CN106099197B - All solid state metal ion battery and preparation method thereof, electric vehicle - Google Patents
All solid state metal ion battery and preparation method thereof, electric vehicle Download PDFInfo
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- CN106099197B CN106099197B CN201610542873.4A CN201610542873A CN106099197B CN 106099197 B CN106099197 B CN 106099197B CN 201610542873 A CN201610542873 A CN 201610542873A CN 106099197 B CN106099197 B CN 106099197B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to a kind of preparation methods of all solid state metal ion battery, comprising the following steps: provides a substrate；At least two hierarchical elements are formed on substrate, the hierarchical element includes anode thin film, negative film and the inorganic solid electrolyte film being arranged between anode thin film and negative film；It is superimposed the hierarchical element.The invention further relates to a kind of all solid state metal ion battery of hierarchical element being superimposed on substrate including at least two and a kind of electric vehicles using above-mentioned all solid state metal ion battery.Have the characteristics that nontoxicity, high security, high energy storage density, battery capacity are big, charge/discharge capacity conservation rate is high using battery prepared by the preparation method of all solid state metal ion battery.
Description
[technical field]
The present invention relates to technical field of energy storage more particularly to a kind of all solid state metal ion battery and preparation method thereof, electricity
Motor-car.
[background technique]
Electric energy is the most universal also most application form of promotion prospect of clean energy resource.Energy storage technology is energy resource structure by passing
The key link that the fossil energy of system adjusts and changes to clean energy resourcies such as wind energy, solar energy.In numerous electric energy memory technologies
In, it is to have both technical maturity and advanced preferred electric power storage skill at present using lithium ion battery as the metal ion battery of representative
Art.
The growth requirement of metal ion battery technology be high safety, high-energy density, high power density, long circulation life,
Low cost.Wherein, improving safety is the primary of the application forms such as current power battery of electric vehicle, familial distribution of cases formula energy-storage system
Demand.Electrolyte solid state is that most potential at present and value lithium ion battery security improves means.
The all-solid-state battery product of the solid polyelectrolyte exploitation prepared at present is launched in a small amount, capacity density
130-220Wh/kg.However, the thermal stability and electrochemical stability of organic polymer solid electrolyte are often unable to satisfy
The demand of complex working condition.
Inorganic solid electrolyte material technology is limited to inorganic material thick film coating critical process, it is difficult to support large capacity complete
The scale application of solid metallic ion battery.Currently based on all-solid lithium-ion battery technical research, laboratory sample energy
Density is 200Wh/kg, 60 DEG C at a temperature of, implement 300 0.1C charging and 0.5C discharge cycles after, battery discharge
Capacity retention ratio is 80%.Although similar hull cell and the integrated preparation of microelectronic component, can solve part microelectronic component
Energy supply problem, but its capacity is limited to the size of battery device, and therefore, it is difficult to meet power battery of electric vehicle, familial distribution of cases formula
The application demands such as energy-storage system.
[summary of the invention]
To overcome the small technical problem of existing battery capacity, the present invention provides a kind of all solid state metal ion battery and its preparation
Method, electric vehicle.
The technical solution that the present invention solves technical problem is to provide a kind of preparation method of all solid state metal ion battery, packet
Step S1 is included, a substrate is provided；Step S2, forms at least two hierarchical elements on substrate, and the hierarchical element includes anode
Film, negative film and the inorganic solid electrolyte film being arranged between anode thin film and negative film；Wherein it is provided to
Simultaneously corresponding target is arranged in few three target positions on target position, and setting power supply is DC power supply, the gas of vacuum vapor deposition
Pressure is 0.35-0.6Pa, and keeping substrate temperature is 10-30 DEG C, and anode collection body thin film is formed on substrate；Power supply is set
For radio-frequency power supply, the air pressure of vacuum vapor deposition is 2-3Pa, and temperature is 600-800 DEG C, on anode collection body thin film successively
Form anode thin film, inorganic solid electrolyte film；Setting power supply is DC power supply, adjusts the air pressure of vacuum vapor deposition
For 0.2-3Pa, temperature is 10-30 DEG C, deposits shape far from the one side of the anode thin film in the inorganic solid electrolyte film
At negative film；Setting power supply is radio-frequency power supply, and the air pressure for adjusting vacuum vapor deposition is 0.2-3Pa, temperature 10-30
DEG C, it deposits to form negative pole currect collecting body thin film in the one side of negative film；Setting power supply is radio-frequency power supply, adjusts vacuum gas-phase
The air pressure of deposition is 1.6-1.8Pa, and temperature is 300-500 DEG C；And step S3, it is superimposed the hierarchical element.
Preferably, when all solid state metal ion battery is lithium ion battery, anode collection body thin film, just very thin is prepared
Film, inorganic solid electrolyte film, negative film and negative pole currect collecting body thin film target be respectively as follows: aluminium simple substance target, ferric phosphate
Lithium compound target, Li7Y3Nb2O12Solid electrolyte compound target, lithium simple substance target and copper simple substance target；Or molybdenum simple substance target
Material, nickel cobalt manganese compound target, Li-La-Ti-O solid electrolyte compound target, lithium simple substance target and copper simple substance target.
Preferably, when all solid state metal ion battery is sodium-ion battery, the inorganic solid electrolyte target packet
Include Na-Mn-O solid electrolyte, Na-Co-O solid electrolyte, Na-Fe-P-O olivine structural solid electrolyte, Na-P-O-F
One or more of mixture in solid electrolyte.
Preferably, when all solid state metal ion battery used is lithium ion battery, the inorganic solid electrolyte target packet
Include Li-Ge-P-S solid electrolyte, Li7La3Ta2O13Solid electrolyte, LiGePO4Solid electrolyte, Li-La-Ti-O
It is any in quaternary system solid electrolyte or anti-perovskite structure solid electrolyte.
Preferably, the barrier layer target is titanium nitride or silicon nitride.
Preferably, the positive target include cobalt acid lithium, it is LiMn2O4, LiFePO4, nickel cobalt manganese, a kind of or several in nickel cobalt aluminium
The mixture of kind.
Preferably, the anode collection body thin film, anode thin film, inorganic solid electrolyte film, negative film, cathode collection
Fluid film and barrier film with a thickness of 10 nanometers to 2 microns；The hierarchical element number is more than or equal to 2.
The technical solution that the present invention solves technical problem is to provide a kind of all solid state metal ion battery, including at least two
The hierarchical element being superimposed on substrate；The hierarchical element include anode thin film, negative film and setting anode thin film with
Inorganic solid electrolyte film between negative film, all solid state metal ion battery is using in the claims 1-7
The preparation method of described in any item all solid state metal ion batteries and prepare.
The technical solution that the present invention solves technical problem is to provide a kind of electric vehicle with all solid state metal ion battery,
It includes all solid state metal ion battery as described above.
Compared with prior art, a kind of all solid state metal ion battery of the present invention and preparation method thereof, electric vehicle have with
Lower advantage:
(1) preparation method of all solid state metal ion battery provided by the present invention deposits at least two hierarchical elements, institute
Stating hierarchical element includes anode thin film, negative film and inorganic solid electrolyte film, and repeated deposition, forms multiple laminations
Multiple hierarchical elements can be arranged, the energy storage for improving unit volume is close in the case where cell device sizes are limited in unit superposition
Degree solves the problems, such as that microelectronic component energizes to improve the capacity of battery.
(2) hierarchical element includes the first hierarchical element, the second hierarchical element, thus a variety of superposition sides can be set
Formula makes all solid state metal ion battery have wide applicability to increase all solid state metal ion battery variety.
In the case of (3) first hierarchical elements, the second hierarchical element are disposed adjacent, the first hierarchical element and the second hierarchical element
Between an anode collection body thin film or negative pole currect collecting body thin film are set, in the case where cell device sizes are limited, one can be reduced
Hierarchical element occupied space, while more hierarchical elements can be set in one timing of cell device sizes, it further increases complete
Solid metallic ion battery energy storage density, to improve battery capacity.
(4) air pressure and the substrate temperature for adjusting vacuum vapor deposition, can guarantee the uniformity of vacuum vapor deposition film forming.
(5) anode collection body thin film, anode thin film, inorganic solid electrolyte film, negative film, negative pole currect collecting body thin film
The number being superimposed with the thickness and hierarchical element of barrier film, can select according to the capacity of all solid state metal ion battery
With, therefore all solid state metal ion battery of combination that laminate film thickness is different and hierarchical element number is different can be prepared, because
And the size range and battery capacity of all solid state metal ion battery are substantially increased, there is wide applicability.
(6) all solid state metal ion battery being superimposed with the hierarchical element big, charge and discharge with battery capacity are prepared
The high advantage of battery capacity conservation rate.
(7) electric vehicle of all solid state metal ion battery provided by the present invention with hierarchical element superposition, has
Long service life, security performance height, the high feature of charge/discharge capacity conservation rate.
[Detailed description of the invention]
Fig. 1 is the preparation method of all solid state metal ion battery of the present invention using magnetic control sputtering device structural schematic diagram.
Fig. 2 is the detailed schematic of target position in magnetic control sputtering device shown in Fig. 1.
Fig. 3 is the preparation method preparation of all solid state metal ion battery of the first embodiment of first embodiment of the invention
Battery device schematic diagram of laminated structure.
Fig. 4 is the preparation method preparation of all solid state metal ion battery of the second embodiment of first embodiment of the invention
Battery device schematic diagram of laminated structure.
Fig. 5 is that all solid state metal ion battery structure of the preparation method preparation of all solid state metal ion battery of the present invention shows
It is intended to.
[specific embodiment]
In order to make the purpose of the present invention, technical solution and advantage are more clearly understood, below in conjunction with attached drawing and embodiment,
The present invention will be described in further detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention,
It is not intended to limit the present invention.
The present invention prepares all solid state metal ion battery using vacuum vapor disposing technique.Vacuum vapor disposing technique includes
The technologies such as sputtering, evaporation, molecular beam epitaxy, laser pulse, chemical vacuum vapor deposition.Have in the present invention more preferably embodiment
Body can are as follows: magnetron sputtered vacuum gas phase deposition technology.
First embodiment of the invention provides a kind of preparation method of all solid state metal ion battery comprising following step
It is rapid:
Step S1, material prepare；
Step S2, the preparation and superposition of hierarchical element；
And step S3, cell package.
Above-mentioned steps S1 specific step is as follows provide prepare all solid state metal ion battery needed for target: plus plate current-collecting body
Target, positive target, inorganic solid electrolyte target, cathode target, negative current collector target, barrier layer target.
In the present invention, in all solid state metal ion battery, the type of metal ion can include but is not limited to lithium
One or more of metal ion mixing in ion, sodium ion, potassium ion, magnesium ion or aluminium ion etc..Specific all solid state metal
Ion battery can include but is not limited to lithium ion battery, sodium-ion battery, kalium ion battery, Magnesium ion battery or aluminium ion
The metal ion battery of one or more of metal ion mixing in battery etc..Species of metal ion has diversity, therefore expands
The scope of application of all solid state metal ion battery.
The anode target, according to the type of metal ion used, selecting can be real by the insertion and deintercalation of metal ion
The condensed state material of existing power storage.It can be selected but be not limited to cobalt acid lithium, LiMn2O4, LiFePO4, nickel cobalt manganese, nickel cobalt aluminium etc. just
The mixture of one or more of pole material.
The inorganic solid electrolyte target, according to the type of metal ion used, selection can conduct above-mentioned metal from
The inorganic solid-state ion conductor of son.Can be selected but be not limited to following material: transition metal oxide, olivine structural oxide,
One or more of mixture in polyanionic structure compound, quaternary system metal salt etc..
The cathode target, according to the type according to metal ion used, selection can pass through the insertion and deintercalation of metal ion
Realize the condensed state material of power storage.Can be selected but be not limited to following material: carbons negative electrode material, lithium titanate, alloy type are negative
The mixture of one or more of pole material, transition metal oxide negative electrode material etc..
The material selection good insulating of the barrier layer target, the solid-state material without electro-chemical activity.
It is inorganic when all solid state metal ion battery used is lithium ion battery in some preferred embodiments of the present invention
Solid electrolyte target can be selected but be not limited to Li7La3Ta2O13、Li7La3Zr2O13、Li7Y3Nb2O13、LiGePO4、Li-Ge-P-
S, Li-La-Ti-O quaternary system solid electrolyte or anti-perovskite structure solid electrolyte.
In some more preferably embodiments of the present invention, the barrier layer target concretely: titanium nitride, silicon nitride.
It is inorganic when all solid state metal ion battery used is sodium-ion battery in some preferred embodiments of the present invention
Solid electrolyte target can be selected but be not limited to following material: Na-Mn-O solid electrolyte, Na-Co-O solid electrolyte, Na-
Fluorophosphates solid electrolytes such as the olivine structurals such as Mn-Fe-P-O solid electrolyte, Na-P-O-F etc. are one or more of to be mixed
Close object.
It is described when all solid state metal ion battery used is lithium ion battery in some more preferably embodiments of the present invention
Plus plate current-collecting body target, positive target, inorganic solid electrolyte target, cathode target, negative current collector target can specifically be distinguished
Are as follows: aluminium simple substance target, LiFePO4 compound target, Li7Y3Nb2O13Solid electrolyte compound target, lithium simple substance target, copper
Simple substance target；Or molybdenum simple substance target, nickel cobalt manganese compound target, Li-La-Ti-O solid electrolyte compound target, lithium simple substance
Target and copper simple substance target.
The plus plate current-collecting body target, positive target, inorganic solid electrolyte target, cathode target, negative current collector target
Material, barrier layer target can according to need, and be configured to different types of all solid state metal ion battery.
Magnetron sputtering device 1 specifically can be used in the preparation method of all solid state metal ion battery provided by the present invention
The preparation of above-mentioned all solid state metal ion battery is carried out, particular content is as described below.
Referring to FIG. 1, magnetic control sputtering device 1 of the present invention, including supporting mechanism 11, loading mechanism 13, rotating mechanism 15, crystalline substance
Regulating mechanism (not shown) of shaking and vacuum chamber (not shown).Vacuum chamber accommodates supporting mechanism 11, loading mechanism 13, rotating mechanism
15, crystal oscillator regulating mechanism.The setting of 13 parallel support mechanism 11 of loading mechanism.The corresponding supporting mechanism 11 of rotating mechanism 15 is arranged, and
Connect one end of loading mechanism 13.Crystal oscillator regulating mechanism is for monitoring vacuum vapor deposition film forming thickness.
Please also refer to Fig. 2, at least one target position 111 is set on supporting mechanism 11.Setting electric power supplies in target position 111
Answer mechanism 1111, magnetic field generation mechanisms 1113, target 1115.The corresponding target 1115 of magnetic field generation mechanisms 1113 is arranged, and electric power supplies
Mechanism 1111 is answered to connect target 1115.
The magnetic field generation mechanisms 1113 include multiple permanent magnets 1112.
At least one substrate 131 is fixed by the loading mechanism 13.It is thick that crystal oscillator regulating mechanism monitors deposition film on substrate 131
Degree.
Vacuum chamber is closed, vacuum degree is evacuated to higher than 10 to vacuum chamber-4Pa or more is passed through argon gas as protective gas.
Loading mechanism 13 is moved away to the target region that sputtering is completed, is moved to substrate 131 corresponding to next target to be sputtered
At 1115 positions.1111 power of power supply mechanism in 1115 place target area 111 of target to be sputtered is adjusted, and adjusts permanent magnet
1112 distributions and density, continue spatter film forming.It repeats operation, prepares multiple material superposition film.
In the above-mentioned steps S2 of the first specific embodiment of first embodiment of the invention, a substrate 131 is provided, successively
Fixed plus plate current-collecting body target, positive target, inorganic solid electrolyte target, cathode target, negative current collector target are in five
On target position 111.Corresponding to the fixed substrate 131 of plus plate current-collecting body target in loading mechanism 13.131 shape of substrate and big
It is small to be consistent with prepared size of devices.At least two first hierarchical element of vacuum vapor deposition.First hierarchical element includes
The successively anode thin film 102- inorganic solid electrolyte film 103- negative film 104 of lamination.It is specific to obtain the first hierarchical element
The step of it is as follows:
Step T1, vacuum vapor deposition anode collection body thin film 101: setting power supply mechanism 1111 is DC power supply,
Adjust the ignition phase of sputtering voltage to plus plate current-collecting body target.Operating air pressure is adjusted to 0.2-3pa.Substrate 131 is located at this time
Plus plate current-collecting body generated beneath, keeping the temperature of substrate 131 is 10-30 DEG C.Start the vacuum vapor deposition anode on substrate 131
Afflux body thin film 101, when crystal oscillator regulating mechanism measures 101 vacuum vapor deposition of anode collection body thin film with a thickness of 10-2000nm,
Close DC power supply.Loading mechanism 13 is moved away into plus plate current-collecting body target region.
Step T2, vacuum vapor deposition anode thin film 102: setting power supply mechanism 1111 is radio-frequency power supply, and adjusting is splashed
Radio is depressed into the ignition phase of positive target.Operating air pressure is adjusted to 0.2-3pa, loading mechanism 13 is moved under positive target
Side, substrate 131 is corresponding at this time is located at positive generated beneath.Substrate is warming up to 200-800 DEG C, and it is just very thin to start vacuum vapor deposition
Film 102 when crystal oscillator regulating mechanism measures 102 vacuum vapor deposition of anode thin film with a thickness of 10-2000nm, closes radio-frequency power supply.
Loading mechanism 13 is moved away into positive target region.
Step T3, vacuum vapor deposition inorganic solid electrolyte film 103: setting power supply mechanism 1111 is radio frequency electrical
Source adjusts the ignition phase of sputtering voltage to inorganic solid electrolyte target.Operating air pressure is adjusted to 0.2-3pa, by material holder
Structure 13 is moved to inorganic solid electrolyte generated beneath.Keep 200-800 DEG C of 131 temperature of substrate, start vacuum vapor deposition without
Machine solid electrolyte film 103, crystal oscillator regulating mechanism measure 103 vacuum vapor deposition of inorganic solid electrolyte film with a thickness of
When 10-2000nm, radio-frequency power supply is closed.Loading mechanism 13 is moved away into inorganic solid electrolyte target region.
Step T4, vacuum vapor deposition negative film 104: setting power supply mechanism 1111 is DC power supply, and adjusting is splashed
Radio is depressed into the ignition phase of cathode target.Operating air pressure is adjusted to 0.2-3pa, loading mechanism 13 is moved under cathode target
Side, substrate 131 is corresponding at this time is located at cathode generated beneath.Substrate 131 is cooled to 10-30 DEG C, starts vacuum vapor deposition cathode
Film 104 when crystal oscillator regulating mechanism measures 104 vacuum vapor deposition of negative film with a thickness of 10-2000nm, closes direct current
Source.Loading mechanism 13 is moved away into cathode target region.
Step T5, vacuum vapor deposition negative pole currect collecting body thin film 105: setting power supply mechanism 1111 is radio-frequency power supply,
Adjust the ignition phase of sputtering voltage to negative current collector target.Operating air pressure is adjusted to 0.2-3pa, by the movement of loading mechanism 13
To negative current collector generated beneath, substrate 131 is corresponding at this time is located at negative current collector generated beneath.Keep 131 temperature 10- of substrate
30℃.Start vacuum vapor deposition negative pole currect collecting body thin film 105, crystal oscillator regulating mechanism measures 105 vacuum of negative pole currect collecting body thin film
When vapor deposition is with a thickness of 10-2000nm, radio-frequency power supply is closed.Loading mechanism 13 is moved away into negative current collector target area
Domain.
The second specific embodiment in first embodiment of the invention and the first specific embodiment the difference is that:
On five target positions 111 successively fix negative current collector target, cathode target, inorganic solid electrolyte target,
Positive target and plus plate current-collecting body target.Successively vacuum vapor deposition at least one second hierarchical element.Second hierarchical element
Negative film 104- inorganic solid electrolyte film 103- anode thin film 102 including successively lamination.
In the first, second specific embodiment of the invention, the anode collection body thin film 101 is set to anode thin film
102 far from 103 side of inorganic solid electrolyte film, and negative pole currect collecting body thin film 105 is set to negative film 104 far from inorganic solid
103 side of state electrolytic thin-membrane.
Repeat the above-mentioned experimental procedure T1- step T5 of the first specific embodiment of the invention, vacuum vapor deposition at least two
A hierarchical element is superimposed the hierarchical element.The hierarchical element includes the first hierarchical element and the second hierarchical element.
Step T6, vacuum vapor deposition barrier film 106: constant resistance layer target is in 1 target position of magnetic control sputtering device
On 111.Setting power supply mechanism 1111 is radio-frequency power supply, adjusts the ignition phase of sputtering voltage to barrier layer target.Change
Gas componant is containing 20% nitrogen, the mixed gas of 80% nitrogen, and adjusting operating air pressure is 0.2-3pa, by loading mechanism 13
It is moved to barrier layer generated beneath, substrate 131 is corresponding at this time is located at barrier layer generated beneath.Substrate 131 is warming up to 200-800
℃.Start vacuum vapor deposition, crystal oscillator regulating mechanism measures 106 vacuum vapor deposition of barrier film with a thickness of 10-2000nm
When, close radio-frequency power supply.Restore there was only single argon gas protective gas, loading mechanism 13 is moved away into barrier layer target region.
In some preferably embodiments of preparation method of all solid state metal ion battery of the present invention, superposition first can be combined
Hierarchical element, the second hierarchical element.First hierarchical element, the second hierarchical element set-up mode include identical lamination list
Member is disposed adjacent to be disposed adjacent with different hierarchical elements.First hierarchical element, the second hierarchical element can combine superposition, because
And a variety of stacked systems can be set, to increase all solid state metal ion battery variety, have all solid state metal ion battery
There is wide applicability.
In some preferably embodiments of preparation method of all solid state metal ion battery of the present invention, can individually it be superimposed identical
Hierarchical element, the identical hierarchical element is disposed adjacent.
It, can alternately superposition first in some preferably embodiments of preparation method of all solid state metal ion battery of the present invention
Hierarchical element, the second hierarchical element, the difference hierarchical element are disposed adjacent.The multiple first hierarchical element and multiple second
When hierarchical element is alternately superimposed, then the first hierarchical element and the second hierarchical element of adjacent superposition, meet thin in negative current collector
105 two sides of film arrange negative film 104 or arrange anode thin film 102 in 101 two sides of anode collection body thin film.Therefore in electricity
In the case that pool size is limited, space occupied by a hierarchical element can be saved, while settable more in one timing of battery size
More hierarchical elements, thus further improve the energy storage density of the unit volume of all solid state metal ion battery.Therefore
In the case where cell device sizes are limited, battery capacity can be increased, solve the problems, such as that microelectronic component energizes.
Referring to FIG. 3, the first hierarchical element vacuum vapor deposition is in when identical hierarchical element is disposed adjacent
On one hierarchical element, negative pole currect collecting body thin film 105- barrier film 106- anode collection body thin film is set between hierarchical element
101。
When identical hierarchical element is disposed adjacent, the second hierarchical element vacuum vapor deposition is in the second hierarchical element
On, anode collection body thin film 101- barrier film 106- negative pole currect collecting body thin film 105 is set between hierarchical element.
Referring to FIG. 4, the second hierarchical element vacuum vapor deposition is in when different hierarchical elements is disposed adjacent
On one hierarchical element, a negative pole currect collecting body thin film 105 is set between the first hierarchical element and the second hierarchical element.
When different hierarchical elements is disposed adjacent, the first hierarchical element vacuum vapor deposition is in the second hierarchical element
On, an anode collection body thin film 101 is set between the first hierarchical element and the second hierarchical element.
When the first hierarchical element is disposed adjacent with substrate 131, in the anode thin film 102 and base of first hierarchical element
Anode collection body thin film 101 is set between piece 131.
When the second hierarchical element is disposed adjacent with substrate 131, in the negative film 104 and base of second hierarchical element
Negative pole currect collecting body thin film 105 is set between piece 131.
When completing whole hierarchical element superposition preparations, the hierarchical element of last vacuum vapor deposition is the first hierarchical element
When, first hierarchical element negative film 104 far from 131 side vacuum vapor deposition negative pole currect collecting body thin film of substrate
105。
When completing whole hierarchical element superposition preparations, the hierarchical element of last vacuum vapor deposition is the second hierarchical element
When, second hierarchical element anode thin film 102 far from 131 side vacuum vapor deposition anode collection body thin film of substrate
101。
In some preferred embodiments of the first, second specific embodiment of the invention, the step T1, the step
In T4, the step T5, it can form a film in following operating air pressure vacuum vapor deposition: 0.2-0.3pa, 0.3-0.5pa, 0.35-
0.6pa, 0.5-0.6pa, 0.6-1.6pa, 1.6-1.8pa, 1.8-2pa, 2-3pa or 2.5-3pa.It is some more preferably in the present invention
Operating air pressure described in embodiment is concretely: 0.2pa, 0.25pa, 0.3pa, 0.35pa, 0.4pa, 0.45pa, 0.5pa,
0.55pa or 0.6pa.
In some preferred embodiments of the first, second specific embodiment of the invention, the step T1, the step
In T4, the step T5, substrate 131 can be in following Temperature Vacuum vapor deposition film-formation: 10-15 DEG C, 15-20 DEG C, 20-25 DEG C
Or 25-30 DEG C.The some more preferably temperature described in embodiment of the present invention concretely: 10 DEG C, 15 DEG C, 20 DEG C or 25 DEG C.
In some preferred embodiments of the first, second specific embodiment of the invention, the step T2, the step
In T3, the step T6, it can form a film in following operating air pressure vacuum vapor deposition: 0.2-0.6pa, 0.5-0.6pa, 0.6-
1.6pa, 1.6-1.8pa, 1.8-2pa, 2-3pa or 2.5-3pa.In some more preferably operating air pressures described in embodiment of the present invention
Concretely: 1pa,
1.2pa, 1.4pa, 1.5pa, 1.6pa, 1.7pa, 1.8pa, 1.9pa or 2pa.
In some preferred embodiments of the first, second specific embodiment of the invention, the step T2, the step
In T3, the step T6, substrate 131 can be in following Temperature Vacuum vapor deposition film-formation: 200-300 DEG C, 300-500 DEG C,
500-600 DEG C or 600-800 DEG C.The some more preferably temperature described in embodiment of the present invention concretely: 300 DEG C, 400 DEG C,
500 DEG C, 600 DEG C, 700 DEG C or 800 DEG C.
In some preferred embodiments of the first, second specific embodiment of the invention, in the step T1-T6, institute
State the anode collection body thin film 101, anode thin film 102, inorganic solid electrolyte film 103, negative film of vacuum vapor deposition
104, negative pole currect collecting body thin film 105 and 106 thickness of barrier film can are as follows: 10-50nm, 10-100nm, 50-100nm, 80-
200nm、100-300nm、200-400nm、300-500nm、500-800nm、800-1000nm、
1000-2000nm.The some more preferably thickness described in embodiment of the present invention concretely: 10nm, 50nm,
80nm、100nm、200nm、300nm、400nm、500nm、600nm、700nm、800nm、900nm、1000nm、
1200nm, 1500nm or 2000nm.
Hierarchical element number described in first, second specific embodiment of the invention is more than or equal to 2.In the present invention first, the
In some preferred embodiments of two specific embodiments, the hierarchical element number be 2-10,5-50,20-100,50-100,
80-150,100-200,200-400,300-500,200-500 or 500-2000.The present invention is some more preferably described in embodiment
Hierarchical element number 10,20,50,100,150,200,300,500 or 1000.
The air pressure for adjusting vacuum vapor deposition and 131 temperature of substrate can guarantee that vacuum gas-phase is heavy to suitable range
Product is at film uniformity.
The number of the hierarchical element and the anode collection body thin film 101, anode thin film 102, inorganic solid-state electrolysis
Matter film 103, negative film 104, negative pole currect collecting body thin film 105 and 106 thickness of barrier film can be according to all solid state metals
The capacity of ion battery is arranged.Therefore it is all solid state that the combination that laminate film thickness is different and hierarchical element number is different can be prepared
Metal ion battery, thus the size range and battery capacity of all solid state metal ion battery are substantially increased, have extensive
Applicability.
Referring to FIG. 5, all solid state metal ion battery preparation method provided by first embodiment of the invention, above-mentioned
The preferred steps of specific cell package are as follows in step S3:
Above-mentioned each anode collection body thin film 101 is electrically connected on the first tab 301, each plus plate current-collecting body
Film 101 is parallel with one another.Each anode collection body thin film 101 is connected by the first tab 301 with external circuit, thus real
Now each hierarchical element is well connected with external circuit.
Above-mentioned each negative pole currect collecting body thin film 105 is electrically connected on the second tab 302, each negative current collector
Film 105 is parallel with one another.Each negative pole currect collecting body thin film 105 is connected by the second tab 302 with external circuit, thus real
Now each hierarchical element is well connected with external circuit.
The operations such as sealed again, shaping obtain all solid state metal ion battery.
Second embodiment of the invention provides a kind of all solid state metal ion battery, and the battery includes at least two present invention
Described in the first specific embodiment and the second specific embodiment in first embodiment on substrate 131 vacuum vapor deposition
The battery device of hierarchical element superposition preparation.Each film of hierarchical element uses above-mentioned all solid state metal ion battery preparation side
Method prepares.The hierarchical element includes the first hierarchical element, the second hierarchical element；First hierarchical element includes successively
The anode thin film 102- inorganic solid electrolyte film 103- negative film 104 of lamination, second hierarchical element include successively
The negative film 104- inorganic solid electrolyte film 103- anode thin film 102 of lamination.The all solid state metal ion battery tool
There is the features such as nontoxicity, high security, high energy storage density, battery capacity are big, charge/discharge capacity conservation rate is high.
It is described using true compared with the all-solid-state battery product of existing preparation in some preferred embodiments of the present invention
Vapor depos prepare all solid state metal ion battery and can improve energy storage density, charge/discharge capacity conservation rate, increase battery capacity
Deng.When all solid state metal ion battery stack unit is 50-100, all solid state metal ion battery energy storage density is reachable
350Wh/Kg or more；After 5C charge and discharge 1000-1500 times circulation, capacitance conservation rate is greater than 90%；Battery capacity is up to 10Ah
More than.
Third embodiment of the invention provides the electric vehicle with all solid state metal ion battery of hierarchical element superposition,
The electric vehicle uses all solid state metal ion battery as described in second embodiment of the invention.The electric vehicle have make
With the features such as service life is long, security performance is high, charge/discharge capacity holding capacity is strong.
Compared with prior art, a kind of all solid state metal ion battery of the present invention and preparation method thereof, electric vehicle have with
Lower advantage:
(1) preparation method of all solid state metal ion battery provided by the present invention deposits at least two hierarchical elements, institute
Stating hierarchical element includes anode thin film, negative film and inorganic solid electrolyte film, and repeated deposition, forms multiple laminations
Multiple hierarchical elements can be arranged, the energy storage for improving unit volume is close in the case where cell device sizes are limited in unit superposition
Degree solves the problems, such as that microelectronic component energizes to improve the capacity of battery.
(2) hierarchical element includes the first hierarchical element, the second hierarchical element, thus a variety of superposition sides can be set
Formula makes all solid state metal ion battery have wide applicability to increase all solid state metal ion battery variety.
In the case of (3) first hierarchical elements, the second hierarchical element are disposed adjacent, the first hierarchical element and the second hierarchical element
Between an anode collection body thin film or negative pole currect collecting body thin film are set, in the case where cell device sizes are limited, one can be reduced
Hierarchical element occupied space, while more hierarchical elements can be set in one timing of cell device sizes, it further increases complete
Solid metallic ion battery energy storage density, to improve battery capacity.
(4) air pressure and the substrate temperature for adjusting vacuum vapor deposition, can guarantee the uniformity of vacuum vapor deposition film forming.
(5) anode collection body thin film, anode thin film, inorganic solid electrolyte film, negative film, negative pole currect collecting body thin film
The number being superimposed with the thickness and hierarchical element of barrier film, can select according to the capacity of all solid state metal ion battery
With, therefore all solid state metal ion battery of combination that laminate film thickness is different and hierarchical element number is different can be prepared, because
And the size range and battery capacity of all solid state metal ion battery are substantially increased, there is wide applicability.
(6) all solid state metal ion battery being superimposed with the hierarchical element big, charge and discharge with battery capacity are prepared
The high advantage of battery capacity conservation rate.
(7) electric vehicle of all solid state metal ion battery provided by the present invention with hierarchical element superposition, has
Long service life, security performance height, the high feature of charge/discharge capacity conservation rate.
The foregoing is merely present pre-ferred embodiments, are not intended to limit the invention, it is all principle of the present invention it
Any modification made by interior, equivalent replacement and improvement etc. should all be comprising within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of all solid state metal ion battery, it is characterised in that: including
Step S1 provides a substrate；
Step S2, forms at least two hierarchical elements on substrate, the hierarchical element include anode thin film, negative film and
Inorganic solid electrolyte film between anode thin film and negative film is set；Wherein provide at least three target positions and in target
Corresponding target is set on material position, and setting power supply is DC power supply, and the air pressure of vacuum vapor deposition is 0.35-0.6Pa, is kept
Substrate temperature is 10-30 DEG C, and anode collection body thin film is formed on substrate；Setting power supply is radio-frequency power supply, vacuum gas-phase
The air pressure of deposition is 2-3Pa, and temperature is 600-800 DEG C, and anode thin film, inorganic solid is sequentially formed on anode collection body thin film
State electrolytic thin-membrane；Setting power supply is DC power supply, and the air pressure for adjusting vacuum vapor deposition is 0.2-3Pa, temperature 10-
It 30 DEG C, deposits to form negative film far from the one side of the anode thin film in the inorganic solid electrolyte film；Electric power is set
It is supplied as radio-frequency power supply, the air pressure for adjusting vacuum vapor deposition is 0.2-3Pa, and temperature is 10-30 DEG C, in the one side of negative film
Deposition forms negative pole currect collecting body thin film；Setting power supply is radio-frequency power supply, and the air pressure for adjusting vacuum vapor deposition is 1.6-
1.8Pa, temperature are 300-500 DEG C, form barrier layer on negative pole currect collecting body thin film；And step S3, it is superimposed the hierarchical element.
2. the preparation method of all solid state metal ion battery as described in claim 1, it is characterised in that: all solid state metal
When ion battery is lithium ion battery, it is thin to prepare anode collection body thin film, anode thin film, inorganic solid electrolyte film, cathode
The target of film and negative pole currect collecting body thin film is respectively as follows:
Aluminium simple substance target, LiFePO4 compound target, Li7Y3Nb2O12Solid electrolyte compound target, lithium simple substance target and
Copper simple substance target；Or molybdenum simple substance target, nickel cobalt manganese compound target, Li-La-Ti-O solid electrolyte compound target, lithium list
Matter target and copper simple substance target.
3. the preparation method of all solid state metal ion battery as described in claim 1, it is characterised in that: all solid state metal
When ion battery is sodium-ion battery, the inorganic solid electrolyte target includes Na-Mn-O solid electrolyte, Na-Co-O solid
State electrolyte, Na-Fe-P-O olivine structural solid electrolyte, mixing one or more of in Na-P-O-F solid electrolyte
Object.
4. the preparation method of all solid state metal ion battery as described in claim 1, it is characterised in that: all solid state metal used
Ion battery be lithium ion battery when, the inorganic solid electrolyte target include Li-Ge-P-S solid electrolyte,
Li7La3Ta2O13Solid electrolyte, LiGePO4Solid electrolyte, Li-La-Ti-O quaternary system solid electrolyte or anti-calcium
It is any in perovskite like structure solid electrolyte.
5. the preparation method of all solid state metal ion battery as described in claim 1, it is characterised in that: the barrier layer target
For titanium nitride or silicon nitride.
6. the preparation method of all solid state metal ion battery as described in claim 1, it is characterised in that: the anode target packet
Include cobalt acid lithium, LiMn2O4, LiFePO4, nickel cobalt manganese, mixture one or more of in nickel cobalt aluminium.
7. the preparation method of all solid state metal ion battery as described in claim 1, it is characterised in that: the plus plate current-collecting body
Film, anode thin film, inorganic solid electrolyte film, negative film, negative pole currect collecting body thin film and barrier film with a thickness of
10 nanometers to 2 microns；The hierarchical element number is more than or equal to 2.
8. a kind of all solid state metal ion battery, it is characterised in that: the hierarchical element being superimposed on substrate including at least two；Institute
Stating hierarchical element includes anode thin film, negative film and the inorganic solid-state electrolysis being arranged between anode thin film and negative film
Matter film, all solid state metal ion battery utilize all solid state metal ion described in any one of the claims 1-7
The preparation method of battery and prepare.
9. a kind of electric vehicle with all solid state metal ion battery, it is characterised in that: including as claimed in claim 8 complete solid
State metal ion battery.
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