CN108963328A - Solid state lithium battery and preparation method based on multi-functional layered composite solid electrolyte - Google Patents
Solid state lithium battery and preparation method based on multi-functional layered composite solid electrolyte Download PDFInfo
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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- H—ELECTRICITY
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- H—ELECTRICITY
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Abstract
Solid state lithium battery disclosed by the invention based on multi-functional layered composite solid electrolyte, including anode, multi-functional layered composite solid electrolyte layer and battery cathode；The multi-functional layered composite solid electrolyte layer is between anode and battery cathode.In addition, the invention also discloses a kind of preparation methods of solid state lithium battery.Solid state lithium battery and preparation method disclosed by the invention based on multi-functional layered composite solid electrolyte, can guarantee between solid electrolyte and electrode active material and solid electrolyte and battery electrode it is soft contact, reduce the interface impedance between solid electrolyte and electrode active material and solid electrolyte and battery electrode.
Description
Technical field
The present invention relates to battery technology fields, more particularly to the solid-state lithium based on multi-functional layered composite solid electrolyte
Battery and preparation method.
Background technique
Currently, lithium ion battery have many advantages, such as specific energy is high, be recycled often, storage time it is long, not only just
It takes such as mobile phone, DV and laptop computer on formula electronic equipment to be used widely, and is widely used in electricity
In terms of the large and medium-sized electrical equipment such as electrical automobile, electric bicycle and electric tool, therefore, not in view of lithium ion battery applications
It is disconnected to expand, so that demand of the market to lithium ion battery energy density is being continuously improved, meanwhile, so as to the peace of lithium ion battery
Full performance requirement is higher and higher.
Currently, the intrinsic essential safety attribute of solid state lithium battery, receives significant attention it.On the one hand, traditional lithium from
There are the security risks that leakage, easy catching fire even explode for sub- battery, therefore, boiling point height and nonflammable solid state electrolysis
Matter becomes the important technology selection for solving lithium ion battery safety problem.On the other hand, the chemical inertness of solid electrolyte is utilized
And high-intensitive mechanical characteristics, inside battery side reaction can be inhibited to occur and Li dendrite is inhibited to be formed, and then optimize and promote lithium electricity
The application that the safety in pond is lithium metal in lithium ion battery provides solution.
Solid electrolyte is the key technology of solid lithium battery.Solid electrolyte mainly includes oxide, sulfide, gathers
Close object and hybrid solid-state electrolyte.Wherein, elasticity is good, easily film forming, machining property is good for polymer dielectric, is easy to work
Industryization preparation, still, lower conductivity at room temperature restricts the large-scale application of polymer dielectric always.
Therefore, there is an urgent need to develop a kind of technologies out at present, can effectively promote the ion-conductance that solid electrolyte has
Conductance, thus guarantee between solid electrolyte and electrode active material and solid electrolyte and battery electrode it is soft contact, reduce
Interface impedance between solid electrolyte and battery electrode.
Summary of the invention
In view of this, the object of the present invention is to provide based on multi-functional layered composite solid electrolyte solid state lithium battery and
Preparation method, the ionic conductivity having by effectively promoting solid electrolyte, to guarantee solid electrolyte and electrode active
Property material and solid electrolyte and battery electrode between it is soft contact, reduce solid electrolyte and electrode active material and solid-state
Interface impedance between electrolyte and battery electrode is conducive to widely production application, is of great practical significance.
For this purpose, the present invention provides the solid state lithium battery based on multi-functional layered composite solid electrolyte, including battery is just
Pole, multi-functional layered composite solid electrolyte layer and battery cathode；
The multi-functional layered composite solid electrolyte layer is between anode and battery cathode.
Wherein, the multi-functional layered composite solid electrolyte layer includes bulk electrolyte layer, the bulk electrolyte layer
Two sides up and down be respectively provided with buffer electrolyte layer.
Wherein, the buffer electrolyte layer includes: weight percent be 10%~90% solid polyelectrolyte,
1%~60% oxidation silicon substrate framework structured compound and 1%~60% ionic liquid.
Wherein, the anode is NEW TYPE OF COMPOSITE anode, including plus plate current-collecting body, the plus plate current-collecting body surface coating
There is one layer of composite solid electrolyte；
The battery cathode is NEW TYPE OF COMPOSITE cathode, including negative current collector, and the negative current collector surface is coated with one
Layer composite solid electrolyte；
The composite solid electrolyte include weight percent be 10%~90% solid polyelectrolyte, 1%~
60% oxidation silicon substrate framework structured compound and 1%~60% ionic liquid.
Wherein, the solid polyelectrolyte includes the lithium salts and 50%~95% that weight percent is 5%~50%
Polymer；
The polymer includes polyethylene glycol oxide PEO, polyacrylonitrile (PAN), Kynoar PVDF, polyethylene glycol oxide PEO
At least one of modified structure and polyacrylonitrile (PAN) modified structure；
The lithium salts includes bis trifluoromethyl sulfimide lithium LiTFSI, lithium hexafluoro phosphate LiPF6, LiBF4 LiBF4
With hexafluoroarsenate lithium LiAsF6At least one of；；
Cation in the ionic liquid includes alkyl-substituted pyrroles, thiazole, piperidines, imidazoles, quaternary ammonium salt He quaternary phosphine
At least one of salt, the anion in the ionic liquid includes tetrachloro aluminate [AlCl4]-, hexafluoro-phosphate radical [PF6]-、
Trifluoromethanesulfonimide root [(CF3SO2)2N]-, trifluoromethane sulfonic acid root [CF3SO3]-, tetrafluoroborate [BF4]-, nitrate anion
[NO3]-, bromide ion Br-With chloride ion Cl-One of.
In addition, the present invention also provides a kind of preparation methods of solid state lithium battery, comprising the following steps:
Step 1: preparing composite solid electrolyte solution；
Step 2: composite solid electrolyte solution is coated on plus plate current-collecting body, then dry, prepares to have and delay
The anode of electrolyte layer is rushed, and composite solid electrolyte solution is coated on negative current collector, is then dried, is obtained
Battery cathode with buffer electrolyte layer；
Step 3: bulk electrolyte layer is placed on the anode with buffer electrolyte layer and there is buffer electrolyte
Between the battery cathode of layer, it is then placed in battery case, prepares solid state lithium battery.
Wherein, in second step, specific drying operation are as follows: be initially positioned in dry atmosphere and dry, drying temperature be 40~
130 DEG C, drying time is 0~20 hour, is then placed in vacuum tank again and carries out secondary drying, and drying temperature is 40~130
DEG C, drying time is 0~60 hour.
Wherein, the bulk electrolyte layer with a thickness of 100 nanometers~100 microns；
The buffer electrolyte layer with a thickness of 100 nanometers~100 microns.
Wherein, the first step specifically includes the following steps:
Polymer and lithium salts are dissolved in preset solvent by the first sub-step, are configured to solid polyelectrolyte solution,
Wherein polymer and lithium salts form solid polyelectrolyte together；
Second sub-step, tetraethyl orthosilicate is dissolved in formic acid, is then mixed with ionic liquid, be configured to by from
First mixed solution of sub- liquid, tetraethyl orthosilicate and formic acid composition；
Third sub-step: solid polyelectrolyte solution and the first mixed solution are mixed according to preset quality ratio
It closes, stirs evenly and obtain composite solid electrolyte solution；
In the first sub-step, the preset solvent is tetrahydrofuran；
In the first sub-step, the solid content of the solid polyelectrolyte solution is 1%~50%, and compound
In the solid content of solid electrolyte, the weight ratio between polymer and lithium salts is (1:1)~(95:5)；
The polymer includes polyethylene glycol oxide PEO, polyacrylonitrile (PAN), Kynoar PVDF, polyethylene glycol oxide PEO
At least one of modified structure and polyacrylonitrile (PAN) modified structure；
The lithium salts includes bis trifluoromethyl sulfimide lithium LiTFSI, lithium hexafluoro phosphate LiPF6, LiBF4 LiBF4
With hexafluoroarsenate lithium LiAsF6At least one of；
In the second sub-step, in first mixed solution, the weight percent of ionic liquid is 1%~30%,
The weight percent of tetraethyl orthosilicate is 1%~20%, and the weight percent of formic acid is 50%~98%；
Cation in the ionic liquid includes alkyl-substituted pyrroles, thiazole, piperidines, imidazoles, quaternary ammonium salt He quaternary phosphine
At least one of salt, the anion in the ionic liquid includes tetrachloro aluminate [AlCl4]-, hexafluoro-phosphate radical [PF6]-、
Trifluoromethanesulfonimide root [(CF3SO2)2N]-, trifluoromethane sulfonic acid root [CF3SO3]-, tetrafluoroborate [BF4]-, nitrate anion
[NO3]-, bromide ion Br-With chloride ion Cl-One of；
In third sub-step, the preset mass ratio is 1:1.
By the above technical solution provided by the invention as it can be seen that compared with prior art, the present invention provides be based on more function
The solid state lithium battery and preparation method of energy stratiform composite solid electrolyte, the ion having by effectively promoting solid electrolyte
Conductivity, thus guarantee between solid electrolyte and electrode active material and solid electrolyte and battery electrode it is soft contact, drop
Interface impedance between low solid electrolyte and electrode active material and solid electrolyte and battery electrode is conducive to widely give birth to
Application is produced, is of great practical significance.
By applying the solid state lithium battery provided by the invention based on multi-functional layered composite solid electrolyte, may be implemented
Using the electrolyte and combination electrode of solid electrolyte and electrode active material and solid electrolyte and interelectrode soft contact
The solid-state finally prepared is advantageously reduced for battery component so as to further prepare the solid state lithium battery of low impedance structure
The impedance of lithium battery is advantageously implemented the large-scale application of solid state lithium battery.
Detailed description of the invention
Fig. 1 is a kind of flow chart of the preparation method of solid state lithium battery provided by the invention；
Fig. 2 is the preparation method of multi-functional layered composite solid electrolyte provided by the invention, is prepared in embodiment 1 new
The oxidizing potential test curve contrast schematic diagram of type composite solid electrolyte and existing polyethylene glycol oxide PEO electrolyte, wherein
A curve indicates that polyethylene glycol oxide PEO, B curve indicate composite solid electrolyte provided by the invention.
Specific embodiment
In order to enable those skilled in the art to better understand the solution of the present invention, with reference to the accompanying drawing with embodiment to this
Invention is described in further detail.
The present invention provides the solid state lithium battery based on multi-functional layered composite solid electrolyte, including it is anode, more
Function stratiform composite solid electrolyte layer and battery cathode；
The multi-functional layered composite solid electrolyte layer is between anode and battery cathode.
In the present invention, in specific implementation, the multi-functional layered composite solid electrolyte layer includes bulk electrolyte layer,
The two sides up and down of the bulk electrolyte layer are respectively provided with buffer electrolyte layer.That is, its structure is from top to bottom successively
For the interlayer structure of buffer electrolyte layer, bulk electrolyte layer and buffer layer electrolyte stratiform, wherein bulk electrolyte layer plays knot
Structure support, the effect of lithium ion transport, and high mechanical strength is provided, prevent penetrating for Li dendrite.And buffer electrolyte layer be by
Solid polyelectrolyte, oxidation silicon substrate skeleton structure and ionic liquid composition.
In specific implementation, the bulk electrolyte layer with a thickness of 100 nanometers~100 microns.
In specific implementation, the buffer electrolyte layer with a thickness of 100 nanometers~100 microns.
In specific implementation, the bulk electrolyte can be traditional solid state battery electrolyte, including polymer, oxidation
Object, sulfide or composite electrolyte.
Wherein, polymer includes polypropylene carbonate PPC, polyethylene glycol oxide PEO, oxide include lithium lanthanum zirconium oxygen LLZO,
Lithium aluminium germanium phosphorus LAGP etc., sulfide include lithium phosphorus sulphur LPS, and composite electrolyte includes the polypropylene carbonate PPC being combined with each other
With the lithium aluminium germanium phosphorus LAGP and polyethylene glycol oxide PEO being combined with each other and lithium lanthanum zirconium oxygen LLZO.
In specific implementation, the buffer electrolyte layer includes: the polymer solid electricity that weight percent is 10%~90%
Xie Zhi, 1%~60% oxidation silicon substrate framework structured compound and 1%~60% ionic liquid.
In the present invention, in specific implementation, the solid polyelectrolyte includes that weight percent is 5%~50%
Lithium salts and 50%~95% polymer.
In specific implementation, the polymer includes polyethylene glycol oxide PEO, polyacrylonitrile (PAN), Kynoar PVDF, gathers
At least one of ethylene oxide PEO modified structure and polyacrylonitrile (PAN) modified structure.
In specific implementation, the lithium salts includes bis trifluoromethyl sulfimide lithium LiTFSI, lithium hexafluoro phosphate LiPF6, four
Lithium fluoroborate LiBF4With hexafluoroarsenate lithium LiAsF6At least one of.
In the present invention, in specific implementation, the cation in the ionic liquid include alkyl-substituted pyrroles, thiazole,
Piperidines, imidazoles, quaternary ammonium salt He one of quaternary alkylphosphonium salt, the anion in the ionic liquid includes tetrachloro aluminate [AlCl4]-、
Hexafluoro-phosphate radical [PF6]-, trifluoromethanesulfonimide root
[(CF3SO2)2N]-, trifluoromethane sulfonic acid root [CF3SO3]-, tetrafluoroborate [BF4]-, nitrate anion [NO3]-, bromine from
Sub- Br-With chloride ion Cl-One of.
It should be noted that for the present invention, the composite solid electrolyte provided, be by solid polyelectrolyte,
Aoxidize silicon substrate framework structured compound and ionic liquid composition.
Wherein, solid polyelectrolyte aoxidizes silicon substrate skeleton structure for constructing main structure and transmitting lithium ion
The fluid dynamics that object is used to carry and limit ionic liquid are closed, ionic liquid and oxidation silicon substrate framework structured compound are for filling out
It fills in solid polyelectrolyte main structure, solid electrolyte and active material and the lithium ion finally prepared may be implemented
The interelectrode soft contact of battery, to reduce the boundary between active material, between the electrode and solid electrolyte of lithium ion battery
Face impedance.
In the present invention, in specific implementation, the anode is preferably NEW TYPE OF COMPOSITE anode, including plus plate current-collecting body,
The plus plate current-collecting body surface is coated with one layer of composite solid electrolyte.
In specific implementation, the composite solid electrolyte includes the polymer solid electricity that weight percent is 10%~90%
Xie Zhi, 1%~60% oxidation silicon substrate framework structured compound and 1%~60% ionic liquid.
In specific implementation, the solid polyelectrolyte includes the lithium salts and 50% that weight percent is 5%~50%
~95% polymer.
In specific implementation, the polymer includes polyethylene glycol oxide PEO, polyacrylonitrile (PAN), Kynoar PVDF, gathers
At least one of ethylene oxide PEO modified structure and polyacrylonitrile (PAN) modified structure.
In specific implementation, the lithium salts includes bis trifluoromethyl sulfimide lithium LiTFSI, lithium hexafluoro phosphate LiPF6, four
Lithium fluoroborate LiBF4With hexafluoroarsenate lithium LiAsF6At least one of.
In the present invention, in specific implementation, the cation in the ionic liquid include alkyl-substituted pyrroles, thiazole,
Piperidines, imidazoles, quaternary ammonium salt He one of quaternary alkylphosphonium salt, the anion in the ionic liquid includes tetrachloro aluminate [AlCl4]-、
Hexafluoro-phosphate radical [PF6]-, trifluoromethanesulfonimide root [(CF3SO2)2N]-, trifluoromethane sulfonic acid root [CF3SO3]-, tetrafluoro boron
Acid group [BF4]-, nitrate anion [NO3]-, bromide ion Br-With chloride ion Cl-One of.
It should be noted that for the present invention, the composite solid electrolyte provided, be by solid polyelectrolyte,
Aoxidize silicon substrate framework structured compound and ionic liquid composition.
Wherein, solid polyelectrolyte aoxidizes silicon substrate skeleton structure for constructing main structure and transmitting lithium ion
The fluid dynamics that object is used to carry and limit ionic liquid are closed, ionic liquid and oxidation silicon substrate framework structured compound are for filling out
It fills in solid polyelectrolyte main structure, solid electrolyte and active material and the lithium ion finally prepared may be implemented
The interelectrode soft contact of battery, to reduce the boundary between active material, between the electrode and solid electrolyte of lithium ion battery
Face impedance.
It should be noted that oxidation silicon substrate framework structured compound: being obtained especially by the method for collosol and gel, i.e., former silicon
Sour tetra-ethyl ester heats generation hydrolysis in formic acid solution, condensation reaction generates silica skeleton structure.The silica skeleton structure
Liquefied compound can be carried, gel is formed.Herein similarly to the prior art, description is not further spread out.
In the present invention, in specific implementation, the battery cathode is preferably NEW TYPE OF COMPOSITE cathode, including negative current collector,
The negative current collector surface be coated with one layer of composite solid electrolyte, the concrete component and outfit of the composite solid electrolyte,
With noted earlier.
In addition, shown in Figure 1, the present invention also provides a kind of preparation methods of solid state lithium battery, for specifically preparing
Mentioned-above solid state lithium battery, this method specifically includes the following steps:
Step 1: preparing composite solid electrolyte solution；
Step 2: composite solid electrolyte solution is coated on plus plate current-collecting body (such as copper foil), then dry, prepares
Obtain have buffer electrolyte layer anode, and by composite solid electrolyte solution be coated to negative current collector (such as
Aluminium foil) on, it then dries, obtains the battery cathode with buffer electrolyte layer；
Step 3: bulk electrolyte layer is placed on the anode with buffer electrolyte layer and there is buffer electrolyte
Between the battery cathode of layer, it is then placed in battery case (such as stainless steel case), prepares solid state lithium battery.
For the present invention, in second step, specific drying operation are as follows: it is initially positioned in dry atmosphere and dries, drying temperature
It is 40~130 DEG C, drying time is 0~20 hour, it is then placed in vacuum tank again and carries out secondary drying, drying temperature 40
~130 DEG C, drying time is 0~60 hour.
For the present invention, the first step specifically includes the following steps:
Polymer and lithium salts are dissolved in preset solvent by the first sub-step, are configured to solid polyelectrolyte solution,
Wherein polymer and lithium salts form solid polyelectrolyte together；
Second sub-step, tetraethyl orthosilicate is dissolved in formic acid, is then mixed with ionic liquid, be configured to by from
First mixed solution of sub- liquid, tetraethyl orthosilicate and formic acid composition；
Third sub-step: solid polyelectrolyte solution and the first mixed solution are mixed according to preset quality ratio
It closes, stirs evenly and obtain composite solid electrolyte solution.
In the present invention, in specific implementation, in the first sub-step, the preset solvent is tetrahydrofuran.
In the present invention, in specific implementation, in the first sub-step, the solid content of the solid polyelectrolyte solution
(weight) is 1%~50%, and in the solid content of composite solid electrolyte, the weight ratio between polymer and lithium salts is
(1:1)~(95:5).
In specific implementation, the polymer includes polyethylene glycol oxide PEO, polyacrylonitrile (PAN), Kynoar PVDF, gathers
At least one of ethylene oxide PEO modified structure and polyacrylonitrile (PAN) modified structure.
In specific implementation, the lithium salts includes bis trifluoromethyl sulfimide lithium LiTFSI, lithium hexafluoro phosphate LiPF6, four
Lithium fluoroborate LiBF4With hexafluoroarsenate lithium LiAsF6At least one of.
In the present invention, in the second sub-step, in first mixed solution, the weight percent of ionic liquid is
1%~30%, the weight percent of tetraethyl orthosilicate is 1%~20%, and the weight percent of formic acid is 50%~98%.
In specific implementation, the cation in the ionic liquid includes alkyl-substituted pyrroles, thiazole, piperidines, imidazoles, season
At least one of ammonium salt He quaternary alkylphosphonium salt, the anion in the ionic liquid includes tetrachloro aluminate [AlCl4]-, hexafluorophosphoric acid
Root [PF6]-, trifluoromethanesulfonimide root [(CF3SO2)2N]-, trifluoromethane sulfonic acid root [CF3SO3]-, tetrafluoroborate
[BF4]-, nitrate anion [NO3]-, bromide ion Br-With chloride ion Cl-One of.
In the present invention, in third sub-step, the preset mass ratio is 1:1.
In specific implementation, the bulk electrolyte layer with a thickness of 100 nanometers~100 microns.
In specific implementation, the buffer electrolyte layer with a thickness of 100 nanometers~100 microns.
In specific implementation, the bulk electrolyte can be traditional solid state battery electrolyte, including polymer, oxidation
Object, sulfide or composite electrolyte.
Below with reference to embodiment 1, illustrate the preparation method of a kind of solid state lithium battery provided according to the present invention, production is based on
The detailed process of the solid state lithium battery of multi-functional layered composite solid electrolyte.
Embodiment 1
In specific embodiment 1, the present invention prepares the solid state lithium battery based on multi-functional layered composite solid electrolyte, including
Following steps:
Step 1: firstly, the lithium salts LiTFSI of the polymer P EO (400,000 molecular weight) of 5g, 5g is taken to be dissolved in the solvent four of 90g
In hydrogen furans, be configured to solid polyelectrolyte solution, weight percentage: polymer P EO is 5%, and lithium salts LiTFSI is
5%；Then, it takes the tetraethyl orthosilicate of 10g to be dissolved in 80g formic acid, and mixes the ionic liquid of 10g, the solion is specific
Are as follows: bis- (trifluoro methylsulfonyl) inferior amine salts of 1- methyl-1-propyl pyrrole alkane are configured to by ionic liquid, tetraethyl orthosilicate and first
First mixed solution of acid composition, wherein weight percentage are as follows: tetraethyl orthosilicate 10%, 1- methyl-1-propyl pyrrole
Bis- (trifluoro methylsulfonyl) inferior amine salts of alkane are 10%, formic acid 80%；Then, solid polyelectrolyte solution and first are mixed
Solution is mixed according to mass ratio 1:1, is stirred evenly and is obtained composite solid electrolyte solution；
Second step is respectively coated using composite solid electrolyte solution prepared by the first step in plus plate current-collecting body and cathode collection
It on fluid, is then placed in dry atmosphere and dries first, drying temperature is 80 DEG C, and drying time is 8 hours, is then placed again
The secondary drying in vacuum tank, drying temperature are 100 DEG C, and drying time is 24 hours.Control the coating of composite solid electrolyte
With a thickness of 5 microns, the anode and battery cathode with buffer electrolyte layer are obtained；
Step 3: bulk electrolyte layer is electric using 20 microns thick of PEO base according to the conventional assembly method of solid state lithium battery
Plasma membrane is solved, bulk electrolyte layer is placed on the anode with buffer electrolyte layer and the battery with buffer electrolyte layer
Between cathode, it is then placed in battery case (such as stainless steel case), finally prepares solid state lithium battery.
Fig. 2 is the preparation method with composite solid electrolyte provided by the invention, in the preparation of embodiment 1 based on novel
The oxidizing potential test curve contrast schematic diagram of composite solid electrolyte and existing polyethylene glycol oxide PEO electrolyte, wherein A
Curve indicates that polyethylene glycol oxide PEO, B curve indicate composite solid electrolyte provided by the invention.
The NEW TYPE OF COMPOSITE solid electrolyte prepared in embodiment 1 is by solid polyelectrolyte, oxidation silicon substrate skeleton knot
Structure compound and ionic liquid composition.Ionic liquid or oxidation silicon substrate gel structure are for being filled in solid polyelectrolyte master
In body structure, may be implemented the lithium ion battery that solid electrolyte is prepared with active material and finally it is interelectrode it is soft contact,
To reduce the interface impedance between active material, between the electrode and solid electrolyte of lithium ion battery, while improving electrolysis
The anti-oxidant current potential of matter.Fig. 2 is that oxidizing potential test result is shown, with pure polyethylene glycol oxide PEO electrolyte phase ratio, the present invention
The New Solid electrolyte of offer has higher oxidizing potential.
Therefore, provided by the invention based on multi-functional layered multiple based on statement above it is found that compared with prior art
The solid state lithium battery and preparation method for closing solid electrolyte, the ionic conductivity having by effectively promoting solid electrolyte,
Soft to guarantee between solid electrolyte and electrode active material and solid electrolyte and battery electrode contacts, and reduces solid-state electricity
The interface impedance between matter and electrode active material and solid electrolyte and battery electrode is solved, widely production application is conducive to,
It is of great practical significance.
By applying the solid state lithium battery provided by the invention based on multi-functional layered composite solid electrolyte, may be implemented
Using the electrolyte and combination electrode of solid electrolyte and electrode active material and solid electrolyte and interelectrode soft contact
The solid-state finally prepared is advantageously reduced for battery component so as to further prepare the solid state lithium battery of low impedance structure
The impedance of lithium battery is advantageously implemented the large-scale application of solid state lithium battery.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. the solid state lithium battery based on multi-functional layered composite solid electrolyte, which is characterized in that including anode, multi-functional
Lamellar composite solid-state electrolyte layer and battery cathode；
The multi-functional layered composite solid electrolyte layer is between anode and battery cathode.
2. solid state lithium battery as described in claim 1, which is characterized in that the multi-functional layered composite solid electrolyte layer packet
Bulk electrolyte layer is included, the two sides up and down of the bulk electrolyte layer are respectively provided with buffer electrolyte layer.
3. solid state lithium battery as described in claim 1, which is characterized in that the buffer electrolyte layer includes: weight percent
For 10%~90% solid polyelectrolyte, 1%~60% oxidation silicon substrate framework structured compound and 1%~60%
Ionic liquid.
4. solid state lithium battery as described in claim 1, which is characterized in that the anode is NEW TYPE OF COMPOSITE anode, including
Plus plate current-collecting body, the plus plate current-collecting body surface are coated with one layer of composite solid electrolyte；
The battery cathode is NEW TYPE OF COMPOSITE cathode, including negative current collector, and the negative current collector surface is coated with one layer again
Close solid electrolyte；
The composite solid electrolyte includes the solid polyelectrolyte that weight percent is 10%~90%, 1%~60%
Oxidation silicon substrate framework structured compound and 1%~60% ionic liquid.
5. solid state lithium battery as described in claim 3 or 4, which is characterized in that the solid polyelectrolyte includes weight
Percentage is 5%~50% lithium salts and 50%~95% polymer；
The polymer includes polyethylene glycol oxide PEO, polyacrylonitrile (PAN), Kynoar PVDF, polyethylene glycol oxide PEO modification
At least one of structure and polyacrylonitrile (PAN) modified structure；
The lithium salts includes bis trifluoromethyl sulfimide lithium LiTFSI, lithium hexafluoro phosphate LiPF6, LiBF4 LiBF4With six
Fluorine arsenic acid lithium LiAsF6At least one of；
Cation in the ionic liquid includes alkyl-substituted pyrroles, thiazole, piperidines, imidazoles, quaternary ammonium salt He in quaternary alkylphosphonium salt
At least one, the anion in the ionic liquid includes tetrachloro aluminate [AlCl4]-, hexafluoro-phosphate radical [PF6]-, trifluoro
Sulfonyl methane imines root [(CF3SO2)2N]-, trifluoromethane sulfonic acid root [CF3SO3]-, tetrafluoroborate [BF4]-, nitrate anion
[NO3]-, bromide ion Br-With chloride ion Cl-One of.
6. a kind of preparation method of solid state lithium battery as described in claim 1, which comprises the following steps:
Step 1: preparing composite solid electrolyte solution；
Step 2: composite solid electrolyte solution is coated on plus plate current-collecting body, then dry, preparing has buffering electricity
The anode of matter layer is solved, and composite solid electrolyte solution is coated on negative current collector, then dries, is had
The battery cathode of buffer electrolyte layer；
Step 3: bulk electrolyte layer is placed on anode with buffer electrolyte layer and with buffer electrolyte layer
Between battery cathode, it is then placed in battery case, prepares solid state lithium battery.
7. preparation method as claimed in claim 6, which is characterized in that in second step, specific drying operation are as follows: be initially positioned at
Dried in dry atmosphere, drying temperature is 40~130 DEG C, and drying time is 0~20 hour, be then placed on again in vacuum tank into
Row secondary drying, drying temperature are 40~130 DEG C, and drying time is 0~60 hour.
8. preparation method as claimed in claim 6, which is characterized in that the bulk electrolyte layer with a thickness of 100 nanometers~
100 microns；
The buffer electrolyte layer with a thickness of 100 nanometers~100 microns.
9. preparation method as claimed in claim 6, which is characterized in that the first step specifically includes the following steps:
Polymer and lithium salts are dissolved in preset solvent by the first sub-step, are configured to solid polyelectrolyte solution, wherein
Polymer and lithium salts form solid polyelectrolyte together；
Second sub-step, tetraethyl orthosilicate is dissolved in formic acid, is then mixed with ionic liquid, is configured to by ionic liquid
First mixed solution of body, tetraethyl orthosilicate and formic acid composition；
Third sub-step: it by solid polyelectrolyte solution and the first mixed solution, is mixed, is stirred according to preset quality ratio
It mixes and uniformly obtains composite solid electrolyte solution；
In the first sub-step, the preset solvent is tetrahydrofuran；
In the first sub-step, the solid content of the solid polyelectrolyte solution is 1%~50%, and in composite solid
In the solid content of electrolyte, the weight ratio between polymer and lithium salts is (1:1)~(95:5)；
The polymer includes polyethylene glycol oxide PEO, polyacrylonitrile (PAN), Kynoar PVDF, polyethylene glycol oxide PEO modification
At least one of structure and polyacrylonitrile (PAN) modified structure；
The lithium salts includes bis trifluoromethyl sulfimide lithium LiTFSI, lithium hexafluoro phosphate LiPF6, LiBF4 LiBF4With six
Fluorine arsenic acid lithium LiAsF6At least one of；
In the second sub-step, in first mixed solution, the weight percent of ionic liquid is 1%~30%, former silicon
The weight percent of sour tetra-ethyl ester is 1%~20%, and the weight percent of formic acid is 50%~98%；
Cation in the ionic liquid includes alkyl-substituted pyrroles, thiazole, piperidines, imidazoles, quaternary ammonium salt He in quaternary alkylphosphonium salt
At least one, the anion in the ionic liquid includes tetrachloro aluminate [AlCl4]-, hexafluoro-phosphate radical [PF6]-, trifluoro
Sulfonyl methane imines root [(CF3SO2)2N]-, trifluoromethane sulfonic acid root [CF3SO3]-, tetrafluoroborate [BF4]-, nitrate anion
[NO3]-, bromide ion Br-With chloride ion Cl-One of；
In third sub-step, the preset mass ratio is 1:1.
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Application publication date: 20181207 |