CN109935909A - A kind of lithium an- ode battery structure and preparation method thereof - Google Patents
A kind of lithium an- ode battery structure and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to technical field of lithium batteries more particularly to a kind of lithium an- ode battery structure and preparation method thereof.Including anode structure, negative pole structure and the solid polyelectrolyte layer being arranged between, the solid polyelectrolyte layer includes solid polyelectrolyte material；The negative pole structure includes lithium metal active material, and the negative pole structure is formed with cathode decorative layer towards the side of solid polyelectrolyte layer.The solid polyelectrolyte layer includes solid polyelectrolyte material, and polymer electrolyte ionic conductivity is high, electrochemically stable, and it keeps it good with the interfacial contact of electrode with high Young's modulus, reduces interface impedance；Cathode decorative layer is formed on negative pole structure simultaneously, cathode decorative layer is as electrolyte thin film layer, so that charge is evenly distributed on cathode decorative layer, limits the formation of Li dendrite well, the stability for enhancing lithium battery structure, improves the service life of lithium battery.
Description
[technical field]
The present invention relates to technical field of lithium batteries more particularly to a kind of lithium an- ode battery structure and preparation method thereof.
[background technique]
The features such as lithium battery is due to energy density with higher, good cyclicity, memory-less effect is by people's
It pays close attention to.
Lithium an- ode material has highest specific capacity (~3862mAh/g), is considered high-energy-density lithium electricity of new generation
The negative electrode material in pond.However during charge and discharge cycles, the lithium battery of lithium metal base can generate Li dendrite, cause battery short
Road is exploded.Polymer ionic electrolytes conductor have ionic conductivity high (>=0.1mS/cm), it is electrochemically stable (>=
The advantages such as 4.5V), are the first choices of flexible lithium battery solid electrolyte, the advantage of high Young's modulus connects the interface of itself and electrode
Touching property is good, and crystal boundary problem is not present, but its modulus of shearing is relatively low, and there are the risks that Li dendrite punctures short circuit.Therefore,
How under the premise of not sacrificial polymer ion conductor existing high-performance parameter, inhibiting the growth of Li dendrite will solve lithium electricity
Pond is applied to the critical issue in high-energy density field.
[summary of the invention]
To overcome current lithium metal base negative pole lithium battery stability not high, energy density still needs to the technical issues of improving, this
Invention provides a kind of electrode interface stabilization, good lithium an- ode battery structure of battery performance and preparation method thereof.
In order to solve the above-mentioned technical problem the present invention, provides a technical solution: a kind of lithium an- ode battery structure, including
Anode structure, negative pole structure and the solid polyelectrolyte layer being arranged between, the anode structure include MxOyType mistake
Cross metal oxide active material；The solid polyelectrolyte layer includes solid polyelectrolyte material；The cathode
Structure includes lithium metal active material, and the negative pole structure is formed with cathode modification towards the side of solid polyelectrolyte layer
Layer, the cathode decorative layer includes the carbuncle type and anti-perovskite type, Li with ionic conduction performance3PO4Equal lithium compounds.
Preferably, the cathode decorative layer includes the Li of carbuncle type7+yLa3Zr2-x-yMxAyO12(2,0≤y≤2 0≤x <
With 0≤x+y≤2, A=Al, Ga, In, Sc, Y, M=Ge, Zr, Hf etc.), the Li of anti-perovskite type3OX (X=Cl, F, Br, I
Deng), Li2OHX (X=Cl, F, Br, I etc.), Li3PO4Equal lithium compounds.
Preferably, cathode decorative layer includes at least one lithium compound.
Preferably, the cathode decorative layer with a thickness of 10-200nm.
Preferably, the solid polyelectrolyte material that the solid polyelectrolyte layer includes is organic polymer electricity
Any one of solution material polyethylene glycol oxide (PEO), Kynoar (PVDF) or non-carbon covalent bond form inorganic
Solid polyelectrolyte material Li2B12FxH12-x, anti-perovskite inorganic polymer Li3OX (X=Cl, F, Br, I etc.), N doping
S based inorganic polymer (LiSxNy) and Li3Se(BH4)、Li3Se(AlH4)、Li3Se(BF4) etc. any in inorganic polymers
Kind.
In order to solve the above-mentioned technical problem the present invention, provides another technical solution, a kind of lithium an- ode battery structure
Preparation method, preparation method include physical vaporous deposition, chemical vapour deposition technique, 3D printing method, slot coated method, scrape cutter painting
Cloth method or micro-gravure coating process.
Specific step is as follows for preparation method:
The preparation of anode structure；
Solid polyelectrolyte layer is formed on anode structure；
Cathode decorative layer is formed on solid polyelectrolyte layer；
Negative film layer is formed on cathode decorative layer；
Negative current collector is formed on negative film layer obtains battery structure.
Preferably, the specific method of solid polyelectrolyte layer is formed on anode structure as by the side of blade coating
Formula coats one layer of polymeric solid electrolyte slurry on anode structure, then realizes in-situ polycondensation reaction, shape by baking
At solid polyelectrolyte layer.
Preferably, the method for cathode decorative layer being formed on solid polyelectrolyte layer is specially magnetron sputtering method,
Magnetron sputtering method is one of physical vaporous deposition, the specific steps are as follows:
It provides one and is formed with the anode structure of solid polyelectrolyte layer as bottom liner；
The installation of cathode decorative layer target；
Back end vacuum pressure is extracted into lower than 5.0 × 10-4Pa；
Heating bottom liner temperature: 25-300 DEG C.
Adjusting air pressure be 0.5-1.5Pa, sputtering power are as follows: 60-120W, sputtering time are as follows: 10-60min, be passed through argon gas into
Row sputtering.
Preferably, air pressure 0.2Pa, sputtering power 70W obtain being formed in negative on solid polyelectrolyte layer
The thickness of pole decorative layer are as follows: 60nm.
Compared with prior art, the solid polyelectrolyte layer includes solid polyelectrolyte material；It is described negative
Pole structure includes lithium metal active material, and the negative pole structure is formed with cathode towards the side of solid polyelectrolyte layer and repairs
Adorn layer.The solid polyelectrolyte layer includes solid polyelectrolyte material, and polymer electrolyte has ion
The advantages such as conductivity height (>=0.1mS/cm), electrochemically stable (>=4.5V), are the first choices of flexible lithium battery solid electrolyte,
The advantage of high Young's modulus keeps it good with the interfacial contact of electrode, overcomes solid polyelectrolyte layer and cathode well
Interface impedance problem between structure, improves the conductive performance of conductive ion；Cathode modification is formed on negative pole structure simultaneously
Layer, cathode decorative layer is arranged between negative pole structure and solid polyelectrolyte layer as electrolyte thin film layer, so that electric
Lotus is evenly distributed on cathode decorative layer, limits the formation of Li dendrite well, enhances the stability of lithium battery structure, mention
The service life of high lithium battery.
The cathode decorative layer includes the lithium compound, so that cathode decorative layer has good ionic conduction performance.
Cathode decorative layer includes at least one lithium compound, preferably alleviates cathode decorative layer and polymer solid electricity
The difference of interfacial concentration between matter layer is solved, so that conductive ion being deposited on cathode decorative layer more evenly, preferably inhibits
The formation of Li dendrite.
The cathode decorative layer with a thickness of 10-200nm, transition modification can be played well, alleviated due to cathode
Interface impedance caused by the difference of Interface composition between structure and solid polyelectrolyte layer, while inhibiting the life of Li dendrite
It is long, guarantee the transmission performance of conductive ion well.
By physical vaporous deposition, chemical vapour deposition technique, 3D printing method, slot coated method, scraper for coating method or
Micro-gravure coating process prepares the lithium battery structure, so that the structural homogeneity for forming each layer is preferable, it is each adjacent to enhance well
The interface impedance between contact, reduction contact interface between two layers, improves electric conductivity.
Preferably, air pressure is preferably 0.2Pa, and sputtering power is preferably 70W, obtains being formed in solid polyelectrolyte layer
On cathode decorative layer thickness are as follows: 60nm preferably inhibits lithium so that the consistency and uniformity of cathode decorative layer are more preferable
The formation of dendrite.Simultaneously conductive ion is preferably conducted between solid polyelectrolyte layer and negative pole structure.
[Detailed description of the invention]
Fig. 1 is the overall structure diagram of lithium an- ode battery structure in the present invention；
Fig. 2 is the flow chart of lithium an- ode battery structure preparation method in the present invention；
Fig. 3 is the flow chart that anode structure is prepared in the present invention；
Fig. 4 is the flow chart for forming solid polyelectrolyte layer in the present invention on anode structure；
Fig. 5 is the flow chart for forming cathode decorative layer in the present invention on solid electrolyte；
Fig. 6 is the flow chart for forming negative film layer in the present invention on cathode decorative layer；
Fig. 7 is to form negative current collector on negative film layer in the present invention to obtain the flow chart of battery structure.
[specific embodiment]
In order to make the purpose of the present invention, technical solution and advantage are more clearly understood, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Referring to Fig. 1, a kind of lithium an- ode battery structure 10, including anode structure 100, negative pole structure 300 and setting
Solid polyelectrolyte layer 200 therebetween, the solid polyelectrolyte layer 200 are electrolysed including polymer solid
Material；The negative pole structure 300 includes lithium metal active material, and the negative pole structure 300 is towards solid polyelectrolyte
The side of layer 200 is formed with cathode decorative layer 400, the cathode decorative layer include the carbuncle type with ionic conduction performance,
Anti-perovskite type, Li3PO4Equal lithium compounds；The anode structure 100, solid polyelectrolyte layer 200, cathode decorative layer
400 and negative pole structure 300 be sequentially overlapped setting, and the cathode decorative layer 400 is contacted with solid polyelectrolyte layer 200.
Anode structure 100 includes plus plate current-collecting body 101 and is formed on the plus plate current-collecting body 101 solid towards polymer
The anode thin film layer 102 of 200 side of state electrolyte layer.Plus plate current-collecting body 101 is selected from Al, Pt, Au, Cu, Ag, Mo, Ni, stainless steel
Wait any one in metal materials, with a thickness of 0.5-2 μm, preferably 1 μm.
Anode thin film layer 102 includes MxOyType transition metal oxide electrode material, MxOyType transition metal oxide active
Material is CuO, NiO, Bi2O3、CoO、FeO、Fe2O3、Mn2O3In one of equal transition metal oxides or its derivative
It is any.MxOyType transition metal oxide electrode material have height ratio capacity (>=700mAh/g) and high voltage platform (>=
4.5V), and manufacturing process is relatively easy, is the preferred of high-energy electrode material of lithium battery.The thickness of the anode thin film layer 102
It is 0.5-5 μm, preferably 2 μm.
Solid polyelectrolyte material included by the solid polyelectrolyte layer 200 is organic polymer electrolysis
Any one of material polyethylene glycol oxide (PEO), Kynoar (PVDF) or non-carbon covalent bond are formed inorganic poly-
Close object solid electrolyte material Li2B12FxH12-x, anti-perovskite inorganic polymer Li3The S of OX (X=Cl, F, Br, I etc.), N doping
Based inorganic polymer (LiSxNy) and Li3Se(BH4)、Li3Se(AlH4)、Li3Se(BF4) etc. any one of inorganic polymers.
Solid polyelectrolyte material has the advantages such as ionic conductivity high (>=0.1mS/cm), electrochemically stable (>=4.5V), is
The first choice of flexible lithium battery solid electrolyte, the advantage of high Young's modulus keep it good with the interfacial contact of electrode, so that
Interface impedance is lower.The solid polyelectrolyte layer 200 with a thickness of 0.5-5 μm, preferably 1 μm.
Negative pole structure 300 includes negative current collector 301 and is formed on the negative current collector 301 solid towards polymer
The negative film layer 302 of 200 side of state electrolyte layer.Negative current collector 301 is selected from Pt, Au, Cu, Ag, Mo, Ni, stainless steel etc.
Any one in metal material, with a thickness of 0.5-2 μm, preferably 1 μm.
Negative film layer 302 includes lithium metal active material.Negative film layer 302 with a thickness of 0.5-2 μm, preferably 1 μm.
Lithium metal active material has highest specific capacity (~3862mAh/g), is high-energy density lithium cell cathode material of new generation
First choice.
The negative pole structure 300 is formed with cathode decorative layer 400 towards the side of solid polyelectrolyte layer 200.It is negative
Pole decorative layer 400 and solid polyelectrolyte layer 200 contact.Cathode decorative layer 400 includes the Li of carbuncle type7+ yLa3Zr2-x-yMxAyO12It is (0≤x < 2,0≤y≤2 and 0≤x+y≤2, A=Al, Ga, In, Sc, Y, M=Ge, Zr, Hf etc.), anti-
The Li of Ca-Ti ore type3OX (X=Cl, F, Br, I etc.), Li2OHX (X=Cl, F, Br, I etc.), Li3PO4Equal lithium compounds.Cathode is repaired
Adoring layer 400 includes at least one lithium compound.Cathode decorative layer 400 with a thickness of 10-200nm.
The lithium compound that cathode decorative layer 400 includes has good ionic conduction performance, guarantees that conductive ion is polymerizeing
It is conducted between object solid-state electrolyte layer 200 and negative pole structure 300, guarantees electric conductivity.Meanwhile cathode decorative layer 400 is used as people
Make SEI film, and be arranged between negative pole structure 300 and solid polyelectrolyte layer 200 so that charge be evenly distributed in it is negative
On pole decorative layer 400, the energy density of lithium battery is improved.Meanwhile the formation of limitation Li dendrite well, enhance lithium battery knot
The stability of structure improves the service life of lithium battery.
Incorporated by reference to Fig. 1 and Fig. 2, the second object of the present invention is to provide a kind of preparation side of lithium an- ode battery structure
Method, preparation method mainly include physical vaporous deposition, chemical vapour deposition technique, 3D printing method, slot coated method, blade coating
Method or micro- gravure coating method etc., the specific steps of which are as follows:
A1: the preparation of anode structure 100；
A2: solid polyelectrolyte layer 200 is formed on anode structure 100；
A3: cathode decorative layer 400 is formed on solid polyelectrolyte layer 200；
A4: negative film layer 302 is formed on cathode decorative layer 400；
A5: negative current collector 301 is formed on negative film layer 302 and obtains battery structure 10.
Referring to Fig. 3, the preparation method of anode structure 100 is specially magnetron sputtering method, magnetron sputtering in above-mentioned steps A1
Method is one of physical vaporous deposition, the specific steps are as follows:
A11: a plus plate current-collecting body 101 is provided and is used as bottom liner；
A12: the installation of anode thin film layer target；
A13: back end vacuum pressure is extracted into lower than 5.0 × 10-4Pa；
A14: heating bottom liner temperature: 25-400 DEG C.
A15: adjusting air pressure is 0.5-1.5Pa, argon gas: oxygen proportion 5:5-0:10, sputtering power are as follows: 60-140W splashes
Penetrate the time are as follows: 1-3h obtains anode structure 100.
In above-mentioned steps A11, the plus plate current-collecting body 101 as substrate specifically selects gold-plated silicon wafer, successively using acetone,
Ethyl alcohol and deionized water carry out the cleaning of 10-30min duration, after cleaning terminates, using gas spray as cleaning agent to substrate
Rifle dries up the moisture on 101 surface of substrate plus plate current-collecting body, is installed in magnetron sputtering substrate frame.
The installation of anode thin film layer target, the specially installation of Cu metal targets in above-mentioned steps A12.
The thickness range for the anode thin film layer 102 that above-mentioned steps A15 sputtering obtains after completing are as follows: 0.5-5 μm.
Preferably, in above-mentioned steps, bottom liner temperature setting are as follows: 400 DEG C, adjusting air pressure is 0.5Pa, sputtering atmosphere are as follows: argon
Gas: oxygen=5:5, sputtering power are as follows: 80W, the thickness for the anode thin film layer 102 that sputtering obtains after completing are as follows: 2 μm.
The uniformity for being formed in the anode thin film layer 102 on the plus plate current-collecting body 101 is obtained by magnetron sputtering method
Preferably, so that the stability of anode structure obtained 100 is strong.
Referring to Fig. 4, it is specific to form solid polyelectrolyte layer 200 on anode structure 100 in above-mentioned steps A2
For on anode thin film layer 102 formed solid polyelectrolyte layer 200, specific method be by way of blade coating
One layer of polymeric solid electrolyte slurry is coated on anode thin film layer 102, and in-situ polycondensation reaction, shape are then realized by baking
At solid polyelectrolyte layer 200, the specific steps are as follows:
A21: solid electrolyte material is subjected to planetary stirring, forms slurry；
A22: slurry is poured on anode thin film layer 102；
A23: it obtains being formed with wet solid polyelectrolyte on anode thin film layer 102 by way of blade coating
The electrode slice of film layer 200；
A24: electrode slice is toasted, and removes solvent, and in-situ polycondensation forms solid polyelectrolyte layer 200.
In above-mentioned steps A23, the rate of coating are as follows: 0.2-5cm/s.
In above-mentioned steps A24, baking temperature are as follows: 50-120 DEG C, after baking terminates, the solid polyelectrolyte of acquisition
Layer 200 with a thickness of 1-20 μm.
Preferably, in above-mentioned steps, rate is coated are as follows: 0.7cm/s, baking temperature: 80 DEG C, the polymer solid electricity of formation
The thickness of solution matter layer 200: 2 μm.
Referring to Fig. 5, cathode decorative layer 400 is formed in above-mentioned steps A3 on solid polyelectrolyte layer 200
Specific method is magnetron sputtering method, the specific steps are as follows:
A31: it provides one and is formed with the anode structure 100 of solid polyelectrolyte layer 200 as bottom liner；
A32: the installation of cathode decorative layer target；
A33: back end vacuum pressure is extracted into lower than 5.0 × 10-4Pa；
A34: heating bottom liner temperature: 25-300 DEG C.
A35: adjusting air pressure is 0.5-1.5Pa, sputtering power are as follows: 60-120W, sputtering time are as follows: 10-60min is passed through argon
Gas is sputtered.
In above-mentioned steps A32, the installation of cathode decorative layer target is specially Li3PO4Installation.
Obtain being formed in the cathode decorative layer on solid polyelectrolyte layer 200 through step A35 sputtering after completing
400, the thickness range of cathode decorative layer 400 are as follows: 10-200nm.
Preferably, in above-mentioned steps A35, air pressure 0.2Pa, sputtering power 70W obtain being formed in polymer solid electricity
Solve the thickness of the cathode decorative layer 400 on matter layer 200 are as follows: 60nm.
Preferably, in other embodiments, the installation of cathode decorative layer target is also possible to pomegranate in above-mentioned steps A32
The Li of stone-type7+yLa3Zr2-x-yMxAyO12(0≤x < 2,0≤y≤2 and 0≤x+y≤2, A=Al, Ga, In, Sc, Y, M=Ge,
Zr, Hf etc.), the Li of anti-perovskite type3OX (X=Cl, F, Br, I etc.), Li2OHX (X=Cl, F, Br, I etc.), Li3PO4Deng at least
A kind of installation of lithium compound, so that the cathode decorative layer 400 that sputtering is formed on solid polyelectrolyte layer 200 includes
At least one lithium compound preferably alleviates interfacial concentration between cathode decorative layer 400 and solid polyelectrolyte layer 200
Difference, so that conductive ion being deposited on cathode decorative layer 400 more evenly, preferably inhibits the formation of Li dendrite.
It obtains being formed in the cathode decorative layer 400 on the solid polyelectrolyte layer 200 by magnetron sputtering method,
The uniformity of obtained cathode decorative layer 400 is preferable, overcomes surface defect phenomenon well so that charge be evenly distributed in it is negative
On pole decorative layer 400, the energy density of lithium battery is improved.Meanwhile the formation of limitation Li dendrite well, enhance lithium battery knot
The stability of structure improves the service life of lithium battery.
Referring to Fig. 6, the side on cathode decorative layer 400 far from anode structure 100 forms negative in above-mentioned steps A4
The method of very thin film layer 302 is thermal resistance evaporation, and step is specific as follows:
A41: the solid polyelectrolyte layer 200 that one forms cathode decorative layer 400 is provided and is used as bottom liner；
A42: installation negative film layer steaming；
A43: the air pressure in cavity is adjusted 10-4Pa or more, sputtering power are as follows: 50-200W, sputtering time are as follows: 10-
60min。
After evaporating through step A43, the thickness of obtained negative film layer 302 are as follows: 0.5-2 μm.
Preferably, in above-mentioned steps, evaporation power 60W, with a thickness of 1 μm.
Referring to Fig. 7, the method for forming negative current collector 301 in above-mentioned steps A5 on negative film layer 302 is specific
For magnetron sputtering method, the specific steps are as follows:
A51: it provides one and is formed with the cathode decorative layer 400 of negative film layer 302 as bottom liner；
A52: the installation of negative current collector target；
A53: back end vacuum pressure is extracted into lower than 5.0 × 10-4Pa；
A54: adjusting air pressure is 0.2-1.0Pa, sputtering power are as follows: 40-60W, sputtering time are as follows: 2-100min.
In above-mentioned steps A52, the installation of negative current collector target is specially the installation of copper metal.
After above-mentioned steps A54 sputtering is completed, the thickness of the negative current collector 301 of acquisition are as follows: 0.5-2 μm.
Preferably, in above-mentioned steps A54, air pressure is preferred are as follows: 0.5Pa, sputtering power 40W, sputtering atmosphere are as follows: argon gas,
Obtain negative current collector 301 with a thickness of 1 μm.
Compared with prior art, the solid polyelectrolyte layer includes solid polyelectrolyte material；It is described negative
Pole structure includes lithium metal active material, and the negative pole structure is formed with cathode towards the side of solid polyelectrolyte layer and repairs
Adorn layer.The solid polyelectrolyte layer includes solid polyelectrolyte material, and polymer electrolyte has ion
The advantages such as conductivity height (>=0.1mS/cm), electrochemically stable (>=4.5V), are the first choices of flexible lithium battery solid electrolyte,
The advantage of high Young's modulus keeps it good with the interfacial contact of electrode, overcomes solid polyelectrolyte layer and cathode well
Interface impedance problem between structure, improves the conductive performance of conductive ion；Cathode modification is formed on negative pole structure simultaneously
Layer, cathode decorative layer is arranged between negative pole structure and solid polyelectrolyte layer as electrolyte thin film layer, so that electric
Lotus is evenly distributed on cathode decorative layer, limits the formation of Li dendrite well, enhances the stability of lithium battery structure, mention
The service life of high lithium battery.
The cathode decorative layer includes the lithium compound, so that cathode decorative layer has good ionic conduction performance.
Cathode decorative layer includes at least one lithium compound, preferably alleviates cathode decorative layer and polymer solid electricity
The difference of interfacial concentration between matter layer is solved, so that conductive ion being deposited on cathode decorative layer more evenly, preferably inhibits
The formation of Li dendrite.
The cathode decorative layer with a thickness of 10-200nm, transition modification can be played well, alleviated due to cathode
Interface impedance caused by the difference of Interface composition between structure and solid polyelectrolyte layer, while inhibiting the life of Li dendrite
It is long, guarantee the transmission performance of conductive ion well.
By physical vaporous deposition, chemical vapour deposition technique, 3D printing method, slot coated method, scraper for coating method or
Micro-gravure coating process prepares the lithium battery structure, so that the structural homogeneity for forming each layer is preferable, it is each adjacent to enhance well
The interface impedance between contact, reduction contact interface between two layers, improves electric conductivity.
Preferably, air pressure is preferably 0.2Pa, and sputtering power is preferably 70W, obtains being formed in solid polyelectrolyte layer
On cathode decorative layer thickness are as follows: 60nm preferably inhibits lithium so that the consistency and uniformity of cathode decorative layer are more preferable
The formation of dendrite.Simultaneously conductive ion is preferably conducted between solid polyelectrolyte layer and negative pole structure.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in original of the invention
Made any modification within then, equivalent replacement and improvement etc. should all be comprising within protection scope of the present invention.
Claims (10)
1. a kind of lithium an- ode battery structure, it is characterised in that: including anode structure, negative pole structure and be arranged between
Solid polyelectrolyte layer, the anode structure includes MxOyType transition metal oxide active material；The polymer is solid
State electrolyte layer includes solid polyelectrolyte material；The negative pole structure includes lithium metal active material, the negative polarity node
Structure is formed with cathode decorative layer towards the side of solid polyelectrolyte layer, and the cathode decorative layer includes having ionic conduction
Carbuncle type, anti-perovskite type, the Li of performance3PO4Equal lithium compounds.
2. lithium an- ode battery structure as described in claim 1, it is characterised in that: the cathode decorative layer includes garnet
The Li of type7+yLa3Zr2-x-yMxAyO12(0≤x < 2,0≤y≤2 and 0≤x+y≤2, A=Al, Ga, In, Sc, Y, M=Ge, Zr,
Hf etc.), the Li of anti-perovskite type3OX (X=Cl, F, Br, I etc.), Li2OHX (X=Cl, F, Br, I etc.), Li3PO4Etc. lithiumations close
Object.
3. lithium an- ode battery structure as claimed in claim 2, it is characterised in that: cathode decorative layer includes at least one institute
State lithium compound.
4. lithium an- ode battery structure as described in claim 1, it is characterised in that: the cathode decorative layer with a thickness of
10-200nm。
5. lithium an- ode battery structure as described in claim 1, it is characterised in that: the solid polyelectrolyte layer packet
The solid polyelectrolyte material included is organic polyelectrolyte material polyethylene glycol oxide (PEO), Kynoar
Or the inorganic polymer solid electrolyte material Li that is formed of non-carbon covalent bond any one of (PVDF)2B12FxH12-x, anti-calcium
Titanium ore inorganic polymer Li3S based inorganic polymer (the LiS of OX (X=Cl, F, Br, I etc.), N dopingxNy) and Li3Se(BH4)、
Li3Se(AlH4)、Li3Se(BF4) etc. any one of inorganic polymers.
6. a kind of preparation method of lithium an- ode battery structure, it is characterised in that: preparation method include physical vaporous deposition,
Chemical vapour deposition technique, 3D printing method, slot coated method, scraper for coating method or micro-gravure coating process.
7. the preparation method of lithium an- ode battery structure as claimed in claim 6, it is characterised in that: preparation method specifically walks
It is rapid as follows:
The preparation of anode structure；
Solid polyelectrolyte layer is formed on anode structure；
Cathode decorative layer is formed on solid polyelectrolyte layer；
Negative film layer is formed on cathode decorative layer；
Negative current collector is formed on negative film layer obtains battery structure.
8. the preparation method of lithium an- ode battery structure as claimed in claim 7, it is characterised in that: the shape on anode structure
Specific method at solid polyelectrolyte layer is to coat a layers of polymer on anode structure by way of blade coating
Then object solid electrolyte slurry realizes in-situ polycondensation reaction by baking, forms solid polyelectrolyte layer.
9. the preparation method of lithium an- ode battery structure as claimed in claim 7, it is characterised in that: in polymer solid electricity
The method that cathode decorative layer is formed on solution matter layer is specially magnetron sputtering method, and magnetron sputtering method is in physical vaporous deposition
It is a kind of, the specific steps are as follows:
It provides one and is formed with the anode structure of solid polyelectrolyte layer as bottom liner；
The installation of cathode decorative layer target；
Back end vacuum pressure is extracted into lower than 5.0 × 10-4Pa；
Heating bottom liner temperature: 25-300 DEG C.
Adjusting air pressure is 0.5-1.5Pa, sputtering power are as follows: 60-120W, sputtering time are as follows: 10-60min is passed through argon gas and is splashed
It penetrates.
10. the preparation method of lithium an- ode battery structure as claimed in claim 9, it is characterised in that: air pressure is preferably
0.2Pa, sputtering atmosphere are argon gas, and sputtering power is preferably 70W, obtain being formed in the cathode on solid polyelectrolyte layer
The thickness of decorative layer are as follows: 60nm.
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| CN110571413A (en) * | 2019-07-31 | 2019-12-13 | 珠海冠宇电池有限公司 | Electrode and lithium cell with composite bed structure |
| CN111725561A (en) * | 2020-07-31 | 2020-09-29 | 南方科技大学 | Solid electrolyte, preparation method thereof and all-solid-state battery |
| CN111952598A (en) * | 2020-07-03 | 2020-11-17 | 南方科技大学 | Negative plate, preparation method thereof and secondary battery |
| CN112151857A (en) * | 2020-09-03 | 2020-12-29 | 浙江锋锂新能源科技有限公司 | High-stability multilayer solid electrolyte, preparation method thereof and solid battery |
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| CN115605436A (en) * | 2020-04-29 | 2023-01-13 | 索尔维公司（Be） | Fluorination of LLZO garnets |
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| CN110504491A (en) * | 2019-08-28 | 2019-11-26 | 中南大学 | Method for modifying all-solid-state lithium battery by modified succinonitrile |
| WO2021213413A1 (en) * | 2020-04-21 | 2021-10-28 | 华为技术有限公司 | Metal negative electrode, preparation method therefor, and secondary battery |
| CN115605436A (en) * | 2020-04-29 | 2023-01-13 | 索尔维公司（Be） | Fluorination of LLZO garnets |
| CN111952598B (en) * | 2020-07-03 | 2021-06-04 | 南方科技大学 | Negative plate, preparation method thereof and secondary battery |
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| CN112151857A (en) * | 2020-09-03 | 2020-12-29 | 浙江锋锂新能源科技有限公司 | High-stability multilayer solid electrolyte, preparation method thereof and solid battery |
| CN112151857B (en) * | 2020-09-03 | 2021-11-19 | 浙江锋锂新能源科技有限公司 | High-stability multilayer solid electrolyte, preparation method thereof and solid battery |
| CN112736282A (en) * | 2020-12-26 | 2021-04-30 | 维达力实业(深圳)有限公司 | Solid electrolyte, solid battery manufacturing equipment and preparation method |
| CN113764722A (en) * | 2021-07-30 | 2021-12-07 | 清华大学 | Solid electrolyte interface film and preparation method thereof |
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