CN110085917A - All-solid lithium-ion battery and preparation method thereof and electrical equipment - Google Patents

All-solid lithium-ion battery and preparation method thereof and electrical equipment Download PDF

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Publication number
CN110085917A
CN110085917A CN201910358078.3A CN201910358078A CN110085917A CN 110085917 A CN110085917 A CN 110085917A CN 201910358078 A CN201910358078 A CN 201910358078A CN 110085917 A CN110085917 A CN 110085917A
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lithium
material layer
anode
electrode material
solid
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CN110085917B (en
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夏晖
夏求应
孙硕
昝峰
徐璟
岳继礼
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THE NORTHERN Research Institute OF NJUST
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Northern Research Institute Nanjing University Of Science & Technology
Tianjin Rui Sheng Hui Neng Technology Co Ltd
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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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention belongs to technical field of secondary batteries, it is related to a kind of all-solid lithium-ion battery and preparation method thereof and electrical equipment.All-solid lithium-ion battery of the invention, including anode and cathode；Wherein, the positive electrode active materials in anode include containing manganese compound；Negative electrode active material in cathode includes containing manganese compound.All-solid lithium-ion battery of the invention, active material in anode and cathode all uses the compound containing manganese, so that it carries out the chemical property for guaranteeing that its is excellent of annealing with regard to crystallinity with higher under room temperature or lower temperature, or excellent chemical property is still able to maintain without annealing crystallization, have the characteristics that without high-temperature process, preparation process, reduction preparation cost can be simplified.And it can prepare, not limited by base material in various substrates；It can also be matched with semiconductor technology and realize that solid state battery is integrated on microcircuit.

Description

All-solid lithium-ion battery and preparation method thereof and electrical equipment
Technical field
The invention belongs to technical field of secondary batteriess, in particular to a kind of all-solid lithium-ion battery and its preparation Method and electrical equipment.
Background technique
Lithium ion battery is numerous excellent due to its high working voltage, high-energy density, long circulation life, memory-less effect etc. Point has in fields such as consumer electronics, medical electronics, electric tool, electric car, rail traffic, aerospaces and widely answers With.However, current commercial lithium ion battery is due to using liquid state organic electrolyte, there is inflammable and explosive volatile spies Point, safety accident takes place frequently in recent years.Thus, solid lithium battery is replaced increasingly by concern in the industry using solid electrolyte For liquid state organic electrolyte, and prepares All-solid film batteries and can effectively solve the safety issue of lithium ion battery.Currently The solid state battery of figure is difficult to realize commercially use at present since electrode/electrolyte interface problem and technology are not mature enough. And by solid state battery filming, and prepare all solid-state thin-film lithium battery and more perfect electrode/electrolyte interface may be implemented, it is mesh Before have been carried out the solid state battery forms of commercial applications.
Currently, most common positive electrode is positive electrode (such as LiCoO containing lithium in solid-State Thin Film Li-Ion Batteries2 Material), most common negative electrode material is lithium metal or lithium alloy cathode.For positive electrode, the positive electrode containing lithium is logical Often only after the high-temperature anneal (such as LiCoO2Need 500 DEG C or more of high annealing) higher high-crystallinity can be just obtained to guarantee Its excellent chemical property.However, high-temperature annealing process be easy to cause positive electrode active materials film peeling, falls off, cause thin Film battery forms micro-short circuit；In addition, pyroprocess and semiconductor technology mismatch, it is difficult to which real solid-state thin-film battery is on microcircuit It is integrated；High-temperature annealing process is but also all solid-state thin-film lithium battery is difficult to the base in some non-refractories, low cost, high flexibility It is prepared on bottom (such as polyimides, aluminium foil).And for negative electrode material, since the fusing point of lithium lower (about 180 DEG C), lithium are easy Water suction or oxygen uptake and fail, thus using lithium anode when is difficult to integrate that (welding temperature is logical when integrated in integrated circuits Often be higher than 180 DEG C), production environment harsh (needing in glove box or in high level ultra-clean chamber), high temperature place be difficult to answer With (being typically only capable to apply at lower than 180 DEG C).Further, since the preparation of anode and cathode uses different technique and sets Standby, production technology and preparation flow are relatively more cumbersome.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of all-solid lithium-ion battery, is all free of lithium, Ke Yi in positive and negative anodes It being prepared in various substrates, positive and negative anodes stability is good, and it is easily prepared, the above problem can be overcome or at least be partially solved above-mentioned Technical problem.
The second object of the present invention is to provide a kind of preparation method of all-solid lithium-ion battery, and this method is simply easy Row is all free of lithium in positive and negative anodes, can prepare in various substrates, and identical instrument and equipment, identical or close can be used Technique prepares positive and negative anodes, simplifies preparation flow, reduces preparation cost.
The third object of the present invention is to provide a kind of electrical equipment, which includes above-mentioned all solid state lithium ion electricity Pond.
To achieve the above object, the technical solution adopted by the present invention are as follows:
According to an aspect of the present invention, the present invention provides a kind of all-solid lithium-ion battery, including anode and cathode；
Positive electrode active materials in the anode include containing manganese compound；
Negative electrode active material in the cathode includes containing manganese compound.
Preferably, the manganese compound that contains includes Mn oxide；
Preferably, the Mn oxide includes one of manganese dioxide, mangano-manganic oxide or manganese sesquioxide managnic oxide or a variety of Combination.
Preferably, the anode includes anode collection layer and the positive electrode material layer for being formed in the anode collection layer surface, The positive electrode material layer includes positive electrode active materials, and the positive electrode active materials include containing manganese compound；
The cathode includes negative pole currect collecting layer and the negative electrode material layer for being formed in the negative pole currect collecting layer surface, the cathode Material layer includes negative electrode active material, and the negative electrode active material includes containing manganese compound；
Preferably, the positive electrode material layer is manganese-salt phosphating；
Preferably, the negative electrode material layer is manganese-salt phosphating.
It preferably, further include the solid electrolyte containing lithium；
Preferably, the all-solid lithium-ion battery includes the anode collection layer being cascading, positive electrode material layer, contains Solid electrolyte, negative electrode material layer and the negative pole currect collecting layer of lithium；
Preferably, the solid electrolyte containing lithium includes LiPON, LiSiON, Li2SiO3、Li7La3Zr2O12、LiBO3、 Li3PO4、Li3OX (X F, Cl or Br) or LiTi2(PO4)3One of or a variety of combinations；
It is highly preferred that the solid electrolyte containing lithium is LiPON.
Preferably, the all-solid lithium-ion battery is hull cell.
According to another aspect of the present invention, the preparation method of all-solid lithium-ion battery described in one kind is provided, respectively Production anode and cathode；
The preparation method of anode and cathode independently includes magnetron sputtering method, pulsed laser deposition, chemical vapour deposition technique Or at least one of coating method, preferably magnetron sputtering method.
Preferably, using magnetron sputtering method to prepare anode includes: using manganese as target, in the item for being passed through oxygen and inert gas Under part, positive electrode material layer is deposited in anode collection layer surface, obtains anode.
Preferably, using magnetron sputtering method to prepare cathode includes: using manganese as target, in the item for being passed through oxygen and inert gas Under part, negative pole currect collecting layer is deposited in negative electrode material layer surface, obtains cathode.
Preferably, the anode includes anode collection layer and positive electrode material layer, and the cathode includes negative pole currect collecting layer and bears Pole material layer；
The anode collection layer surface be sequentially prepared positive electrode material layer, the solid electrolyte containing lithium, negative electrode material layer and Negative pole currect collecting layer obtains the all-solid lithium-ion battery；
Preferably, positive electrode material layer is first deposited in anode collection layer surface using magnetron sputtering method, then uses magnetron sputtering Method prepares the solid electrolyte containing lithium in positive electrode layer surface, then using magnetron sputtering method in the solid electrolyte table containing lithium Wheat flour finally deposits negative pole currect collecting layer in negative electrode material layer surface using magnetron sputtering method for negative electrode material layer.
According to another aspect of the present invention, the present invention also provides a kind of electrical equipment, including all solid lithium from Sub- battery.
Compared with prior art, the beneficial effects of the present invention are:
1, all-solid lithium-ion battery provided by the invention, anode and cathode in active material all use the chemical combination containing manganese Object, i.e., positive electrode active materials replace the positive electrode active materials such as existing cobalt acid lithium, cathode using the compound containing manganese in the battery Active material replaces the negative electrode active materials such as existing lithium metal using the compound containing manganese, so that it is in room temperature or lower temperature Under carry out the chemical property for guaranteeing that its is excellent of annealing with regard to crystallinity with higher under (be lower than 400 DEG C), or without moving back Fire crystallization be still able to maintain excellent chemical property, have without high-temperature process, can simplify preparation process, reduce be prepared into This features such as.Lithium is all free of in the positive and negative anodes of the battery system, can be prepared in various substrates, not by the limit of base material System；It can also be matched with semiconductor technology and realize that solid state battery is integrated on microcircuit.
2, compound specific capacity with higher and energy density containing manganese, using the compound containing manganese as positive-active Material and negative electrode active material can effectively improve the capacity and energy density of all-solid lithium-ion battery；And positive and negative anodes are steady It is qualitative good, help to improve the cyclical stability and service life of battery；Positive and negative pole material is cheap simultaneously, can substantially drop The production cost of low all-solid lithium-ion battery.
3, the preparation method of all-solid lithium-ion battery provided by the invention, it is easy to operate, it is easy to implement, phase can be used With instrument and equipment, identical or close technique prepare the anode and cathode of battery, simplify preparation flow, reduce and be prepared into This, it is easy to accomplish industrially scalable metaplasia produces.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the structural schematic diagram of all-solid lithium-ion battery provided in an embodiment of the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of manganese-salt phosphating in the embodiment of the present invention 1；
Fig. 3 is the X-ray diffractogram of manganese-salt phosphating in the embodiment of the present invention 1；
Fig. 4 is the scanning electron microscope (SEM) photograph for the all-solid lithium-ion battery that the embodiment of the present invention 1 provides；
Fig. 5 is the all-solid lithium-ion battery charging and discharging curve figure and cycle performance figure that the embodiment of the present invention 1 provides, In, (a) is charging and discharging curve figure, (b) is charge-discharge performance figure；
Fig. 6 is the scanning electron microscope (SEM) photograph of manganese-salt phosphating in the embodiment of the present invention 2；
Fig. 7 is the X-ray diffractogram of manganese-salt phosphating in the embodiment of the present invention 2；
Fig. 8 is the scanning electron microscope (SEM) photograph for the all-solid lithium-ion battery that the embodiment of the present invention 2 provides；
Fig. 9 is the charging and discharging curve figure for the all-solid lithium-ion battery that the embodiment of the present invention 2 provides.
Icon: 1- plus plate current-collecting body；2- positive electrode material layer；Solid electrolyte of the 3- containing lithium；4- negative electrode material layer； 5- negative current collector.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiments and examples, but this field skill Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and are not construed as limiting model of the invention It encloses.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts Every other embodiment, shall fall within the protection scope of the present invention.The person that is not specified actual conditions, according to normal conditions or manufacturer builds The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase Product.
All solid-state thin-film lithium battery belongs to one of solid state secondary battery, and all solid-state thin-film lithium battery is in conductive liner Each element of battery is sequentially prepared into film according to the sequence of anode, electrolyte, cathode on bottom, finally encapsulation constitutes one Whole battery, working principle are similar with commercial li-ion battery.All solid-state thin-film lithium battery and the commercialization for using liquid electrolyte Lithium ion battery is compared, and has the advantage that (1) stock utilization is very big, it can be achieved that end-point energy density is very big；(2) it works Temperature range is wide, can be used in -40 DEG C to 180 DEG C wide temperature ranges；(3) self-discharge rate is low, year self-discharge rate < 3%； (4) it has extended cycle life, is recycled tens of thousands of times；(5) charge-discharge velocity is fast, it can be achieved that fast charging and discharging；It (6) can be with semiconductor technology Matching, can be internally integrated in electricity consumption device.In addition, that there are also packaging efficiencies is higher for all solid-state thin-film lithium battery, power supply system can be reduced The good characteristic that all solid-state thin-film lithium battery has the features such as the volume of idle space in system makes it in microelectronic device, such as It has a wide range of applications in fields such as smart card, electronic tag, integrated circuit, MEMS, wearable electronic, space flight Prospect.Contain lithium in view of at least one in the anode and cathode of existing all solid-state thin-film lithium battery, that there are preparation sections is many and diverse, The problems such as working condition is harsh, high temperature place is difficult to apply, base material is limited, stability is poor, the present inventor's warp Cross further investigation, it is creative provide a kind of positive and negative anodes be all free of lithium without lithium type all-solid lithium-ion battery, it is above-mentioned to alleviate Technical problem.
In a first aspect, providing a kind of all-solid lithium-ion battery at least one embodiment, including anode and cathode；
Positive electrode active materials in the anode include containing manganese compound；
Negative electrode active material in the cathode includes containing manganese compound.
It should be noted that " comprising " of the present invention, it is intended that it can also include in addition to the component or component Other components or component, these other components assign positive electrode active materials or the different characteristic of negative electrode active material.In addition to this, " comprising " of the present invention, may be replaced by enclosed " for " or " by ... form ".
For example, the all-solid lithium-ion battery can also include electrolyte in addition to including anode and cathode.
For another example, positive electrode active materials include containing manganese compound, could alternatively be enclosed literary style, that is, positive-active material Material is containing manganese compound.Negative electrode active material includes containing manganese compound, could alternatively be enclosed literary style, that is, negative electrode active Material is containing manganese compound.
All-solid lithium-ion battery of the invention is that positive and negative anodes all use the full solid thin film lithium-ion electric containing manganese compound Pond, positive electrode active materials replace the positive electrodes such as cobalt acid lithium using the compound containing manganese in the battery, and negative electrode material, which uses, contains manganese Compound replace replace lithium metal.It can be under room temperature or lower temperature with cathode with the anode containing manganese compound (being lower than 400 DEG C) is prepared.The battery system mainly has the advantage that (1) battery system can use identical instrument Device, technique preparation, can simplify preparation flow, reduce preparation cost.(2) it is not necessarily to high-temperature process, can simplify and prepared Journey reduces preparation cost, promotes the stability of electrode, can also match with semiconductor technology and realize solid-state thin-film battery micro- It is integrated on circuit；(3) battery system can be prepared in various substrates, both include conventional stainless steel resistant to high temperature, oxygen Change aluminium, silicon wafer, glass sheet substrate, can also lightweight, non-refractory paper on, polymer (such as polyimide) base material Upper preparation, and unique all solid state " paper battery " can be developed.
Meanwhile compound specific capacity with higher and energy density containing manganese, such as under normal circumstances, the oxidation containing manganese Theoretical specific capacity when object is as anode is about 300mAh/g, and energy density is about 870Wh/Kg, theoretical ratio when as cathode Capacity is about 1000mAh/g.It therefore, can be effective using the compound containing manganese as positive electrode active materials and negative electrode active material The capacity and energy density of ground raising all-solid lithium-ion battery.And the compound containing manganese is not necessarily to high annealing, preparation efficiency Height, preparation cost are low；Meanwhile the compound-material containing manganese is cheap, therefore, using the compound-material containing manganese as battery Positive and negative anodes active material, the production cost of all-solid lithium-ion battery can be greatly reduced；And work can be prepared with semiconductor Skill matches, and improves cell capacity.
After tested, the positive and negative anodes stability of above-mentioned battery is good, and specific capacity is high, good cycle, long service life；Such as work Make voltage in 0V to 4.5V, under the electric current of 25mA/g, specific capacity is up to 135mAh/g；The charge and discharge under the electric current of 200mA/g Capacity retention ratio is about 81% after electricity circulation 200 times.
It is understood that including positive electrode active materials in anode, positive electrode active materials are containing manganese compound；It is wrapped in cathode Containing negative electrode active material, negative electrode active material is containing manganese compound.
It should be noted that above-mentioned " containing manganese compound " refers to the compound comprising manganese, including but not limited to comprising manganese Oxide, chloride comprising manganese etc. preferably include the oxide of manganese.
In some preferred embodiments, the manganese compound that contains includes Mn oxide；Preferably, described to be closed containing manganese Object is Mn oxide；
Preferably, the Mn oxide includes one of manganese dioxide, mangano-manganic oxide or manganese sesquioxide managnic oxide or a variety of Combination.
It should be noted that the Mn oxide in anode and cathode can be with independent choice, i.e. manganese oxygen in anode and cathode Compound may be the same or different.
Further, Mn oxide can be manganese dioxide, can be manganese sesquioxide managnic oxide, can be mangano-manganic oxide, can be with For the combination of manganese dioxide and manganese sesquioxide managnic oxide, it can be the combination of manganese sesquioxide managnic oxide and mangano-manganic oxide, can be titanium dioxide The combination of manganese and mangano-manganic oxide, or the combination of manganese dioxide, manganese sesquioxide managnic oxide and mangano-manganic oxide.
It according to the present invention, is preferably Mn oxide containing manganese compound, Mn oxide is referred to as manganese oxide, refers to and includes The oxide of manganese, is expressed as MnOx.Object phase, the crystallinity of the positive and negative anodes active material Mn oxide are not unique, including but not Be limited to manganese dioxide, mangano-manganic oxide, three oxidation and manganese and more than several Mn oxides compound phase.
In some preferred embodiments, the anode includes anode collection layer and is set to the anode collection layer table The positive electrode material layer in face, the positive electrode active materials in the positive electrode material layer are containing manganese compound；
The cathode includes negative pole currect collecting layer and the negative electrode material layer for being set to the negative pole currect collecting layer surface, the cathode Negative electrode active material in material layer is containing manganese compound；
Preferably, the positive electrode material layer is manganese-salt phosphating；
Preferably, the negative electrode material layer is manganese-salt phosphating.
According to the present invention, which includes anode and cathode, and anode includes anode collection layer and positive material The bed of material, cathode include negative pole currect collecting layer and negative electrode material layer；Wherein the positive electrode active materials in positive electrode material layer are to close containing manganese Object preferably contains Mn oxide, and the negative electrode active material in negative electrode material layer is preferably to contain Mn oxide containing manganese compound.
Anode thin film of the invention is manganese oxide film, and negative film is manganese-salt phosphating, and manganese-salt phosphating has Good chemical property, chemical stability is good, has good charging and discharging circulation reversibility, and battery is long.
It should be noted that positive electrode material layer of the invention can only include positive electrode active materials, that is, the positive electrode material layer For simple manganese-salt phosphating.In addition, the positive electrode material layer is in addition to including positive electrode active materials, it can also include conductive agent And binder or other can improve the substance of Mn oxide performance.
Likewise, the negative electrode material layer of invention can only include negative electrode active material, that is, the negative electrode material layer is simple Manganese-salt phosphating.In addition, the negative electrode material layer is in addition to including negative electrode active material, it can also include conductive agent and bonding Agent or other can improve the substance of Mn oxide performance.
Preferably, which is simple manganese-salt phosphating, and negative electrode material layer is that simple Mn oxide is thin Film is added without the substances such as other conductive agents.It, can using simple manganese-salt phosphating as positive electrode material layer and negative electrode material layer To simplify production technology, production cost is reduced, the stability of positive and negative pole material is improved, and positive and negative anodes is made to keep higher specific capacity And energy density.
It is understood that above-mentioned anode collection layer is plus plate current-collecting body, above-mentioned negative pole currect collecting layer is negative pole currect collecting Body.The present invention is not particularly limited the concrete type of plus plate current-collecting body and negative current collector, and those skilled in the art can be selected Plus plate current-collecting body and negative current collector known to member, such as plus plate current-collecting body and negative current collector are respectively included but are not limited to stainless Steel, copper, aluminium, gold, platinum, titanium, silver, nickel etc..Preferably, plus plate current-collecting body is platinum/titanium, and negative current collector is copper.
In some preferred embodiments, the all-solid lithium-ion battery is hull cell.
It in some preferred embodiments, further include the solid electrolyte containing lithium；
Preferably, the solid electrolyte containing lithium includes LiPON, LiSiON, Li2SiO3、Li7La3Zr2O12、LiBO3、 Li3PO4、Li3OX (X F, Cl or Br) or LiTi2(PO4)3One of or a variety of combinations；For example, this contains the solid-state of lithium Electrolyte can be LiPON, can be LiSiON, can be Li2SiO3, can be Li7La3Zr2O12, can for LiPON and The combination of LiSiON can be LiBO3、Li3PO4And Li3The combination of OX can be Li7La3Zr2O12、LiBO3、Li3PO4、 Li3OX and LiTi2(PO4)3Combination etc..
It is highly preferred that the solid electrolyte containing lithium is LiPON.
According to the present invention, which includes substrate material layer, anode, the solid electrolyte containing lithium and bears Pole, all-solid lithium-ion battery have layer structure, the substrate material layer, anode, the solid electrolyte containing lithium and cathode according to Secondary fitting.Further, which includes the substrate material layer being cascading, anode collection layer, just Pole material layer, the solid electrolyte containing lithium, negative electrode material layer and negative pole currect collecting layer.When all-solid lithium-ion battery is hull cell When, positive electrode material layer is manganese-salt phosphating, the solid electrolyte containing lithium is solid electrolyte film, and negative electrode material layer is manganese oxygen Compound film.
The present invention does not have base material special limitation, such as can be the sheet glass of platinum plating, or is coated with Polyimides, alumina wafer, paper of conductive current collector layer etc. can also be stainless steel, aluminium foil and respective metal foil etc..It utilizes Compound containing manganese has base material from a wealth of sources as positive electrode active materials and negative electrode active material, adaptable to wait spies Point, and the battery system is allowed to have wider application space.
The present invention does not have the solid electrolyte containing lithium special limitation, can use solid state electrolysis well known in the art Matter, the polymer including but not limited to containing lithium, the oxide containing lithium, sulfide containing lithium etc., it is typical but non-limiting for example It can be LiPON, LiSiON, Li2SiO3、Li7La3Zr2O12、LiBO3、Li3PO4、Li3OX or LiTi2(PO4)3In at least one Kind.
In some preferred embodiments, positive electrode material layer (manganese-salt phosphating) with a thickness of 50~5000nm, it is excellent It is selected as 400nm；
Negative electrode material layer (manganese-salt phosphating) with a thickness of 50~5000nm, preferably 400nm；
Anode collection layer with a thickness of 10~200nm, preferably 40nm；
Negative pole currect collecting layer with a thickness of 10~200nm, preferably 40nm；
Solid electrolyte film with a thickness of 200~5000nm, preferably 2000nm.
The thickness of positive electrode material layer and/or negative electrode material layer is not easy excessive or too small, suitable positive electrode material layer and/or bears The thickness of pole material layer helps to improve the utilization rate of positive and negative pole material, optimizes the cycle performance and fast charging and discharging energy of battery Power.The thickness of solid electrolyte film be not easy excessive or too small, suitable solid electrolyte film with a thickness of 2000nm, help In the short circuit ratio for reducing battery, improves the preparation yields of battery and guarantee battery fast charging and discharging ability.
Second aspect provides a kind of preparation method of all-solid lithium-ion battery at least one embodiment, comprising: point It Zhi Zuo not anode and cathode；
The preparation method of anode and cathode independently includes magnetron sputtering method, pulsed laser deposition, chemical vapour deposition technique Or at least one of coating method, preferably magnetron sputtering method.
For example, the preparation method of positive or negative pole can be magnetron sputtering method, it can be pulsed laser deposition, can be chemistry Vapour deposition process can be coating method, or magnetron sputtering method and the combination of pulsed laser deposition etc..
All-solid lithium-ion battery of the invention, the positive electrode active materials in anode be containing manganese compound, it is negative in cathode Pole active material is so that the battery system can use identical instrument, prepared by technique, i.e., only to need one containing manganese compound The preparation of anode and cathode can be completed in set equipment, not only reduces equipment cost, and simplify preparation flow, reduces system Standby cost；Also without high-temperature process, energy consumption is reduced；It can also be matched with semiconductor technology and real solid film is electric Pond is integrated on microcircuit.It will be appreciated to those of skill in the art that above for described by all-solid lithium-ion battery Feature and advantage, be still applied to the preparation method of the all-solid lithium-ion battery, details are not described herein.
Above-mentioned preparation method includes: successively to make anode, solid electrolyte and cathode containing lithium, makes the anode, containing lithium Solid electrolyte and after cathode is successively bonded, obtain the all-solid lithium-ion battery.
It should be understood that anode includes anode collection layer and positive electrode material layer, cathode includes negative pole currect collecting layer and cathode Material layer, as long as above-mentioned magnetron sputtering method, pulsed laser deposition, chemical vapour deposition technique or coating method are used to prepare positive electrode Layer and negative electrode material layer；Further, mainly for the preparation of manganese-salt phosphating and solid electrolyte film.
According to the present invention, the production method of anode and film and solid electrolyte film in cathode includes but is not limited to Magnetron sputtering method, pulsed laser deposition, chemical vapour deposition technique or coating method etc..It is preferred that carrying out preparing manganese oxygen using magnetron sputtering method Compound film and solid electrolyte film, the film compactness using magnetron sputtering method preparation is high, purity is high, between layers Close in conjunction with comparing, battery performance obtained is good, and preparation method is easy, and process conditions are mild, facilitates control thin The thickness of film is conducive to large batch of industrialized production and manufacture.
In some preferred embodiments, using magnetron sputtering method to prepare anode includes: to be passed through oxygen using manganese as target Under conditions of gas and inert gas, positive electrode material layer is deposited in anode collection layer surface, obtains anode.
In some preferred embodiments, using magnetron sputtering method to prepare cathode includes: to be passed through oxygen using manganese as target Under conditions of gas and inert gas, negative pole currect collecting layer is deposited in negative electrode material layer surface, obtains cathode.
Above-mentioned inert gas sputters manganese ion, is passed through oxygen and is capable of providing oxonium ion, sputter for bombarding manganese target The oxonium ion that manganese ion and ionization obtain deposits to base material, metal current collector layer or solid electrolyte film surface to obtain Manganese-salt phosphating.Using pure manganese (Mn) metallic target as target, cost of material can be saved, improves throughput rate.
Above-mentioned inert gas can select several inert gases commonly used in the art, such as can be helium, neon, argon Gas, Krypton etc., preferably argon gas.
Preferably, the vacuum degree for sputtering initial vacuum chamber is (0.5~5) × 10- 4Pa；
The volume flow for being passed through inert gas is 50~100sccm；
The volume flow for being passed through oxygen is 10~30sccm；
The temperature (temperature of magnetron sputtering) of base material is 20~400 DEG C；
Sputtering power density is 1~2W/cm2, sputtering time be 1.0~for 24 hours.
Magnetron sputtering is carried out under above-mentioned preferred magnetron sputtering operating condition, is more advantageous to the life of manganese-salt phosphating At can guarantee sputtering raste, improve quality of forming film, the chemical property of film layer is good, the energy density and power of battery obtained Density is also preferable, is more advantageous to actual production.
In some preferred embodiments, the anode includes anode collection layer and positive electrode material layer, the cathode packet Include negative pole currect collecting layer and negative electrode material layer；
The anode collection layer surface be sequentially prepared positive electrode material layer, the solid electrolyte containing lithium, negative electrode material layer and Negative pole currect collecting layer obtains the all-solid lithium-ion battery；
Preferably, one layer of positive electrode material layer is first deposited in anode collection layer surface using magnetron sputtering method, then uses magnetic control Sputtering method prepares the solid electrolyte containing lithium in positive electrode layer surface, then using magnetron sputtering method in solid-state electrolyte layer table Wheat flour finally deposits one layer of negative pole currect collecting layer in negative electrode material layer surface using magnetron sputtering method for negative electrode material layer.
According to the present invention, above-mentioned all-solid lithium-ion battery during the preparation process, is sequentially prepared in base material layer surface Anode collection layer, positive electrode material layer, the solid electrolyte containing lithium, negative electrode material layer and negative pole currect collecting layer.Such as in base material Layer surface is sequentially prepared plus plate current-collecting body, manganese-salt phosphating, solid electrolyte film, manganese-salt phosphating and negative pole currect collecting Body.It is preferred that preparing manganese-salt phosphating, solid electrolyte film by the way of magnetron sputtering.
It should be understood that is be not described in detail in the explanation of above-mentioned all-solid lithium-ion battery and preparation method thereof is interior Hold, such as remaining operating parameter of magnetron sputtering method is the Common Parameters that those skilled in the art are readily apparent that, therefore can be with Omit detailed description thereof.
The third aspect, provides a kind of electrical equipment at least one embodiment, including above-described all solid lithium from Sub- battery.
The electrical equipment includes above-mentioned all-solid lithium-ion battery, thus is at least had and above-mentioned all solid state lithium ion electricity The identical advantage in pond, details are not described herein.
It should be noted that above-mentioned electrical equipment can be for example electronic device, electric tool, electric vehicle or electric power storage Deposit system etc..Concretely, above-mentioned electrical equipment can be smart card, electronic tag, integrated circuit, wearable electronic Deng.
Combined with specific embodiments below, comparative example and attached drawing, the invention will be further described.
Embodiment 1
As shown in Figure 1, a kind of all-solid lithium-ion battery, including anode, solid electrolyte and cathode containing lithium.Into one Step, which includes the plus plate current-collecting body 1, positive electrode material layer 2, the solid state electrolysis containing lithium being cascading Matter 3, negative electrode material layer 4 and negative current collector 5.
Wherein, plus plate current-collecting body 1 is platinum/titanium (Pt/Ti), and positive electrode material layer 2 is manganese dioxide membrane, the solid-state electricity containing lithium Solution matter 3 is LiPON solid electrolyte film, and negative electrode material layer 4 is manganese dioxide membrane, and negative current collector 5 is copper (Cu).
The preparation method of the all-solid lithium-ion battery, comprising the following steps:
The preparation of S1, anode: direct current magnetron sputtering process, using pure Mn metallic target as target, platinum plating sheet glass conduct are used Base material plates Pt/Ti as plus plate current-collecting body on it.After installing target and plus plate current-collecting body, sputtering chamber is closed, it will Sputtering chamber is evacuated to 1.0 × 10- 4Pa is hereinafter, be passed through 50sccm argon gas and the oxygen of 20sccm, then by chamber indoor gas pressure Emphasize section to 1Pa；
At room temperature, sputtering power density is set as 1.4W/cm2, target-substrate distance 80mm, pre-sputtering 5min, with clear The impurity for managing target material surface, sputters 2h at room temperature, directly can obtain amorphous manganese dioxide membrane in plating Pt/Ti substrate；
The preparation of S2, solid electrolyte film: on the surface of obtained amorphous manganese dioxide membrane, continue to splash using magnetic control The mode of penetrating prepares LiPON solid electrolyte film, i.e., with Li3PO4For target, Ar and N2Gas is working gas, utilizes radio frequency magnetron Sputtering is prepared；
S3, the preparation of cathode and battery encapsulation: on obtained LiPON solid electrolyte film surface, continue using magnetic Control sputtering mode prepares the manganese dioxide membrane of cathode (sputtering technology is identical as anode)；Utilize magnetically controlled DC sputtering, metallic copper (Cu) it is used as target, directly sputters to obtain Cu film as negative current collector on negative film surface, is obtained finally by encapsulation Solid-State Thin Film Li-Ion Batteries.
Fig. 2 is the scanning electron microscope (SEM) photograph of manganese-salt phosphating in the embodiment of the present invention 1, from figure 2 it can be seen that obtained The film that manganese-salt phosphating is made of nanometer sheet.
Fig. 3 is the X-ray diffractogram of manganese-salt phosphating in the embodiment of the present invention 1, from figure 3, it can be seen that acquired Film object be mutually noncrystal membrane.
Fig. 4 is the scanning electron microscope (SEM) photograph for the all-solid lithium-ion battery that the embodiment of the present invention 1 provides, figure 4, it is seen that Entire all-solid lithium-ion battery has good interfacial contact.
Fig. 5 is the all-solid lithium-ion battery charging and discharging curve figure and cycle performance figure that the embodiment of the present invention 1 provides, In, (a) is charging and discharging curve figure, (b) is charge-discharge performance figure.From figure 5 it can be seen that the full solid thin film lithium ion Battery operating voltage is in 0V to 4.5V, under the electric current of 25mA/g, specific capacity 135mAh/g；Under the electric current of 200mA/g Capacity retention ratio is about 81% after charge and discharge cycles 200 times.
Embodiment 2
A kind of all-solid lithium-ion battery, including be cascading plus plate current-collecting body 1, positive electrode material layer 2, containing lithium Solid electrolyte 3, negative electrode material layer 4 and negative current collector 5.
Wherein, plus plate current-collecting body 1 is plating Pt/Ti mica sheet, and positive electrode material layer 2 is trimanganese tetroxide film, consolidating containing lithium State electrolyte 3 is LiPON solid electrolyte film, and negative electrode material layer 4 is trimanganese tetroxide film, and negative current collector 5 is copper (Cu)。
The preparation method of the all-solid lithium-ion battery, the difference from embodiment 1 is that:
In the preparation of step S1 anode, it is passed through 100sccm argon gas and the oxygen of 20sccm；
Base material is heated to 200 DEG C of sputtering 2h.
Fig. 6 is the scanning electron microscope (SEM) photograph of manganese-salt phosphating in the embodiment of the present invention 2, as can be seen from Figure 6 obtained It is the flat film formed by little particle.
Fig. 7 is the X-ray diffractogram of manganese-salt phosphating in the embodiment of the present invention 2, as can be seen from Figure 7 obtained Film object is mutually mangano-manganic oxide.
Fig. 8 is the scanning electron microscope (SEM) photograph for the all-solid lithium-ion battery that the embodiment of the present invention 2 provides, as can be seen from Figure 8, The solid-State Thin Film Li-Ion Batteries have good interfacial contact.
Fig. 9 is the charging and discharging curve figure for the all-solid lithium-ion battery that the embodiment of the present invention 2 provides, can from Fig. 9 Out, the all-solid lithium-ion battery operating voltage is in 0V to 4.5V, and under the electric current of 25mA/g, specific capacity is up to 105mAh/ g。
Embodiment 3
A kind of all-solid lithium-ion battery, including be cascading plus plate current-collecting body 1, positive electrode material layer 2, containing lithium Solid electrolyte 3, negative electrode material layer 4 and negative current collector 5.
Wherein, plus plate current-collecting body 1 is stainless steel, and positive electrode material layer 2 is trimanganese tetroxide film, the solid electrolyte containing lithium 3 be LiSiON solid electrolyte film, and negative electrode material layer 4 is trimanganese tetroxide film, and negative current collector 5 is molybdenum (Mo).
The preparation method of the all-solid lithium-ion battery, comprising the following steps:
The preparation of S1, anode: direct current magnetron sputtering process is used, using pure Mn metallic target as target, using stainless steel as base Bottom material and plus plate current-collecting body.After installing target and plus plate current-collecting body, sputtering chamber is closed, sputtering chamber is evacuated to 1.0×10- 4Pa is hereinafter, be passed through 40sccm argon gas and the oxygen of 10sccm, then gas pressure intensity in chamber is adjusted to 1Pa；
Substrate is heated to 300 DEG C, sets sputtering power density as 2W/cm2, target-substrate distance 80mm, pre-sputtering 5min sputters 4h, directly can obtain trimanganese tetroxide film in stainless steel base to clear up the impurity of target material surface；
The preparation of S2, solid electrolyte film: on the surface of obtained trimanganese tetroxide film, continue using magnetron sputtering Mode prepares LiSiON solid electrolyte film, i.e., with Li2SiO3For target, Ar and N2Gas is working gas, utilizes radio frequency magnetron Sputtering is prepared；
S3, the preparation of cathode and battery encapsulation: on obtained LiSiON solid electrolyte film surface, continue using magnetic Control sputtering mode prepares the trimanganese tetroxide film (sputtering technology is identical as anode) and metal molybdenum (Mo) negative pole currect collecting of cathode Body obtains solid-State Thin Film Li-Ion Batteries after encapsulation.
The operating voltage for the all-solid lithium-ion battery that the present embodiment obtains is in 0V to 4.5V, in the electric current of 25mA/g Under, specific capacity is up to 92mAh/g.
Embodiment 4
A kind of all-solid lithium-ion battery, including be cascading plus plate current-collecting body 1, positive electrode material layer 2, containing lithium Solid electrolyte 3, negative electrode material layer 4 and negative current collector 5.
Wherein, plus plate current-collecting body 1 is platinum/titanium (Pt/Ti), and positive electrode material layer 2 is manganese dioxide membrane, the solid-state electricity containing lithium Solution matter 3 is LiPON solid electrolyte film, and negative electrode material layer 4 is manganese dioxide membrane, and negative current collector 5 is copper (Cu).
The preparation method of the all-solid lithium-ion battery, comprising the following steps:
The preparation of S1, anode: radio-frequency magnetron sputter method is used, with manganese dioxide (MnO2) for target as target, surface is smooth Paper as base material, platinum plating/titanium (Pt/Ti) is used as plus plate current-collecting body on it.Install target and plus plate current-collecting body Afterwards, sputtering chamber is closed, sputtering chamber is evacuated to 1.0 × 10- 4Pa is hereinafter, be passed through 100sccm argon gas and the oxygen of 20sccm Gas, then gas pressure intensity in chamber is adjusted to 1Pa；
At room temperature, rf sputtering power density is set as 1.4W/cm2, target-substrate distance 80mm, pre-sputtering 5min, with clear The impurity for managing target material surface, sputters 3h at room temperature, amorphous manganese dioxide membrane can be directly obtained in above-mentioned substrate；
The preparation of S2, solid electrolyte film: on the surface of obtained amorphous manganese dioxide membrane, continue to splash using magnetic control The mode of penetrating prepares LiPON solid electrolyte film, i.e., with Li3PO4For target, Ar and N2Gas is working gas, utilizes radio frequency magnetron Sputtering is prepared；
The preparation of S3, cathode: it will be splashed on obtained LiPON solid electrolyte film surface using radio-frequency magnetron sputter method It penetrates chamber and is evacuated to 1.0 × 10- 4Pa is hereinafter, be passed through 100sccm argon gas and the oxygen of 20sccm, then by chamber indoor gas pressure Emphasize section to 1Pa；Sputtering power density is set as 1.4W/cm2, target-substrate distance 80mm, pre-sputtering 5min, to clear up target The impurity on surface, sputters 2h at room temperature, and amorphous manganese dioxide membrane can be obtained on electrolyte；
The encapsulation of S4, negative current collector and battery: utilizing magnetically controlled DC sputtering, and metallic copper (Cu) is used as target, directly exists Negative film surface sputters to obtain Cu film as negative current collector, obtains full solid thin film lithium-ion electric finally by encapsulation Pond.
The solid-State Thin Film Li-Ion Batteries operating voltage that the present embodiment obtains is in 0V to 4.5V, in the electric current of 25mA/g Under, specific capacity is about 75mAh/g.
Embodiment 5
A kind of all-solid lithium-ion battery, including be cascading plus plate current-collecting body 1, positive electrode material layer 2, containing lithium Solid electrolyte 3, negative electrode material layer 4 and negative current collector 5.
Wherein, plus plate current-collecting body 1 is molybdenum (Mo), and positive electrode material layer 2 is manganese dioxide membrane, the solid electrolyte 3 containing lithium For LiPON solid electrolyte film, negative electrode material layer 4 is manganese dioxide membrane, and negative current collector 5 is molybdenum (Mo).
The preparation method of the all-solid lithium-ion battery, comprising the following steps:
The preparation of S1, anode: radio-frequency magnetron sputter method is used, with manganese dioxide (MnO2) target is as target, polyimides As base material, molybdenum (Mo) plus plate current-collecting body is plated on it.After installing target and plus plate current-collecting body, sputtering chamber is closed, Sputtering chamber is evacuated to 1.0 × 10- 4Pa is hereinafter, be passed through 100sccm argon gas and the oxygen of 20sccm, then by chamber Indoor Air Body pressure is adjusted to 1Pa；
Substrate is heated to 200 DEG C, sets rf sputtering power density as 1.4W/cm2, target-substrate distance 80mm, pre-sputtering 5min sputters 3h, directly can obtain manganese dioxide membrane in above-mentioned substrate to clear up the impurity of target material surface；
The preparation of S2, solid electrolyte film: on the surface of obtained amorphous manganese dioxide membrane, continue to splash using magnetic control The mode of penetrating prepares LiPON solid electrolyte film, i.e., with Li3PO4For target, Ar and N2Gas is working gas, utilizes radio frequency magnetron Sputtering is prepared；
The preparation of S3, cathode: it will be splashed on obtained LiPON solid electrolyte film surface using radio-frequency magnetron sputter method It penetrates chamber and is evacuated to 1.0 × 10- 4Pa is hereinafter, be passed through 40sccm argon gas and the oxygen of 10sccm, then by gas pressure intensity in chamber Adjust 1Pa.Substrate is heated to 200 DEG C, sets sputtering power density as 1.4W/cm2, target-substrate distance 80mm splashes in advance 5min is penetrated, to clear up the impurity of target material surface, 2h is sputtered at room temperature, manganese dioxide membrane can be obtained on electrolyte；
The encapsulation of S4, negative current collector and battery: utilizing magnetically controlled DC sputtering, and metal molybdenum (Mo) is used as target, directly exists Negative film surface sputters to obtain Mo film as negative current collector, obtains full solid thin film lithium-ion electric finally by encapsulation Pond.
The solid-State Thin Film Li-Ion Batteries operating voltage that the present embodiment obtains is in 0V to 4.5V, in the electric current of 25mA/g Under, specific capacity is about 95mAh/g.
Embodiment 6
A kind of all-solid lithium-ion battery, including be cascading plus plate current-collecting body 1, positive electrode material layer 2, containing lithium Solid electrolyte 3, negative electrode material layer 4 and negative current collector 5.
Wherein, plus plate current-collecting body 1 is molybdenum (Mo), and positive electrode material layer 2 is manganese dioxide membrane, the solid electrolyte 3 containing lithium For LiPON solid electrolyte film, negative electrode material layer 4 is manganese dioxide membrane, and negative current collector 5 is molybdenum (Mo).
The preparation method of the all-solid lithium-ion battery, comprising the following steps:
The preparation of S1, anode: radio-frequency magnetron sputter method is used, with manganese dioxide (MnO2) target is as target, silicon wafer conduct Base material plates molybdenum (Mo) plus plate current-collecting body on it.After installing target and plus plate current-collecting body, sputtering chamber is closed, will be splashed It penetrates chamber and is evacuated to 1.0 × 10- 4Pa is hereinafter, be passed through 100sccm argon gas and the oxygen of 20sccm, then by chamber indoor gas pressure Emphasize section to 1Pa；
Substrate is heated to 400 DEG C, sets rf sputtering power density as 1.4W/cm2, target-substrate distance 80mm, pre-sputtering 5min sputters 3h, directly can obtain manganese dioxide membrane in above-mentioned substrate to clear up the impurity of target material surface；
The preparation of S2, solid electrolyte film: on the surface of obtained amorphous manganese dioxide membrane, continue to splash using magnetic control The mode of penetrating prepares LiPON solid electrolyte film, i.e., with Li3PO4For target, Ar and N2Gas is working gas, utilizes radio frequency magnetron Sputtering is prepared；
The preparation of S3, cathode: it will be splashed on obtained LiPON solid electrolyte film surface using radio-frequency magnetron sputter method It penetrates chamber and is evacuated to 1.0 × 10- 4Pa is hereinafter, be passed through 40sccm argon gas and the oxygen of 10sccm, then by gas pressure intensity in chamber Adjust 1Pa.Substrate is heated to 200 DEG C, sets sputtering power density as 1.4W/cm2, target-substrate distance 80mm splashes in advance 5min is penetrated, to clear up the impurity of target material surface, 2h is sputtered at room temperature, manganese dioxide membrane can be obtained on electrolyte；
The encapsulation of S4, negative current collector and battery: utilizing magnetically controlled DC sputtering, and metal molybdenum (Mo) is used as target, directly exists Negative film surface sputters to obtain Mo film as negative current collector, obtains full solid thin film lithium-ion electric finally by encapsulation Pond.
The solid-State Thin Film Li-Ion Batteries operating voltage that the present embodiment obtains is in 0V to 4.5V, in the electric current of 25mA/g Under, specific capacity is about 110mAh/g.
Comparative example 1
A kind of existing all-solid lithium-ion battery, including be cascading plus plate current-collecting body, positive electrode material layer, contain Solid electrolyte, negative electrode material layer and the negative current collector of lithium.
Wherein, plus plate current-collecting body Pt/Ti, positive electrode material layer LiCoO2, the solid electrolyte containing lithium is LiPON, is born Pole material layer is lithium metal, and negative current collector is copper.
Preparation method includes:
The preparation of S1, anode: radio-frequency magnetron sputter method is used, with cobalt acid lithium (LiCoO2) target is as target, polyimides As base material, Pt/Ti is plated on it as plus plate current-collecting body.After installing target and plus plate current-collecting body, sputtering chamber is closed Sputtering chamber is evacuated to 1.0 × 10 by room- 4Pa, then will be in chamber hereinafter, be passed through 100sccm argon gas and the oxygen of 20sccm Gas pressure intensity is adjusted to 1Pa；
Substrate is heated to 300 DEG C, sets rf sputtering power density as 1.4W/cm2, target-substrate distance 80mm, pre-sputtering 5min sputters 3h to clear up the impurity of target material surface at room temperature, directly can obtain LiCoO in above-mentioned substrate2Film；
The preparation of S2, solid electrolyte film: in obtained LiCoO2The surface of film is continued using magnetron sputtering mode LiPON solid electrolyte film is prepared, i.e., with Li3PO4For target, Ar and N2Gas is working gas, utilizes rf magnetron sputtering system It is standby to obtain；
The preparation of S3, cathode: on obtained LiPON solid electrolyte film surface, using thermal evaporation, in electrolyte meter Face evaporation plates one layer of metal Li film；
The encapsulation of S4, negative current collector and battery: utilizing magnetically controlled DC sputtering, and metallic copper (Cu) is used as target, directly exists Negative film surface sputters to obtain Cu film as negative current collector, obtains full solid thin film lithium-ion electric finally by encapsulation Pond.
Above as can be seen that the positive electrode material layer and negative electrode material layer of comparative example 1 are different from the embodiment of the present invention 1.It is right The solid-State Thin Film Li-Ion Batteries of ratio 1 are due to LiCoO2Sputter temperature be 300 DEG C, not thermally treated, crystallinity has Limit, in the operating voltage of 3V to 4.2V, under the electric current of 25mA/g, specific capacity is about 30mAh/g.If improving its heat treatment Temperature, substrate then be easy temperature distortion, decomposition and fail.In addition, the anode and cathode in the battery system use difference Equipment preparation, preparation technological parameter it is different, and lithium metal need in glove box or in high-level ultra-clean chamber Preparation could save.And the positive and negative anodes of the embodiment of the present invention are when all using Mn oxide, it can be using identical equipment, close Technique prepares positive and negative pole material, and can prepare and save under dry atmospheric environment, and technique and equipment cost obviously drop It is low.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution The range of scheme.

Claims (10)

1. a kind of all-solid lithium-ion battery, which is characterized in that including anode and cathode；
Positive electrode active materials in the anode include containing manganese compound；
Negative electrode active material in the cathode includes containing manganese compound.
2. all-solid lithium-ion battery according to claim 1, which is characterized in that the manganese compound that contains includes manganese oxidation Object；
Preferably, the Mn oxide includes one of manganese dioxide, mangano-manganic oxide or manganese sesquioxide managnic oxide or a variety of groups It closes.
3. all-solid lithium-ion battery according to claim 1, which is characterized in that it is described anode include anode collection layer and It is formed in the positive electrode material layer of the anode collection layer surface, the positive electrode material layer includes positive electrode active materials, the anode Active material includes containing manganese compound；
The cathode includes negative pole currect collecting layer and the negative electrode material layer for being formed in the negative pole currect collecting layer surface, the negative electrode material Layer includes negative electrode active material, and the negative electrode active material includes containing manganese compound；
Preferably, the positive electrode material layer is manganese-salt phosphating；
Preferably, the negative electrode material layer is manganese-salt phosphating.
4. described in any item all-solid lithium-ion batteries according to claim 1~3, which is characterized in that further include consolidating containing lithium State electrolyte；
Preferably, the all-solid lithium-ion battery includes the anode collection layer being cascading, positive electrode material layer, containing lithium Solid electrolyte, negative electrode material layer and negative pole currect collecting layer；
Preferably, the solid electrolyte containing lithium includes LiPON, LiSiON, Li2SiO3、Li7La3Zr2O12、LiBO3、 Li3PO4、Li3OX or LiTi2(PO4)3One of or a variety of combinations, wherein X be F, Cl or Br；
It is highly preferred that the solid electrolyte containing lithium is LiPON.
5. described in any item all-solid lithium-ion batteries according to claim 1~3, which is characterized in that all solid lithium from Sub- battery is hull cell.
6. the preparation method of the described in any item all-solid lithium-ion batteries of Claims 1 to 5, which is characterized in that make respectively Anode and cathode；
The preparation method of anode and cathode independently includes magnetron sputtering method, pulsed laser deposition, chemical vapour deposition technique or painting At least one of embrane method, preferably magnetron sputtering method.
7. the preparation method of all-solid lithium-ion battery according to claim 6, which is characterized in that use magnetron sputtering method Preparing anode includes: under conditions of being passed through oxygen and inert gas, to deposit anode in anode collection layer surface using manganese as target Material layer obtains anode.
8. the preparation method of all-solid lithium-ion battery according to claim 6, which is characterized in that use magnetron sputtering method Preparing cathode includes: under conditions of being passed through oxygen and inert gas, to deposit cathode in negative electrode material layer surface using manganese as target Current collector layer obtains cathode.
9. according to the preparation method of the described in any item all-solid lithium-ion batteries of claim 6~8, which is characterized in that described Anode includes anode collection layer and positive electrode material layer, and the cathode includes negative pole currect collecting layer and negative electrode material layer；
Positive electrode material layer, the solid electrolyte containing lithium, negative electrode material layer and cathode are sequentially prepared in the anode collection layer surface Current collector layer obtains the all-solid lithium-ion battery；
Preferably, positive electrode material layer is first deposited in anode collection layer surface using magnetron sputtering method, then is existed using magnetron sputtering method Positive electrode layer surface prepares the solid electrolyte containing lithium, then using magnetron sputtering method in the solid electrolyte surface system containing lithium Standby negative electrode material layer finally deposits negative pole currect collecting layer in negative electrode material layer surface using magnetron sputtering method.
10. a kind of electrical equipment, which is characterized in that including the described in any item all-solid lithium-ion batteries of Claims 1 to 5.
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