CN108110217A - A kind of solid state lithium battery composite negative pole and preparation method thereof - Google Patents
A kind of solid state lithium battery composite negative pole and preparation method thereof Download PDFInfo
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- H01M4/00—Electrodes
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Abstract
The present invention relates to technical field of lithium batteries more particularly to a kind of solid state lithium battery composite negative pole and preparation method thereof.A kind of solid state lithium battery composite negative pole, including solid electrolyte film layer and cathode of lithium layer, the cathode of lithium layer includes lithium an- ode material, and the lithium an- ode material is incorporated in formation cathode of lithium layer on the solid electrolyte film layer with molten condition.Lithium an- ode material, which is incorporated in molten condition on the solid electrolyte film layer, to be formed cathode of lithium layer and can improve wetting property between cathode of lithium layer and solid electrolyte film layer very well, inhibit the formation of Li dendrite well, improve the lithium battery security performance for including the negative pole structure；Reduce the interface impedance between cathode of lithium layer and solid electrolyte film layer well simultaneously, improve migration rate of the conductive ion between cathode of lithium layer and solid electrolyte film layer, improve the conductive capability of cathode of lithium layer.
Description
【Technical field】
The present invention relates to technical field of lithium batteries more particularly to a kind of solid state lithium battery composite negative pole and preparation method thereof.
【Background technology】
Before lithium metal battery realizes commercialization, need to overcome security and stable circulation for lithium anode structure
There are larger challenges for property etc..Referring to Fig. 1, wellability between solid-state electrolyte layer 1011 and lithium anode layer 1021
Poor, lithium ion deposition is uneven in cyclic process, and Li dendrite is easily generated during charge and discharge cycles, causes battery short
Road, there are serious security risks；The contact between solid-state electrolyte layer 1011 and lithium anode layer 1021 can form resistance simultaneously
Anti- very high boundary layer, so as to restrict the migration back and forth of lithium ion in the battery.Current obtained All-solid film batteries are more
It is the structure of lamination, interfacial contact impedance is very big, while cycle performance is very poor.Need how further research improves boundary layer
Impedance and infiltration problem, the wellability improved between solid-state electrolyte layer 1011 and lithium anode layer 1021 could realize metal
The breakthrough of lithium battery security and high electric conductivity.
【The content of the invention】
To overcome the problems, such as that current lithium battery structure security is not high and poorly conductive, the present invention provide a kind of solid state electrolysis
Matter layer and lithium anode effect of impregnation are good, high solid state lithium battery composite negative pole of conductivity and preparation method thereof.
In order to solve the above-mentioned technical problem the present invention, provides a technical solution：A kind of solid state lithium battery composite negative pole, including
Solid electrolyte film layer and cathode of lithium layer, the cathode of lithium layer include lithium an- ode material, the lithium an- ode material
Formation cathode of lithium layer on the solid electrolyte film layer is incorporated in molten condition.
Preferably, buffer layer is also formed on the solid electrolyte film layer, the buffer layer is located at solid state electrolysis
Between matter film layer and cathode of lithium layer, the buffer layer includes the oxide, polymer or gel electrolyte buffering of close lithium
Layer material.
Preferably, the one side of the cathode of lithium layer away from solid electrolyte film layer is formed with current collector layers.
In order to solve the above-mentioned technical problem the present invention, provides another technical solution：It is a kind of to prepare solid state lithium battery Compound Negative
The method of pole：The electrolyte is synthesized using solid-phase synthesis, then a substrate is provided, using magnetron sputtering method by described in
Electrolyte sputtering obtains solid electrolyte film layer on the substrate, then makes lithium an- ode material with molten condition
It is incorporated in formation cathode of lithium layer on the solid electrolyte film layer.
Preferably, lithium metal is deposited on formation cathode of lithium layer on the solid electrolyte film layer using PVD technique,
The PVD technique is included using solid electrolyte film layer as substrate, which is heated to 80-
170 DEG C, lithium an- ode material as steaming, by the lithium an- ode material be deposited on the solid electrolyte film layer it
On, form cathode of lithium layer.
Preferably, using solid electrolyte film layer as substrate, PVD technique deposit lithium metal negative material, lithium gold are utilized
Belong to and the solid electrolyte film layer that the deposition has lithium an- ode material is heated to 80-170 DEG C after negative material deposits
So that lithium an- ode material molten forms cathode of lithium layer on the solid electrolyte film layer.
Preferably, using solid electrolyte film layer as substrate, lithium an- ode material is first heated, it is in molten to make it
Then the lithium an- ode material of the molten condition is coated on the solid electrolyte film layer by state, then by described in
The temperature of solid electrolyte film layer is heated to 80-170 DEG C so that the infiltration of liquid lithium metal negative material is in solid-state electricity
It solves and cathode of lithium layer is formed on matter film layer.
Preferably, using solid electrolyte film layer as substrate, lithium an- ode material hot pressing is formed in the solid-state
On electrolyte thin film layer, hot pressing temperature is 80-170 DEG C, forms cathode of lithium layer.
Preferably, using solid electrolyte film layer as substrate, using PVD technique the solid electrolyte film layer it
Upper formation buffer layer.
Preferably, one side of the cathode of lithium layer away from electrolyte thin film layer forms a negative current collector layer.
Compared with the prior art, the cathode of lithium layer includes lithium an- ode material, and the lithium an- ode material is with molten
Melt combinations of states and form cathode of lithium on the solid electrolyte film layer.Lithium an- ode material is incorporated in molten condition
On the solid electrolyte film layer, lithium an- ode material is in melt-flow state so that lithium an- ode material is very
Between the good electrolyte molecule for being formed in solid electrolyte film layer surface and being entrenched in solid electrolyte film layer
Gap enhances the wellability between the cathode of lithium layer of solid electrolyte film layer so that in the mistake of charge and discharge cycles well
Cheng Zhong, conductive lithium ion are more uniformly deposited on the cathode of lithium layer, are limited in lithium during charge and discharge cycles well
The formation of dendrite is assembled into battery and carries out charge-discharge test, apparent lithium is not formed after carrying out the loop test of 100 times or more
Dendrite improves well since the formation of Li dendrite causes battery short circuit.
Further, lithium an- ode material is incorporated in molten condition on the solid electrolyte film layer, enhancing
Wellability between solid electrolyte film layer and cathode of lithium layer can reduce solid electrolyte film layer and cathode of lithium layer well
Between interface impedance.Interface impedance between solid electrolyte film layer and cathode of lithium layer is in tens Europe to hundreds of Europe quantity
Grade.Enhance migration rate of the conductive ion between solid electrolyte film layer and cathode of lithium layer, and then enhance the cathode of lithium layer
Electric conductivity.
Further, buffer layer is also formed on the solid electrolyte film layer, the buffer layer is located at solid-state
Between electrolyte thin film layer and cathode of lithium layer, the buffer layer includes oxide, polymer or the gel electrolyte of close lithium
Cushioning layer material.The padded coaming of close lithium causes lithium an- ode material preferably to fit in the solid electrolyte film
Layer further improves the effect of impregnation of lithium an- ode material and solid electrolyte film layer, is assembled into battery and carries out charge and discharge
Electrical testing does not form apparent Li dendrite after carrying out the loop test of 150 times or more, the formation of Li dendrite is avoided to cause short circuit
The phenomenon that.Preferably reduce the interface impedance between cathode of lithium layer and solid electrolyte film layer, solid electrolyte film layer and
Interface impedance between cathode of lithium layer is in more than ten Europe to the tens Europe orders of magnitude.Enhance conductive ion in solid electrolyte film layer and
Migration rate between cathode of lithium layer, and then enhance the electric conductivity of the cathode of lithium layer.
【Description of the drawings】
Fig. 1 is effect of impregnation structure diagram between solid-state electrolyte layer and lithium an- ode layer in background technology；
Fig. 2 is effect of impregnation structure diagram between solid electrolyte film layer and lithium an- ode layer in the present invention；
Fig. 3 is the flow chart that solid electrolyte film layer is formed in the present invention；
Fig. 4 is lithium an- ode layer and the flow chart of the B1 modes of solid electrolyte film layer melt binding in the present invention；
Fig. 5 is lithium an- ode layer and the flow chart of the B2 modes of solid electrolyte film layer melt binding in the present invention；
Fig. 6 is lithium an- ode layer and the flow chart of the B3 modes of solid electrolyte film layer melt binding in the present invention；
Fig. 7 is lithium an- ode layer and the flow chart of the B4 modes of solid electrolyte film layer melt binding in the present invention；
Fig. 8 is the cooperation schematic diagram between negative current collector layer and lithium an- ode layer in the present invention；
Fig. 9 is the structure diagram for being formed with buffer layer in the present invention on solid electrolyte film layer.
【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. 2, first embodiment, a kind of solid state lithium battery composite negative pole 10, including solid electrolyte film layer 101
With cathode of lithium layer 102, the cathode of lithium layer 102 includes lithium an- ode material, and the lithium an- ode material is with molten condition
It is incorporated on the solid electrolyte film layer 101 and forms cathode of lithium layer 102, the solid electrolyte film layer 101 includes
Electrolyte.The electrolyte includes the Li of garnet structure7La3Zr5O12Or the Li7La3Zr5O12Doping change
Property substance, the Li7La3Zr5O12Doping vario-property element can be any one of Ca, Nb, Ta.
A kind of preparation method of solid state lithium battery composite negative pole synthesizes the electrolysis material first with solid-phase synthesis
Material, then provides a substrate, and electrolyte sputtering is obtained solid state electrolysis on the substrate using magnetron sputtering method
Then matter film layer 101 makes lithium an- ode material be incorporated in shape on the solid electrolyte film layer 101 with molten condition
Into cathode of lithium layer 102.
Referring to Fig. 3, described above sputtered the electrolyte using magnetron sputtering method is obtained on the substrate
The step of to solid electrolyte film layer 101, is specific as follows, with Li in the present invention7La3Zr5O12It is lifted as electrolyte
Example explanation：
A1：A substrate is provided in substrate frame；
A2：The installation of electrolyte target；
A3：Vacuum is extracted into 5 X 10-4Below Pa；
A4：Heating substrate frame makes the temperature of substrate be approximately at 50-400 DEG C；
A5：Adjust that air pressure is 0.5-1.5Pa, the ratio of argon gas and oxygen is 7:3-9:1st, sputtering power for 80-120W into
Row sputtering.
Substrate used in above-mentioned steps A1 is any in quartz or slide.
Above-mentioned steps A5 sputtering times are 0.5-1.0h, obtain being formed in the solid electrolyte film layer on the substrate
101, the thickness of the solid electrolyte film layer 101 is 5-40nm.
After obtaining solid electrolyte film layer 101 by magnetron sputtering method, make lithium an- ode material with molten condition
Being incorporated in the concrete mode of formation cathode of lithium layer 102 on the solid electrolyte film layer 101 includes B1, B2, B3 and B4.
B1：Lithium an- ode material is deposited on the solid electrolyte film layer 101 using PVD technique and forms lithium
Negative electrode layer 102, the PVD technique is included using solid electrolyte film layer 101 as substrate, by the solid electrolyte film layer
101 substrates are heated to 80-170 DEG C, which is deposited on the solid-state by lithium an- ode material as steaming
On electrolyte thin film layer 101, cathode of lithium layer 102 is formed.
Referring to Fig. 4, mode B1 described above is comprised the following specific steps that：
B11：101 substrate of solid electrolyte film layer is placed in base station；
B12：It is 99.9% by purity, metal lithium sheet of the thickness more than 3mm is put into tantalum crucible (or molybdenum crucible, tungsten crucible)
In；
B13：It is 10 to adjust cavity air pressure-6Torr, and ensure that cavity oxygen content is less than 0.01ppm, moisture is less than
0.01ppm；
B14：Base station is heated, the temperature for maintaining solid electrolyte film layer 101 is 80-170 DEG C；
B15：Adjusting deposition power is 50-130W, sedimentation time 0.5-1.0h.
In above-mentioned steps B13, before cavity is vacuumized, cycle into cavity through argon gas, the purity of argon gas
For 99.999%, repetitive operation 3 times or more.
In above-mentioned steps B14, base station is heated, the temperature for maintaining solid electrolyte film layer 101 is 80-170
DEG C so that the lithium an- ode material being deposited on the solid electrolyte film layer 101 is in melt-flow state, well
Form cathode of lithium layer 102.Lithium an- ode material is in melt-flow state and lithium an- ode material is formed in well
101 surface of solid electrolyte film layer is simultaneously entrenched between the electrolyte molecule of solid electrolyte film layer 101
Gap enhances the wellability between the cathode of lithium layer 102 of solid electrolyte film layer 101 so that follow in charge and discharge well
During ring, conductive lithium ion is more uniformly deposited on the cathode of lithium layer 102, is limited in charge and discharge cycles well
The formation of Li dendrite in the process improves well since the formation of Li dendrite causes battery short circuit.
Further, lithium an- ode material with melt-flow state be formed in the solid electrolyte film layer 101 it
On, it is thin to reduce solid electrolyte well for the wellability between enhancing solid electrolyte film layer 101 and cathode of lithium layer 102
Interface impedance between film layer 101 and cathode of lithium layer 102.Enhance conductive ion in solid electrolyte film layer 101 and cathode of lithium
Migration rate between layer 102, and then enhance the electric conductivity of the cathode of lithium layer 102.
After obtaining solid electrolyte film layer 101 by magnetron sputtering method, make lithium an- ode material with molten condition
It is incorporated in and the concrete mode B2 of cathode of lithium layer 102 is formed on the solid electrolyte film layer 101 is：It is thin with solid electrolyte
Film layer 101 is used as substrate, and using PVD technique deposited metal lithium titanate cathode material, lithium anode material sinks this after depositing
The solid electrolyte film layer 101 that product has lithium anode material is heated to 80-170 DEG C so that lithium anode material molten exists
Cathode of lithium layer 102 is formed on the solid electrolyte film layer 101.
It is referring to Fig. 5, specific as follows the step of utilizing PVD technique deposited metal lithium titanate cathode material described in above-mentioned B2：
B21：Solid electrolyte film layer 101 is mounted in base station；
B22：It is 99.9% by purity, metal lithium sheet of the thickness more than 3mm is put into tantalum crucible (or molybdenum crucible, tungsten crucible)
In；
B23：It is 10 to adjust cavity air pressure-6Torr, and ensure that cavity oxygen content is less than 0.01ppm, moisture is less than
0.01ppm；
B24：Adjusting deposition power is 50-130W, sedimentation time 0.5-1.0h.
After above-mentioned steps B24 depositions are completed, by the solid electrolyte film layer 101 of the deposited metal lithium titanate cathode material
It is transferred to during heating is set and is heated, the temperature of solid electrolyte film layer 101 is heated to 80-170 DEG C so that be deposited on
Lithium an- ode material on the solid electrolyte film layer 101 is in molten condition, lithium an- ode material molten knot
It closes on institute's solid electrolyte film layer 101, forms cathode of lithium layer 102.By by the deposited metal lithium titanate cathode material
Solid electrolyte film layer 101 is transferred to during heating is set and is heated, and the temperature of solid electrolyte film layer 101 is heated to
80-170 DEG C so that the lithium an- ode material being deposited on the solid electrolyte film layer 101 is in melt-flow state,
Cathode of lithium layer 102 is formed well.Lithium an- ode material is in melt-flow state can equally improve due to lithium branch well
The problem of brilliant formation causes battery short circuit, while can also reduce solid electrolyte film layer 101 and cathode of lithium layer 102 well
Between interface impedance.Enhance migration rate of the conductive ion between solid electrolyte film layer 101 and cathode of lithium layer 102,
And then enhance the electric conductivity of the cathode of lithium layer 102.
After obtaining solid electrolyte film layer 101 by magnetron sputtering method, make lithium an- ode material with molten condition
It is incorporated in and the concrete mode B3 of cathode of lithium layer 102 is formed on the solid electrolyte film layer 101 is：It is thin with solid electrolyte
Film layer first heats lithium an- ode material, makes it in molten condition, then by the lithium an- ode of the molten condition as substrate
Then the temperature of the solid electrolyte film layer 101 is heated to by material coated on the solid electrolyte film layer
80-170 DEG C so that the lithium an- ode material infiltration of melting forms cathode of lithium on the solid electrolyte film layer 101
Layer 102.
Referring to Fig. 6, aforesaid way B3 is comprised the following specific steps that：
B31：Solid electrolyte film layer 101 is transferred in melt coating equipment；
B32：Solid electrolyte film layer 101 is heated to 80-170 DEG C；
B33：It is 99.9% by purity, metal lithium sheet of the thickness more than 3mm is placed on coating warm table, and heating temperature is
80-170 DEG C so that lithium an- ode material is in molten condition；
B34：It is 10 to adjust cavity air pressure-6Torr, and ensure that cavity oxygen content is less than 0.01ppm, moisture is less than
0.01ppm；
B35：It is 80-170 DEG C of solid electrolyte film that molten metal lithium titanate cathode material is coated on temperature in the B32
On layer 101.
In above-mentioned steps B32, solid electrolyte film layer 101 is heated to 80-170 DEG C, can maintain to be coated on well
The molten condition of lithium an- ode material on solid electrolyte film layer 101 so that the dimension of lithium an- ode material longer time
Melt-flow state is held, preferably enhances the wellability between the cathode of lithium layer 102 of solid electrolyte film layer 101 so that
During charge and discharge cycles, conductive lithium ion deposition ground is evenly changed, and avoids the lithium branch during charge and discharge cycles well
Brilliant formation, causes battery short circuit.Further, lithium metal is formed in the solid electrolyte film layer with melt-flow state
On 101, the wetting property between the cathode of lithium layer 102 of enhancing solid electrolyte film layer 101 reduces enhancing solid-state well
Interface impedance between the cathode of lithium layer 102 of electrolyte thin film layer 101.Enhance conductive ion in solid electrolyte film layer 101
Migration rate between cathode of lithium layer 102, and then enhance the electric conductivity of the conductive cathode of lithium layer 102.Pass through coating simultaneously
Mode lithium an- ode material is coated on the solid electrolyte film layer 101, improve coating efficiency well.
After obtaining solid electrolyte film layer 101 by magnetron sputtering method, make lithium an- ode material with molten condition
It is incorporated in and the concrete mode B4 of cathode of lithium layer 102 is formed on the solid electrolyte film layer 101 is：It is thin with solid electrolyte
Film layer 101 is used as substrate, lithium metal material hot pressing is formed on the solid electrolyte film layer 101, hot pressing temperature is
80-170 DEG C, form cathode of lithium layer 102.
Referring to Fig. 7, aforesaid way B4 is as follows：
B41：101 substrate of solid electrolyte film layer is transferred in hot-press equipment；
B42：The ultra-thin lithium paper tinsel that purity is 99.9% is placed on hot-platen；
B43：It is 10 to adjust cavity air pressure-6Torr, and ensure that cavity oxygen content is less than 0.01ppm, moisture is less than
0.01ppm；
B44：101 base reservoir temperature of heating solid electrolyte film layer reaches 80 DEG C -170 DEG C；
B45：By purity be 99.9% ultra-thin lithium paper tinsel close to 101 surface of solid electrolyte film layer, be by purity
99.9% ultra-thin lithium paper tinsel material hot pressing forms cathode of lithium layer 102 on the solid electrolyte film layer 101.
In above-mentioned steps, the temperature of solid electrolyte film layer 101 is heated to 80 DEG C -170 DEG C, by lithium an- ode material
Material is and thin in the solid electrolyte by the metal negative electrode material hot pressing close to 101 surface of solid electrolyte film layer
On film layer 101, in hot pressing so that be deposited on the metal negative electrode material on the solid electrolyte film layer 101 and be in
Molten condition, molten lithium metal have good mobility so that lithium metal is entrenched in solid electrolyte film layer 101 well
Electrolyte molecule between gap, enhance well between solid electrolyte film layer 101 and cathode of lithium layer 102
Wellability so that during charge and discharge cycles, conductive lithium ion deposition ground is evenly changed, and avoids following in charge and discharge well
The formation of Li dendrite, causes battery short circuit during ring.
Further, in hot pressing, purity be 99.9% ultra-thin lithium paper tinsel be formed in melt-flow state it is described solid
On state electrolyte thin film layer 101, the wetting property between enhancing solid electrolyte film layer 101 and cathode of lithium layer 102 is fine
Reduction enhancing solid electrolyte film layer 101 and cathode of lithium layer 102 between interface impedance.Enhance conductive ion in solid-state electricity
The migration rate between matter film layer 101 and cathode of lithium layer 102 is solved, and then enhances the electric conductivity of the conductive cathode of lithium layer 102.
Referring to Fig. 8, the one side away from solid electrolyte film 101 is formed with cathode collection on the cathode of lithium layer 102
Fluid layer 104, negative current collector layer 104 include negative current collector material, and the negative current collector material is metallic copper, silver or molybdenum
In one kind.It is substrate with cathode of lithium layer 102, negative current collector material is deposited on the cathode of lithium layer 102 using PVD technique
One side away from electrolytic thin-membrane 101 forms negative current collector layer 104.
Preferably, the negative current collector layer 104 includes carbon-based current collector material, and the carbon-based current collector material is bonded
On the one side of the cathode of lithium layer 102 away from solid electrolyte film layer 101, then by the lithium by way of hot pressing
The melting of negative electrode layer 102 is fitted in negative current collector layer 104, and hot pressing temperature is 80-170 DEG C.The preparation of carbon-based current collector material
Mode is：By carbon nanotubes or graphene dispersion in a solvent, by filtering thin film-forming method, obtain that there is the carbon-based of supporting role
Current collector material.
In the present embodiment, 102 melt binding of cathode of lithium layer is on the solid electrolyte film layer 101, solid-state electricity
The interface impedance between matter film layer 101 and cathode of lithium layer 102 is solved in tens Europe to the hundreds of Europe orders of magnitude.It is assembled into battery progress
Charge-discharge test does not form apparent Li dendrite after carrying out the loop test of 100 times or more.
Second embodiment, referring to Fig. 9, a kind of solid state lithium battery composite negative pole 20, including solid electrolyte film layer 101
With cathode of lithium layer 102, the cathode of lithium layer 102 and the solid electrolyte film layer 101 melting cooperation, the solid electrolyte
Film layer 101 includes electrolyte.Buffer layer 103, the buffering are also formed on the solid electrolyte film layer 101
For layer 103 between solid electrolyte film layer 101 and cathode of lithium layer 102, the buffer layer 103 includes the oxidation of close lithium
Object, polymer or gel electrolyte cushioning layer material.
The generation type of solid electrolyte film layer 101 in present embodiment is identical with first embodiment, and includes
With same electrolyte in first embodiment.
Please continue to refer to Fig. 9, using solid electrolyte film layer 101 as substrate, using PVD technique by the buffer structure
Layer material is deposited on formation buffer layer 103 on the solid electrolyte film layer 101.
In the present embodiment, the lithium an- ode material is with being formed in the solid electrolyte in first embodiment
102 same mode of cathode of lithium layer is obtained in film layer 101, is formed on the buffer layer 103 and obtains cathode of lithium layer 102.
The buffer layer 103 includes oxide, polymer or the gel electrolyte cushioning layer material of close lithium so that lithium
Metal negative electrode material preferably fits in the solid electrolyte film layer 101, improves solid electrolyte film layer 101 and lithium is born
The wellability of pole layer 102 further reduces the interface impedance of solid electrolyte film layer 101 and cathode of lithium layer 102.
Please continue to refer to Fig. 9, negative current collector layer 104, negative current collector layer are formed on the cathode of lithium layer 102
104 include negative current collector material, and the negative current collector material is one kind in metallic copper, silver or molybdenum.With cathode of lithium layer 102
For substrate, negative current collector material is deposited on one of the cathode of lithium layer 102 away from electrolytic thin-membrane 101 using PVD technique
Side forms negative current collector layer 104.
Preferably, the negative current collector layer 104 includes carbon-based current collector material, and the carbon-based current collector material is bonded
On the one side of the cathode of lithium layer 102 away from solid electrolyte film layer 101, then by the lithium by way of hot pressing
The melting of negative electrode layer 102 is fitted in negative current collector layer 104, and hot pressing temperature is 80-170 DEG C.The preparation of carbon-based current collector material
Mode is：By carbon nanotubes or graphene dispersion in a solvent, by filtering thin film-forming method, obtain that there is the carbon-based of supporting role
Current collector material.
In the present embodiment, it is formed between the solid electrolyte film layer 101 of buffer layer 103 and cathode of lithium layer 102
Interface impedance is in more than ten Europe to the tens Europe orders of magnitude.
In the present embodiment, the solid state lithium battery composite negative pole for being formed with buffer layer 103 is assembled into battery and carries out charge and discharge
Electrical testing does not form apparent Li dendrite after carrying out the loop test of 150 times or more.
Compared with the prior art, the cathode of lithium layer includes lithium an- ode material, and the lithium an- ode material is with molten
Melt combinations of states and form cathode of lithium on the solid electrolyte film layer.Lithium an- ode material is incorporated in molten condition
On the solid electrolyte film layer, lithium an- ode material is in melt-flow state so that lithium an- ode material is very
It is thin to enhance solid electrolyte well for the good gap being entrenched between the electrolyte molecule of solid electrolyte film layer
Wellability between the cathode of lithium layer of film layer so that during charge and discharge cycles, conductive lithium ion is more uniformly deposited on
On the cathode of lithium layer, the formation of Li dendrite during charge and discharge cycles is limited in well, is improved well due to lithium branch
Brilliant formation causes battery short circuit.
Further, lithium an- ode material is incorporated in molten condition on the solid electrolyte film layer, enhancing
Wellability between solid electrolyte film layer and cathode of lithium layer can reduce solid electrolyte film layer and cathode of lithium layer well
Between interface impedance.Enhance migration rate of the conductive ion between solid electrolyte film layer and cathode of lithium layer, Jin Erzeng
The electric conductivity of the strong cathode of lithium layer.
Further, buffer layer is also formed on the solid electrolyte film layer, the buffer layer is located at solid-state
Between electrolyte thin film layer and cathode of lithium layer, the buffer layer includes oxide, polymer or the gel electrolyte of close lithium
Cushioning layer material.The padded coaming of close lithium causes lithium an- ode material preferably to fit in the solid electrolyte film
Layer, further improves the effect of impregnation of lithium an- ode material and solid electrolyte film layer, preferably avoids Li dendrite
The interface impedance preferably reduced between cathode of lithium layer and solid electrolyte film layer is formed, enhancing conductive ion is in solid state electrolysis
Conductive performance between matter film layer and cathode of lithium layer.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all originals in the present invention
Any modification made within then, equivalent substitution and improvement etc. should all be included within protection scope of the present invention.
Claims (10)
1. a kind of solid state lithium battery composite negative pole, it is characterised in that：Including solid electrolyte film layer and cathode of lithium layer, the lithium
Negative electrode layer includes lithium an- ode material, and the lithium an- ode material is incorporated in the solid electrolyte film with molten condition
Cathode of lithium layer is formed on layer.
2. solid state lithium battery composite negative pole as described in claim 1, it is characterised in that：On the solid electrolyte film layer
Buffer layer is also formed with, for the buffer layer between solid electrolyte film layer and cathode of lithium layer, the buffer layer includes parent
Oxide, polymer or the gel electrolyte cushioning layer material of lithium.
3. solid state lithium battery composite negative pole as claimed in claim 1 or 2, it is characterised in that：The cathode of lithium layer is away from solid-state
The one side of electrolyte thin film layer is formed with current collector layers.
A kind of 4. method for preparing solid state lithium battery composite negative pole：It is characterized in that：The electrolysis is synthesized using solid-phase synthesis
Then material provides a substrate, electrolyte sputtering is obtained solid-state on the substrate using magnetron sputtering method
Then electrolyte thin film layer is made lithium an- ode material be incorporated in molten condition on the solid electrolyte film layer and is formed
Cathode of lithium layer.
5. the method as claimed in claim 4 for preparing solid state lithium battery composite negative pole, it is characterised in that：It will using PVD technique
Lithium metal is deposited on formation cathode of lithium layer on the solid electrolyte film layer, and the PVD technique is included with solid electrolyte
Film layer is heated to 80-170 DEG C as substrate, by the solid electrolyte film layer substrate, lithium an- ode material as steaming,
The lithium an- ode material is deposited on the solid electrolyte film layer, forms cathode of lithium layer.
6. the method as claimed in claim 4 for preparing solid state lithium battery composite negative pole, it is characterised in that：It is thin with solid electrolyte
Film layer is as substrate, and using PVD technique deposit lithium metal negative material, lithium an- ode material has the deposition after depositing
The solid electrolyte film layer of lithium an- ode material is heated to 80-170 DEG C and causes lithium an- ode material molten described solid
Cathode of lithium layer is formed on state electrolyte thin film layer.
7. the method as claimed in claim 4 for preparing solid state lithium battery composite negative pole, it is characterised in that：It is thin with solid electrolyte
Film layer first heats lithium an- ode material, makes it in molten condition, then by the lithium an- ode of the molten condition as substrate
Then the temperature of the solid electrolyte film layer is heated to 80- by material coated on the solid electrolyte film layer
170 DEG C so that the infiltration of liquid lithium metal negative material forms cathode of lithium layer on the solid electrolyte film layer.
8. the method as claimed in claim 4 for preparing solid state lithium battery composite negative pole, it is characterised in that：It is thin with solid electrolyte
Lithium an- ode material hot pressing is formed on the solid electrolyte film layer, hot pressing temperature 80- by film layer as substrate
170 DEG C, form cathode of lithium layer.
9. the method for preparing solid state lithium battery composite negative pole as any one of claim 4-8, it is characterised in that：With solid
State electrolyte thin film layer forms buffer layer using PVD technique as substrate on the solid electrolyte film layer.
10. the method as claimed in claim 9 for preparing solid state lithium battery composite negative pole, it is characterised in that：Cathode of lithium layer is separate
The one side of electrolyte thin film layer forms a negative current collector layer.
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