, are polymer, have the property of adhesive, therefore anode sizing agent is coated
When plus plate current-collecting body, can firmly it be adhered on collector.
Second aspect contains poly- carbonic acid alkenyl esters, is drying in step s 2 in solid electrolyte film layer and anode sizing agent
During dry, poly- carbonic acid alkenyl esters can decompose, and due to the decomposition of poly- carbonic acid alkenyl esters, will form hole in positive electrode material layer；
Poly- carbonic acid alkenyl esters in solid electrolyte film layer can also decompose, inorganic present in solid electrolyte layer after its decomposition
Composition granule can fill in the hole formed to positive electrode material layer, form the positive electrode material layer and solid-state of fine and close mutual extrusion infiltration
Dielectric film bed boundary.
The third aspect, in step S3, using the method for magnetron sputtering, sputtering forms silicon layer work in solid electrolyte film layer
For cathode, since, there are hole, the silicon particle of sputtering can be filled to hole existing for solid electrolyte film layer in solid electrolyte film layer
In, therefore also will form the solid electrolyte film layer and silicon layer of fine and close mutual extrusion infiltration, the solid electrolyte film layer of formation
There is firm binding force between silicon layer, and using between the silicon layer itself and solid electrolyte film layer of magnetron sputtering method sputtering
Binding force with regard to fine, therefore between silicon layer and solid electrolyte film layer have firm binding force, will not fall off；In step
In rapid S4, magnetron sputtering forms layers of copper or nickel layer on silicon layer, due to the method using magnetron sputtering, makes silicon layer and layers of copper or nickel
There is firm binding force between layer.
In conclusion the all-solid-state battery that preparation method according to the present invention obtains, has firm knot between layers
With joint efforts, therefore it can be used alone, and not have to additionally use pressurizer, it can be used alone.It is additional due to not having to
Using pressurizer, self-holding pressure is realized, to improve its energy density.
In addition, preparation method according to the present invention, in step S3 and step S4, using the method for magnetron sputtering,
Sputtering forms silicon layer as cathode in solid electrolyte film layer, very strong to the impact force of sputtering surface when due to magnetron sputtering, meeting
The high temperature for forming moment can make the solid electrolyte contacted with silicon particle when solid electrolyte is sulfide solid electrolyte
The sulfide on the surface of film layer is changed into glassy state or amorphous state, to further improve the ionic conductance of all-solid-state battery
Rate.
The all-solid-state battery that method produced according to the present invention obtains both can be normal without additional pressurizer
Operation, the opposite all-solid-state battery for needing additional pressurizer, improves energy density.
Detailed description of the invention
Fig. 1 is that the scanning electron microscope (SEM) photograph that silicon layer amplification factor is 10000 times is sputtered in comparative example 1；
Fig. 2 is that the scanning electron microscope (SEM) photograph that silicon layer amplification factor is 30000 times is sputtered in comparative example 1；
Fig. 3 is the diffraction pattern of the copper current collector and copper current collector after sputtering silicon layer before sputtering silicon layer in comparative example 1.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the application can
To be combined with each other.
Below in conjunction with specific embodiment, the present invention will be described in detail.The application is made below in conjunction with specific embodiment
It is described in further detail, these embodiments should not be understood as limiting the application range claimed.In embodiment not
Actual conditions person is indicated, is carried out according to conventional conditions or manufacturer's recommended conditions.Factory is not specified in agents useful for same or instrument
Shang Zhe is the conventional products that can be obtained by commercially available purchase.
According to an aspect of the invention, there is provided a kind of preparation method of all-solid-state battery, comprising:
Step S1: the anode sizing agent containing poly- carbonic acid alkenyl esters is coated on plus plate current-collecting body；
Step S2: the solid electrolyte membrane stacking containing poly- carbonic acid alkenyl esters is placed in coated with the anode sizing agent just
After the collector of pole, drying；
Step S3: the solid electrolyte film surface after the drying carries out magnetron sputtering, forms silicon layer；
Step S4: magnetron sputtering is carried out in silicon surface, forms nickel layer or layers of copper.
The preparation method of all-solid-state battery according to the present invention, in a first aspect, in step S1, in anode sizing agent, containing poly-
Carbonic acid alkenyl esters, preferably comprise polypropylene carbonate, are polymer, have the property of adhesive, therefore anode sizing agent is applied
When being overlying on plus plate current-collecting body, can firmly it be adhered on collector.
Second aspect contains poly- carbonic acid alkenyl esters, is drying in step s 2 in solid electrolyte film layer and anode sizing agent
During dry, poly- carbonic acid alkenyl esters can decompose, and due to the decomposition of poly- carbonic acid alkenyl esters, will form hole in positive electrode material layer；
Poly- carbonic acid alkenyl esters in solid electrolyte film layer can also decompose, inorganic present in solid electrolyte layer after its decomposition
Composition granule can fill in the hole formed to positive electrode material layer, form the positive electrode material layer and solid-state of fine and close mutual extrusion infiltration
Electrolyte membrane layer.
The third aspect, in step S3, using the method for magnetron sputtering, sputtering forms silicon layer work in solid electrolyte film layer
For cathode, since, there are hole, the silicon particle of sputtering can be filled to hole existing for solid electrolyte film layer in solid electrolyte film layer
In, therefore also will form the solid electrolyte film layer and silicon layer of fine and close mutual extrusion infiltration, the solid electrolyte film layer of formation
There is firm binding force between silicon layer, and using between the silicon layer itself and solid electrolyte film layer of magnetron sputtering method sputtering
Binding force with regard to fine, therefore between silicon layer and solid electrolyte film layer have firm binding force, will not fall off；In step
In rapid S4, magnetron sputtering forms layers of copper or nickel layer on silicon layer, due to the method using magnetron sputtering, makes silicon layer and layers of copper or nickel
There is firm binding force between layer.
In conclusion the all-solid-state battery that preparation method according to the present invention obtains, has firm knot between layers
With joint efforts, therefore it can be used alone, and not have to additionally use pressurizer, it can it is used alone, it is additional due to not having to
Using pressurizer, self-holding pressure is realized, to improve its energy density.
In addition, preparation method according to the present invention, in step S3 and step S4, using the method for magnetron sputtering,
Sputtering forms silicon layer as cathode in solid electrolyte film layer, very strong to the impact force of sputtering surface when due to magnetron sputtering, meeting
The high temperature for forming moment can make the solid electrolyte contacted with silicon particle when solid electrolyte is sulfide solid electrolyte
The sulfide on the surface of film layer is changed into glassy state or amorphous state, to further improve the ionic conductance of all-solid-state battery
Rate.
A kind of embodiment of method produced according to the present invention, the poly- carbonic acid alkenyl esters include at least one in following
Kind: poly- ethylene carbonate, polypropylene carbonate, poly- butylene, polycyclohexene.
Above-mentioned poly- carbonic acid alkenyl esters all have the effect of binder, are added in anode sizing agent, and the anode sizing agent of formation exists
When on coating to plus plate current-collecting body, positive electrode and plus plate current-collecting body can be made firmly to be combined together.In addition, in drying
When using the temperature for being higher than its decomposition temperature, above-mentioned material can also be decomposed, and formed hole on positive electrode surface, made solid state electrolysis
Plasma membrane layer is filled into the hole on positive electrode surface, and solid electrolyte film layer and positive electrode material layer are firmly combined together,
It can also make to form hole in solid electrolyte membrane layer, make the particles filled hole formed to solid electrolyte film layer of magnetron sputtering
In.
A kind of embodiment of method produced according to the present invention, anode sizing agent include positive electrode and solvent, positive electrode
Including poly- carbonic acid alkenyl esters, poly- carbonic acid alkenyl esters account for 2~6% by percentage to the quality of positive electrode.
A kind of embodiment of method produced according to the present invention, in step s 2, poly- carbonic acid alkenyl esters account for solid electrolyte
4~6% by percentage to the quality of film layer.
A kind of embodiment of method produced according to the present invention, poly- carbonic acid alkenyl esters are polypropylene carbonate, poly- carbonic acid third
The molecular weight of enester is 150000~500000；It include the positive electrode active materials of sulfur-bearing in positive electrode；Solid electrolyte film layer
In include sulfide solid electrolyte.
A kind of embodiment of method produced according to the present invention, drying temperature be 220~250 DEG C, drying time be 30~
60min。
Preparation method according to the present invention, when the molecular weight of polypropylene carbonate is 150000~500000, molecular weight
Relatively high, viscosity is larger, on the one hand, can make the solid electrolyte obtained when the polypropylene carbonate amount of addition is less
Film forming, wherein the accounting of sulfide solid electrolyte is opposite to be improved, so that the ionic conductivity of solid electrolyte is improved, and by
Less in its additive amount, fast decoupled is complete when can also enable its drying；On the other hand, the poly- carbonic acid third of addition can be made
The anode sizing agent that enester amount obtains when less has good adhesive property, to allow to preferably be bonded in anode collection
On body, fast decoupled is complete when can also enable its drying.
Wherein, the molecular weight of polypropylene carbonate is typical but without limitation preferably: 150000,180000,200000,
250000、300000、350000、400000、450000、500000。
Preparation method of the invention, polypropylene carbonate decomposition temperature is at 230 DEG C or so, when the molecule of polypropylene carbonate
When amount is 150000~500000, decomposition temperature is within the scope of 220~250 DEG C, and in the temperature range, positive electrode is sulphur
When compound, when solid electrolyte is sulfide solid electrolyte, during the drying process, not only polypropylene carbonate can be decomposed, shape
Between inorganic sulphide, a degree of crosslinking can also occur for pore-forming, so as to so that between positive electrode, positive electrode and
Combination between sulfide solid electrolyte is even closer, to further increase positive electrode material layer and solid electrolyte membrane
Binding force between layer, to further improve the self-holding pressure energy power of all-solid-state battery.
Wherein, drying temperature is typically but without limitation preferably 220 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, 250
℃。
Drying time typically but 30min, 35min preferred without limitation, 40min, 45min, 50min, 55min,
60min。
A kind of embodiment of method produced according to the present invention, solid electrolyte film layer with a thickness of 2um~300 μm.
If the thickness of solid electrolyte film layer is greater than 300 μm, the flexibility of film layer is deteriorated, and interface resistance becomes larger；
If the thickness of film layer is less than 2 μm, film layer is easily broken, and short circuit easily occurs for battery；Film layer with a thickness of 10~80 μm when, it is soft
Toughness is best, and interface resistance is smaller, and the comprehensive performance of film layer is best, and preferably 10 μm~80 μm, wherein Typical non-limitingly
It is preferred that 10 μm, 15 μm, 20 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm and 80 μm.
A kind of embodiment of method produced according to the present invention is in step s3, stable being formed in magnetron sputtering
Under conditions of plasma arc, vacuum degree is 2~80 millitorrs, and the time is 0.1~2 hour.
Wherein, specific operating procedure are as follows: the magnetron sputtering of silicon layer is completed in multi-target magnetic control sputtering instrument, selects silicon target
It etc. corresponding target position is installed on, closes and sputters gate, opening vacuum pump makes sputter chamber be subsequently passed micro argon gas close to vacuum
Stream opens shielding power supply, and power is 300 watts, and vacuum degree is adjusted to 2~80 millitorrs, preferably 10 millitorrs, adjusts sputtering current and electricity
Pressure etc., forms stable sputter plasma arc light, rotates base seat, adjusts sputtering time, and the control time is 0.1 to 2 small
When, preferably 0.3 hour, form the amorphous si-layer of 500~8000nm.
Under the sputtering condition, the silicon layer of formation is amorphous si-layer, therefore the silicon particle sputtered can be filled to containing
The solid-state electrolyte layer in hole enhances to form the interface of solid-state electrolyte layer and silicon layer interlaced, squeeze, permeate
The binding force of solid-state electrolyte layer and silicon layer, to realize the self-holding pressure performance of all-solid-state battery.
A kind of embodiment according to the present invention, the preferred 500nm~8000nm of the thickness of silicon layer.
The thickness of silicon layer is lower than 500nm, then battery energy density can be too low, and is higher than 8000nm, then the easy dusting of silicon materials,
Cause capacity retention ratio low, so the thickness of silicon layer preferred 500nm~8 000nm, most preferably 1000nm in the present invention~
4000nm。
The thickness of silicon layer is typical but preferred without limitation 1000nm, 1500nm, 2000nm, 2500nm, 3000nm,
3500nm and 4000nm.
Wherein, those skilled in the art can adjust the condition of magnetic control sputtering, such as sputter according to the method for magnetron sputtering
Power, sputtering time etc., come control sputtering silicon layer thickness.
A kind of embodiment of method produced according to the present invention, the wherein thickness of layers of copper or nickel layer preferably 1~10um, allusion quotation
Type but unrestricted preferred 1um, 2um, 3um, 4um, 5um, 6um, 7um, 8um, 9um, 10um.
Wherein, those skilled in the art can adjust the condition of magnetic control sputtering, such as sputter according to the method for magnetron sputtering
Power, sputtering time etc., to control the layers of copper of sputtering or the thickness of nickel layer.
In the present invention, the sputtering condition of layers of copper is general are as follows: opens shielding power supply, power is 300 watts, opening metal copper target
Shielding door, vacuum degree adjust to 2 to 80 millitorrs, and preferably 10 millitorrs adjust sputtering current and voltage etc., form stable sputtering etc.
Gas ions arc light, rotates base seat, adjusts sputtering time, and the control time is 0.1 to 1 hour, preferably 0.2 hour.
The sputtering condition of nickel layer is general in the present invention are as follows: opens shielding power supply, power is 300 watts, opening metal nickel target
Shielding door, vacuum degree adjust to 2 to 80 millitorrs, and preferably 10 millitorrs adjust sputtering current and voltage etc., form stable sputtering etc.
Gas ions arc light, rotates base seat, adjusts sputtering time, and the control time is 0.1 to 1 hour, preferably 0.2 hour.
Preparation method according to the present invention, in step sl, anode sizing agent are prepared using positive electrode and solvent,
Wherein positive electrode includes: positive electrode active materials, sulfide solid electrolyte, poly- carbonic acid alkenyl esters, conductive agent；Wherein poly- carbonic acid
The 2~6% of alkenyl esters Zhan Sizhe gross mass, four mass ratio is general are as follows: 65~80:20~35:2~6:2~8.It will be positive
Material is scattered in solvent, and anode sizing agent is prepared, and anode sizing agent is coated on plus plate current-collecting body (such as: aluminium foil), slurry
Preferably 2 μm~300 μm of thickness.General select carries out under an inert atmosphere in step sl.
Positive electrode active materials are preferably cobalt sulfide, ferrous disulfide, titanium sulfide in the present invention, can also be selected, LiNbO3It receives
Nickle cobalt lithium manganate, the LiNbO of rice layer cladding3The cobalt acid lithium or LiMn2O4 of nanometer layer cladding.When poly- carbonic acid alkenyl esters select poly- carbon
When acid propylene ester, positive electrode active materials are preferably one or more of cobalt sulfide, ferrous disulfide, titanium sulfide.
When poly- carbonic acid alkenyl esters select polypropylene carbonate, the solid electrolyte raw material in the present invention is preferably sulfide
Solid electrolyte, wherein sulfide solid electrolyte is more preferably Li2S、P2S5、Al2S3、GeS2、SiS2And SnS2In extremely
It is two kinds few.
The preferred acetylene black of conductive agent, carbon nanotube, graphene, electrically conductive graphite, conductive carbon black, Ketjen black, in carbon fiber
It is at least one；One of the preferred 1,2- dichloroethanes of solvent, methyl phenyl ethers anisole and chloroform.Wherein, the dosage of solvent is about positive material
Expect the 3%-20% of weight.
In step S1 of the invention, it can also be dried after anode sizing agent is coated on plus plate current-collecting body
Dry, drying temperature is higher than the decomposition temperature of poly- carbonic acid alkenyl esters, poly- carbonic acid alkenyl esters can be made to decompose complete.It can also be stacked
It is dried after solid electrolyte film layer, drying temperature is higher than the decomposition temperature of poly- carbonic acid alkenyl esters, decomposes it completely.
In the preparation process in accordance with the present invention, the preparation method of the solid electrolyte film layer comprising poly- carbonic acid alkenyl esters, packet
Include following steps:
(A), the raw material or sulfide solid electrolyte for preparing sulfide solid electrolyte matrix are weighed by certain quality
Matrix, and mixed with the poly- carbonic acid alkenyl esters of certain mass, it then puts it into tophan box, certain solvent is added, adds
Mill ball seals tophan box；
(B), sealing tophan box rotation is driven, centrifugal breaking is carried out, obtains slurry；
(C), slurry is scratched to plate object, obtains sulfide composite solid electrolyte film layer after dry.
In the preparation process in accordance with the present invention, sulfide solid electrolyte matrix is that the sulfide of not compound other materials is solid
State electrolyte；It is prepared by preparing the raw material of sulfide solid electrolyte matrix.Prepare sulfide solid electrolyte
Raw material generally preferably Li2S and P2S5, additionally, it is preferred that further comprising Al2S3、GeS2、SiS2And SnS2At least one of.?
In step (A), the preferred Li of sulfidic materials2S and P2S5, mixed by the molar ratio of 7:3 best.
In step (A), poly- carbonic acid alkenyl esters are preferably dried in vacuo at 30 DEG C for 24 hours, to remove water therein before addition
Point.
In step (A), whole operation crosses range request O2And H2O partial pressure is less than the closed gloves full of argon gas of 0.1ppm
It is carried out in case.Since sulfidic materials are more sensitive to water and oxygen, water partial pressure height can generate toxic H2S gas, therefore it is required that
Water and partial pressure of oxygen in glove box is small as far as possible, can be by sulfidic materials to the quick of water and oxygen when its partial pressure is respectively less than 0.1ppm
Sensitivity drops to lower.
In step (B), any one of the material preferably polytetrafluoroethylene of tophan box, corundum, zirconium oxide are selected
Tophan box material is heat-resisting and does not react with raw material；Mill ball is zirconia ball.
In step (B), sealing tophan box can be placed in centrifugal crusher by centrifugal breaking, first mix with low speed several
Minute, it is broken then to increase revolving speed progress high speed centrifugation；To obtain slurry.Wherein, low speed preferably 300~800rpm, low speed
The time of progress preferably 5~30min, high speed preferably 1000~2000rpm, the time being carried out at high speed preferably 10~90min.
A large amount of heat is generated to machine loss to avoid continuing shattering process, is preferably provided with the broken completion of high speed centrifugation
Afterwards, it is spaced 10min, then carries out centrifugal breaking experiment next time.
Solvent includes at least one of 1,2- dichloroethanes, methyl phenyl ethers anisole and chloroform.
Wherein, one of solvent preferably 1,2- dichloroethanes, methyl phenyl ethers anisole and chloroform, further preferred methyl phenyl ethers anisole steam
Air pressure is lower, volatilizees slower, can make the surfacing of film forming.
Preparation method according to the present invention contains 4~6% poly- carbon by percentage to the quality in solid electrolyte film layer
Sour alkenyl esters.Wherein, the mass fraction of poly- carbonic acid alkenyl esters is 4~6%, and poly- carbonic acid alkenyl esters can be formed in right amount after disassembly
Hole, make when sputtering silicon layer, silicon particle is filled into hole, and the silicon layer of staggered densification, enhancing solid electrolyte membrane are formed
The binding force of layer and silicon layer, makes the stronger of two layers of combination.
Wherein, dry temperature control is 80~120 DEG C, and the time is 1~5h, can remove at such a temperature solvent at
Film, and poly- carbonic acid alkenyl esters can not be made to decompose.
A kind of embodiment of preparation method according to the present invention, single battery core is stacked, and is assembled into the electricity of multiplication of voltage output
Core；Then the battery core of stacking hot melt vulcanized rubber is sealed into four side of battery core, be transferred in aluminum plastic film, carry out Tetrapack brick packet
Dress, finally encapsulation isolation steam.Battery after encapsulation, does not need pressurizing device, can directly use.
According to another aspect of the present invention, a kind of all-solid-state battery that method produced according to the present invention obtains is provided.
The all-solid-state battery that method produced according to the present invention obtains both can be normal without additional pressurizer
Operation, the opposite all-solid-state battery for needing additional pressurizer, improves energy density.
In order to preferably explain the present invention, in order to understand, below with reference to embodiment, the present invention is described in detail.It needs
Illustrate, embodiment is only used for that the present invention will be described, can't limit claims of the invention
System.
Embodiment 1
Step S1 is carried out first: the anode sizing agent containing polypropylene carbonate is coated on plus plate current-collecting body.Wherein, lazy
Under property atmosphere, by positive electrode active materials (a ferrous sulfide lithium), sulfide solid electrolyte, polypropylene carbonate (PPC) (molecule
Amount is 357000) (3wt.% of Zhan Sizhe total weight), acetylene black, mixes by weight the ratio of 65:30:3:2, uses methyl phenyl ethers anisole
It is prepared into anode sizing agent as solvent, anode sizing agent is coated on plus plate current-collecting body aluminium foil, the thickness range of slurry is in 100 μ
m。
Then it carries out step S2: the solid electrolyte membrane stacking containing polypropylene carbonate is placed in coated with anode sizing agent
Plus plate current-collecting body after, drying；Wherein, 5% poly- propylene carbonate by percentage to the quality is contained in solid electrolyte film layer
Ester, solid electrolyte are sulfide solid electrolyte, solid electrolyte film layer with a thickness of 50 μm, drying temperature is 230 DEG C,
30min。
The solid electrolyte film surface of step S3 after the drying is carried out later, carries out magnetron sputtering, forms silicon layer；
Solid electrolyte film layer is placed in magnetron sputtering base seat, rf-mode sputtered silicon upwards, intracavitary sputtering pressure is 10 millitorrs, function
Rate is 300 watts, the time is 8 minutes；Form the silicon layer with a thickness of 500nm.
Followed by step S4: carrying out magnetron sputtering in silicon surface, form nickel layer or layers of copper.Close silicon target masking
Door opens the copper target material shielding door of installation, and adjustment sputtering power is 300 watts, sputters 15 minutes, forms the layers of copper with a thickness of 5um；
Finally, the single battery core of formation is stacked, it is assembled into the battery core of multiplication of voltage output；By the battery core of stacking hot melt sulphur
Change rubber and seal four side of battery core, be transferred in aluminum plastic film, carries out Tetrapack brick type packaging, all-solid-state battery is prepared.
Embodiment 2
The present embodiment is identical as other conditions of embodiment 1, the difference is that, in step sl, positive electrode includes:
LiNbO3Nickle cobalt lithium manganate (NCM), the Li coated2S-P2S5Sulfide solid electrolyte, polypropylene carbonate, acetylene black；Four
The weight ratio of person is 80:15:3:2；
Embodiment 3
Other conditions of the embodiment and embodiment 1 are all the same, the difference is that, positive electrode packet in step sl
It includes: positive electrode active materials (LiTiS2), sulfide solid electrolyte, polypropylene carbonate, acetylene black；Four weight ratio is
55:40:3:2。
Embodiment 4
Other conditions of the embodiment and embodiment 1 are all the same, the difference is that, polypropylene carbonate accounts for positive electrode
2% by percentage to the quality.
Embodiment 5
Other conditions of the embodiment and embodiment 1 are all the same, the difference is that, polypropylene carbonate accounts for positive electrode
4% by percentage to the quality.
Embodiment 6
Other conditions of the embodiment and embodiment 1 are all the same, the difference is that, polypropylene carbonate accounts for positive electrode
5% by percentage to the quality.
Embodiment 7
Other conditions of the embodiment and embodiment 1 are all the same, the difference is that, polypropylene carbonate accounts for positive electrode
6% by percentage to the quality.
The embodiment of embodiment 8 and the other conditions of embodiment 1 are all the same, the difference is that, in solid electrolyte film layer
Contain 4% polypropylene carbonate by percentage to the quality.
The embodiment of embodiment 9 and the other conditions of embodiment 1 are all the same, the difference is that, in solid electrolyte film layer
Contain 6% polypropylene carbonate by percentage to the quality.
Comparative example 1
In a kind of the comparative example, silicon layer is sputtered on copper current collector, sputtering condition is identical as the sputtering condition in embodiment 1.
Amplification 1000 times (as shown in Figure 1) and 3000 times (as shown in Figure 2) have been carried out after silicon layer being sputtered in comparative example 1
Scanning electron microscope (SEM) photograph, from scanning electron microscope (SEM) photograph, it can be seen that the silicon layer formed under the sputtering condition is amorphous silicon.
By the collector after the copper current collector and sputtering silicon layer in comparative example 1, silicon crystal diffraction pattern (XRD) inspection has been carried out
It surveys, testing result is as shown in Figure 3.In Fig. 3, line a is the XRD diagram of copper current collector, and line b is the XRD of collector after sputtering silicon layer
Figure, it is substantially corresponding with copper foil characteristic peak as can be seen that the characteristic peak of crystalline silicon does not occur in silicon layer from the line b of Fig. 3；Thus
Illustrate to be formed under the sputtering condition is unformed silicon.
It in summary it can be seen, under the conditions of magnetron sputtering of the invention, the silicon layer of formation is amorphous silicon, therefore sputter
Silicon particle can be filled to containing porose solid-state electrolyte layer, staggeredly squeeze the solid-state electrolyte layer permeated and silicon layer to be formed
Interface, the binding force of solid-state electrolyte layer and silicon layer is enhanced, to realize the self-holding pressure performance of all-solid-state battery.
Comparative example 2
(1) it by the dry powder blend of positive electrode, suppresses powder and plus plate current-collecting body (aluminium foil) forms anode pole piece；Wherein just
The composition and ratio of pole material are identical as the positive electrode in embodiment 1, but do not include polypropylene carbonate wherein；
(2) sulfur compound solid electrolyte film layer is prepared, in the other compositions and embodiment 1 of the solid electrolyte film layer
Solid electrolyte film layer is identical, but is wherein free of polypropylene carbonate；
(3) anode pole piece/solid electrolyte film layer/silicium cathode pole piece is stacked, the pressure of 20MPa or more is applied；
(4) above-mentioned solid state battery battery core is encapsulated into isolation steam using aluminum plastic film or holding pressure vessel.
Comparative example 3
The comparison and other conditions of embodiment 1 are all the same, the difference is that, drying temperature is 120 DEG C.
Comparative example 4
Other conditions of the embodiment and embodiment 1 are all the same, the difference is that, drying temperature is 200 DEG C.
When having carried out all-solid-state battery obtained in embodiment 1-9 and comparative example 2~4 to have 20MPa pressure and no pressure
The test of open-circuit voltage, in 0.1c, the test result of discharge platform voltage is as shown in table 1:
Table 1
It can be seen that compared with comparative example 2 according to the result in table 1, the all-solid-state battery of Examples 1 to 9 is in no pressure
Under the conditions of when detecting, all have preferable discharge voltage plateau, excellent coulombic efficiency, this illustrates that Examples 1 to 9 obtains complete
Solid state battery realizes the performance for pressure of controlling oneself, does not need pressurizer.And when being detected under the conditions of no pressure in comparative example 2,
Silicon wafer cathode cannot carry out dense contact with electrolyte membrane layer, lead to Resistance Maximum or open circuit, further result in battery without work
Property, it is unable to normal use.
The Comparative result of the result of comparative example 3 and 4 and Examples 1 to 9 is found, the excellent degree drop of coulombic efficiency
It is low, this is because PPC therein pyrolysis not exclusively affects the capacity performance of positive electrode active materials, reduces the ion of battery
Conductivity and capacity retention ratio.
To sum up, pressure of controlling oneself may be implemented in the all-solid-state battery that preparation method of the present invention is prepared, and functional.
The above described is only a preferred embodiment of the present invention, being not the limitation for doing other forms to the present invention, appoint
What those skilled in the art can use the equivalence enforcement that technology contents disclosed above were changed or be modified as equivalent variations
Example.But without departing from the technical solutions of the present invention, according to the technical essence of the invention to the above embodiments
What simple modification, equivalent variations and remodeling, still falls within the protection scope of technical solution of the present invention.
Claims (10)
1. a kind of preparation method of all-solid-state battery characterized by comprising
Step S1: the anode sizing agent containing poly- carbonic acid alkenyl esters is coated on plus plate current-collecting body；
Step S2: the solid electrolyte membrane stacking containing poly- carbonic acid alkenyl esters is placed in the anode coated with the anode sizing agent and is collected
After fluid, drying；
Step S3: the solid electrolyte film surface after the drying carries out magnetron sputtering, forms silicon layer；
Step S4: magnetron sputtering is carried out in silicon surface, forms nickel layer or layers of copper.
2. preparation method according to claim 1, which is characterized in that the poly- carbonic acid alkenyl esters include in following at least
It is a kind of: poly- ethylene carbonate, polypropylene carbonate, poly- butylene, polycyclohexene.
3. preparation method according to claim 2, which is characterized in that in step sl, the anode sizing agent includes anode
Material and solvent, the positive electrode include poly- carbonic acid alkenyl esters, the poly- carbonic acid alkenyl esters account for the positive electrode with matter
Measure the 2~6% of percentages.
4. preparation method according to claim 2, which is characterized in that in step s 2, the poly- carbonic acid alkenyl esters account for institute
State 4~6% by percentage to the quality of solid electrolyte film layer.
5. preparation method according to claim 3, which is characterized in that
The poly- carbonic acid alkenyl esters are polypropylene carbonate, and the molecular weight of the polypropylene carbonate is 150000~500000；
It include the positive electrode active materials of sulfur-bearing in the positive electrode；
It include sulfide solid electrolyte in the solid electrolyte film layer.
6. preparation method according to claim 5, which is characterized in that the drying temperature is 220~250 DEG C, when drying
Between be 30~60min.
7. preparation method according to claim 1, which is characterized in that in step s3, in the magnetron sputtering, in shape
Under conditions of stable plasma arc, vacuum degree is 2~80 millitorrs, and the time is 0.1~2 hour.
8. preparation method according to claim 1, which is characterized in that the solid electrolyte film layer with a thickness of 2~300
μm。
9. preparation method according to claim 1, which is characterized in that the layers of copper or nickel layer with a thickness of 1 μm~10 μm.
10. a kind of all-solid-state battery that the preparation method any according to claim 1~9 obtains.
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| CN108232320A (en) * | 2018-02-08 | 2018-06-29 | 天津瑞晟晖能科技有限公司 | The preparation method and solid-State Thin Film Li-Ion Batteries of solid-State Thin Film Li-Ion Batteries |
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| CN105702919A (en) * | 2016-04-06 | 2016-06-22 | 中国科学院青岛生物能源与过程研究所 | Lithium battery electrode preparation method including polymer material with stable interface and application of lithium battery electrode in solid lithium battery |
| CN108232320A (en) * | 2018-02-08 | 2018-06-29 | 天津瑞晟晖能科技有限公司 | The preparation method and solid-State Thin Film Li-Ion Batteries of solid-State Thin Film Li-Ion Batteries |
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| CN112151875A (en) * | 2020-10-20 | 2020-12-29 | 深圳聚锂能源有限公司 | Current collector-free battery core, preparation method thereof and lithium ion battery |
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