CN109935898A - Solid electrolyte and its lithium battery electric core, lithium battery - Google Patents
Solid electrolyte and its lithium battery electric core, lithium battery Download PDFInfo
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- CN109935898A CN109935898A CN201711371513.3A CN201711371513A CN109935898A CN 109935898 A CN109935898 A CN 109935898A CN 201711371513 A CN201711371513 A CN 201711371513A CN 109935898 A CN109935898 A CN 109935898A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to field of lithium, in particular to solid electrolyte and lithium battery electric core, lithium battery with the solid electrolyte, the solid electrolyte includes LiaMbFxH12‑x, wherein M includes combination any one or several in B, Ga or Al.Compared to existing solid electrolyte, the compound with F atom can have bigger molecular volume, therefore can be the Li+Bigger space is provided, to improve the transfer ability of lithium ion.Further, M-F key can form rock-steady structure, therefore, solid electrolyte can electrochemical window with higher and flexibility structural stability and cycle performance can be improved in lithium ion fast transferring.Based on above structure feature, solid electrolyte modulus of shearing with higher and Young's modulus can be made.
Description
[technical field]
The present invention relates to field of lithium, in particular to a kind of solid electrolyte and its lithium battery electric core, lithium battery.
[background technique]
For conventional liquid electrolyte, all solid state electrolyte has many advantages, such as that mechanical strength is big, safety is good.So
And existing solid state electrolysis plastidome, other than sulfide, lithium ion conductivity is lower, general ionic conductivity at room temperature
Respectively less than 10-3S/cm, therefore, sulfide solid electrolyte material are the hot spot of people's research all the time.However sulfide
Solid state electrolysis confrontation water, air are very sensitive, and deposit after solid electrolyte material and positive and negative electrode material in the prior art
In biggish interface resistance, cause cycle life shorter.
The inorganic powder or thin-film material that general solid electrolyte material uses, are polycrystalline material, and do not have flexibility, existing
There is the mechanical performance of solid electrolyte poor.It would therefore be highly desirable to provide a kind of technical side of high performance sulfide solid electrolyte
Case.
[summary of the invention]
To overcome the problems, such as that existing solid electrolyte performance is bad, the present invention provides a kind of solid electrolyte and its lithium electricity
Pond battery core, lithium battery.
It is as follows that the present invention provides a technical solution to solve above-mentioned technical problem: a kind of solid electrolyte comprising
LiaMbFxH12-x, wherein M includes combination one or more of in B, Ga or Al, and numerical value a, b and x are expressed as positive number.
Preferably, the solid electrolyte includes Li2B12FxH12-x, wherein x is expressed as 1-12.
Preferably, the solid electrolyte includes Li2B12F12。
It is as follows that the present invention provides a technical solution to solve above-mentioned technical problem: a kind of lithium battery electric core, has institute as above
State solid electrolyte.
Preferably, the solid electrolyte with a thickness of 200nm-20 μm.
Preferably, the lithium battery electric core includes anode layer, and the solid electrolyte is formed in the one side of the anode layer,
Negative electrode layer is arranged in the one side far from the anode layer in the solid electrolyte.
Preferably, the anode layer includes column crystal positive electrode, and the negative electrode layer includes that lithium metal or lithium silicon-carbon are multiple
Close cathode.
Preferably, the lithium battery electric core further includes two collectors, and the collector includes two opposite main surfaces,
The anode layer is formed in one of main surface, using the anode structure as the lithium battery electric core；It is formed in another main surface
Negative electrode layer, using the negative pole structure as another lithium battery electric core.
It is as follows that the present invention provides a technical solution to solve above-mentioned technical problem: a kind of lithium battery comprising at least two
Lithium battery electric core as described above is arranged in continuous lamination, and it is positive and negative to share one between at least two lithium battery electric cores being directly superposed
Copolar collector, the positive and negative copolar collector include two opposite main surfaces, form the anode in one of main surface
Layer, using the anode structure as a wherein lithium battery electric core, forms negative electrode layer in another main surface, using as another lithium battery
The negative pole structure of core.
Preferably, it shares between two lithium battery electric cores of a positive and negative copolar collector as series connection；The lithium battery
It further include encapsulating structure, the surface for defining the lithium battery electric core parallel with the Direction of superposition of multiple lithium battery electric cores is side
Face, the encapsulating structure are disposed around the side of the lithium battery electric core.
Compared with prior art, solid electrolyte and its lithium battery electric core provided by the present invention, lithium battery have as follows
The utility model has the advantages that
One solid electrolyte and lithium battery electric core, lithium battery including the solid electrolyte are provided in the present invention, wherein
The solid electrolyte includes LiaMbFxH12-x, wherein M includes combination one or more of in B, Ga or Al, and a, b and x are indicated
For positive number.Since the structure of F atom is big compared with H atom, compared to the solid-state electricity for containing only Li atom, B atom and H atom
Xie Zhi, the compound with F atom can have bigger molecular volume, therefore bigger space can be provided for the lithium ion,
To improve the transfer ability of lithium ion.
Further, using one of B-F key, Ga-F key or Al-F key or combinations thereof, rock-steady structure can be formed, because
This, the solid electrolyte can electrochemical window with higher, electrochemical window can reach 5V or more.The solid state electrolysis
Matter further comprises face-centered cubic crystal structure (FCC, face-centered cubic), in conjunction with B-F key, Ga-F key or Al-
One of F key or combinations thereof, can make the solid electrolyte stable structure, therefore modulus of shearing with higher and higher
Young's modulus.Specifically, the modulus of shearing of solid electrolyte provided in the present embodiment can reach 2-4Gpa, Young's modulus
It can reach 6-8Gpa.
In conjunction with one of B-F key, Ga-F key or Al-F key or combinations thereof, it can further make the solid electrolyte molecule
Framework flexibility with higher, thus can guarantee lithium ion in solid electrolyte when fast transferring, LiaMbFxH12-xPoint
Subrack structure can keep stable, to improve the cycle performance and service life of the solid electrolyte.
Further, there is B-B key etc. in solid electrolyte provided by the present invention, due to compound there is stickiness and soft
Property, therefore, the solid electrolyte can be soft material, and with preferable interfacial adhesion and and electrode interface infiltration
Property, therefore, the solid electrolyte contacts well with the surface of electrode.
The present invention also provides a kind of lithium battery electric core and lithium batteries comprising solid electrolyte as described above, wherein collecting
Fluid includes two opposite main surfaces, and column crystal anode layer is formed in one of main surface, using as a lithium battery
The anode structure of core forms negative electrode layer in another main surface, using the negative pole structure as another lithium battery electric core.By in afflux
Positive and negative anodes are set on two faces of body, to form the collector of positive and negative copolar, it can be achieved that prepared by multiple lithium battery electric core laminations, from
And realize the preparation of large area solid lithium battery.
[Detailed description of the invention]
Fig. 1 is the schematic diagram of a layer structure of lithium battery electric core provided by second embodiment of the invention.
Fig. 2 is the schematic diagram of a layer structure of lithium battery electric core provided by third embodiment of the invention.
Fig. 3 is the schematic diagram of laminated structure of lithium battery provided by fourth embodiment of the invention.
Fig. 4 is the schematic diagram of laminated structure of lithium battery provided by fifth embodiment of the invention.
Fig. 5 is the schematic diagram of laminated structure of lithium battery provided by sixth embodiment of the invention.
Fig. 6 is the schematic diagram of laminated structure of the lithium battery provided by seventh embodiment of the invention with encapsulating structure.
Fig. 7 is the flow diagram of lithium battery electric core preparation method provided by eighth embodiment of the invention.
[specific embodiment]
In order to make the purpose of the present invention, technical solution and advantage are more clearly understood, below in conjunction with attached drawing and embodiment,
The present invention will be described in further detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention,
It is not intended to limit the present invention.
The first embodiment of the present invention provides a kind of solid electrolyte comprising has LiaMbFxH12-xThe chemical combination of structural formula
Object, wherein M includes combination one or more of in B, Ga or Al, and a, b and x are expressed as positive number.
As in some embodiments, when M is B, corresponding a numerical value can be that the numerical value of 2, b can be 12.Some
In particular embodiment, the LiaMbFxH12-xStructural formula can be further represented as Li2B12FxH12-x, wherein x is expressed as positive number,
Specifically, the numerical value of x is represented by 1-12.
In other specific embodiments, when M is Al, then it can be 12 that corresponding a numerical value, which can be the numerical value of 2, b,.?
In some particular embodiments, the LiaMbFxH12-xStructural formula can be further represented as Li2Al12FxH12-x, specifically, the number of x
Value is represented by 1-12.
In other specific embodiments, when M is Ga, then it can be 12 that corresponding a numerical value, which can be the numerical value of 2, b,.?
In some particular embodiments, the LiaMbFxH12-xStructural formula can be further represented as Li2Ga12FxH12-x, specifically, the number of x
Value is represented by 1-12.
In some special embodiments of the present invention, when the numerical value of x is 12, then the solid electrolyte includes
Li2B12F12.The Li2B12F12For tetragonal structure.Since the structure of F atom is big compared with H atom, compared to containing only
The solid electrolyte of Li atom, B atom and H atom, the compound with F atom can have bigger molecular volume, therefore can
For the Li+Bigger space is provided, to improve the transfer ability of lithium ion.
It is appreciated that in the present invention, the solid electrolyte may include appointing in the specific embodiment as above enumerated
One or more of combinations, the mode specifically combined can be according to the performance requirement of the solid electrolyte.
Further, the stability of molecular structure can be improved in B-F key, and therefore, the solid electrolyte can be with higher
Electrochemical window, electrochemical window can reach 5V or more.Based on aforementioned stable molecular structure, the solid electrolyte can be made to have
There are higher modulus of shearing and higher Young's modulus.Specifically, the shearing mould of solid electrolyte provided in the present embodiment
Amount can reach 2-4Gpa, and Young's modulus can reach 6-8Gpa.
Referring to Fig. 1, the second embodiment of the present invention provides a kind of lithium battery electric core 10 comprising in first embodiment
The solid electrolyte 11, the lithium battery electric core 10 further include anode layer 12 and negative electrode layer 13,11 shape of solid electrolyte
Negative electrode layer is arranged in the one side far from the anode layer 12 in wherein one side, the solid electrolyte 11 of anode layer 12 described in Cheng Yu
13。
The afflux is respectively set in the one side of the anode layer 12 and negative electrode layer 13 far from the solid electrolyte 11
Body 19, for providing the electric connection structure connecting with external circuits for the lithium battery electric core 10.
In the present embodiment, the solid electrolyte 11 with a thickness of 200nm-20 μm.Specifically, the solid electrolyte
11 with a thickness of 200nm, 250nm, 300nm, 380nm, 400nm, 470nm, 580nm, 860nm, 980nm, 1 μm, 2.5 μm, 4.1
μm, 5.3 μm, 6.1 μm, 8.2 μm, 11.2 μm, 15 μm, 17 μm, 19 μm or 20 μm.
In some specific embodiments of the present invention, the anode layer 12 includes column crystal positive electrode, described negative
Pole layer 13 includes lithium metal or lithium silicon-carbon composite cathode.
Specifically, the material of the column crystal positive electrode is specially MOxOxide specifically may include but unrestricted
In:
1) oxide electrolyte, such as Li1+xAlxTi2-x(PO4)3(LATP)、Li7La3Zr2O 12(LLZO)、La2/3- xLi3xTiO3(LLTO)、Li1+xAlxGe2-x(PO4)3(LAGP) and LiPON solid electrolyte (LiPON)；
2) sulfide electrolyte, such as Li4-xGe1-xPxS4、Li2S-P2S5、Li2S-SiS2And Li2S-B2S3-P2S；
3) compound of lithium, such as lithium niobate (LiNbO3) and lithium tantalate (LiTaO3)；
4) inorganic ceramic oxide, such as LiAlO2、Al2O3、MgO、TiO2、Ca CO3、ZrO2、ZnO2And SiO2。
Referring to Fig. 2, the third embodiment of the present invention provides a kind of lithium battery electric core 20, the present embodiment and above-mentioned second is in fact
The difference for applying example is: the lithium battery electric core 20 further includes the first collector 291 and the second collector 292, wherein described
One collector 291 and the second collector 292 include two opposite main surfaces 209, wherein a master of the first collector 291
Anode layer 22 is formed on surface 2911, the second collector 292 is negative towards being formed in a main surface 2921 of the anode layer 22
Pole layer 23.Solid electrolyte 24 is arranged between the anode layer 22 and the negative electrode layer 23.Limit in relation to solid electrolyte 24
Fixed identical with above-mentioned first embodiment, details are not described herein.
The anode layer 22 forms anode structure 201, the negative electrode layer 22 and described second with first collector 291
Collector 292 forms anode structure 202.
Negative electrode layer 281 can be formed in another main surface of the not set anode layer 22 of first collector 291, using as another
The negative pole structure of one lithium battery electric core.
The another side main surface of the not set negative electrode layer 23 of second collector 292 can be formed anode layer 282 using as
The anode structure of another lithium battery electric core.
As shown in Figure 2, in some specific embodiments of the present invention, the anode layer 22 is using magnetron sputtering, electricity
The PVD techniques such as beamlet evaporation, pulse laser deposition and atomic layer deposition sink in a wherein main surface for the first collector 291
Product is formed.
Similarly, the column to form another lithium battery electric core can also be deposited in the same way on the second collector 292
The anode layer 282 of shape crystal.
Referring to Fig. 3, the fourth embodiment of the present invention provides a kind of lithium battery 30, the lithium battery 30 may include two companies
The first lithium battery electric core 301 and the second lithium battery electric core 302 of continuous lamination setting.First lithium battery electric core 301, described
Two lithium battery electric cores 302 are lithium battery electric core described in above-mentioned second embodiment and 3rd embodiment, first lithium-ion electric
Core 301 and second lithium-ion electric core 302 include solid electrolyte 34 as described in the first embodiment.As shown in Figure 3, institute
It states and shares a positive and negative copolar collector 31, the positive and negative copolar between the first battery battery core 301 and second lithium battery electric core 302
Collector 31 includes two opposite main surfaces 310, and anode layer 311 is formed in one of main surface 310, using as the first lithium
The anode structure of battery battery core 301 forms negative electrode layer 312 in another main surface 310, using as the second lithium battery electric core 302
Negative pole structure.
Continue as shown in Figure 3, further includes negative current collector 32 in first lithium battery electric core 301, described second
Lithium battery electric core 302 includes plus plate current-collecting body 35.Wherein, it is formed on negative current collector 32 towards 311 side of anode layer
Negative electrode layer 321, the plus plate current-collecting body 35 are equipped with anode layer 351 towards the surface of the positive and negative copolar collector 31, wherein have
The restriction of pass negative electrode layer 321 and anode layer 351 is as shown in above-mentioned second embodiment and 3rd embodiment, and details are not described herein.
Referring specifically to Fig. 4, the fifth embodiment of the present invention provides a lithium battery 40, and the lithium battery 40 includes multiple lithiums
Battery battery core 10, the lithium battery 40 can be made by way of being successively superimposed, the overlapping quantity of specific lithium battery electric core 10
It is unrestricted.
The lithium battery electric core 10 includes the first collector 41 of overlapping setting, anode layer 44, solid-state electrolyte layer 43, bears
Pole layer 45 and the second collector 42.The lithium battery electric core 10 being disposed adjacent is by sharing a plus plate current-collecting body 41 or negative pole currect collecting
Body 42 is superimposed together.Specifically restriction is identical with above-mentioned first embodiment for above-mentioned solid-state electrolyte layer 43, no longer limits herein.
As shown in Figure 4, the second collector 42 is shared at the superposition for two lithium battery electric cores 10 being disposed adjacent, that is, the
Two collectors 42 are positive and negative copolar collector.In the present embodiment, the material of second collector 42 is aluminium copper
AlxCu1-x, wherein 0.1≤x≤0.9.
As shown in Figure 4, be arranged in is respectively anode layer 44 and cathode on 42 two faces being oppositely arranged of the second collector
Layer 45.
Continue as shown in Figure 4, having can be to be connected in series between the multiple lithium battery electric cores 10 for sharing collector.Work as lithium
It, can be directly using the collector positioned at 40 two sides of lithium battery as lithium battery when lithium battery electric core 10 is connected in series in battery
Electrode, to simplify the encapsulating structure of the lithium battery 40.
Referring to Fig. 5, providing a lithium battery 50, in the present embodiment, the lithium battery in the sixth embodiment of the present invention
In 50 include 5 lithium battery electric cores, respectively successively lamination setting the first lithium battery electric core 501, the second lithium battery electric core
502, third lithium battery electric core 503, the 4th lithium battery electric core 504 and the 5th lithium battery electric core 505.As shown in Figure 5, with above-mentioned
Multiple lithium battery electric cores may each comprise: the first collector 51, anode layer 54, solid-state electrolyte layer 53, negative electrode layer 55 and the second collection
Fluid 52.
As shown in Figure 5, the second collector 52 is shared between the first lithium battery electric core 501 and the second lithium battery electric core 502.
In the present embodiment, the material of second collector 52 is aluminium copper AlxCu1-x, wherein 0.1≤x≤0.9.
Negative electrode layer 55 is respectively provided in two opposite main surfaces of second collector 52, it is seen then that the first lithium battery
It can be to be connected in parallel between core 501 and the second lithium battery electric core 502.
Between the second lithium battery electric core 502 and third lithium battery 503, the second collector 52 is equally also shared, and in institute
It states and anode layer 54 and negative electrode layer 55 is respectively set in two opposite main surfaces of the second collector 52, it is seen then that the second lithium battery
It can be series connection between battery core 502 and third lithium battery electric core 503.
Further, the first of the second collector 532 of third lithium battery electric core 503 and the 4th lithium battery electric core 504
The overlapping setting of collector 541, and the first collector 532 and the second collector 541 are expressed as the third lithium battery electric core
503 and the 4th lithium battery electric core 504 plus plate current-collecting body or negative current collector.As it can be seen that the third lithium battery electric core 503
With the 4th lithium battery electric core 504 parallel connectivity can be formed by external circuitry.
In the present embodiment, above-mentioned anode layer 54 is opposite with negative electrode layer 55, the first collector 51 and the second collector 52
Position is adjustable.
Merely illustrative shown in Fig. 5, in actual lithium battery 50, specific connection type can be according to practical lithium battery
Performance requirement adjusts, not as the limitation of the invention herein.
Referring to Fig. 6, providing a lithium battery 60, the present embodiment and the above-mentioned 4th to the 6th in the seventh embodiment of the present invention
The difference of lithium battery provided in embodiment is: the lithium battery 60 further includes encapsulating structure 69, definition with it is multiple described
The surface of the parallel lithium battery electric core 601 of the Direction of superposition of lithium battery electric core 61 is side 611, and the encapsulating structure 69 is disposed around
The side 611 of the lithium battery electric core 601.
As shown in Figure 6, the lithium battery electric core 601 successively includes the first collection along multiple lithium battery electric core Direction of superposition
Fluid 64, anode layer 62, solid electrolyte 61, negative electrode layer 63 and the second collector 65.Wherein, second collector 65 is institute
The positive and negative anodes for stating lithium battery electric core 601 and another lithium battery electric core 601 share collector.
In the present embodiment, solid electrolyte 10 described in the restriction and above-mentioned first embodiment in relation to solid electrolyte 61
Definitions relevant it is identical, details are not described herein.
As shown in Figure 6, the encapsulating structure 69 encloses the process for setting the side 611 can include:
(1) a prefabricated encapsulating structure 69 is provided, then directly by the encapsulating structure by way of hot pressing or bonding
69 are fixed on the side 611.Or
(2) encapsulating structure 69 is directly formed on the side of the lithium battery electric core 601.
In some particular embodiments of the present embodiment, the encapsulating structure 69 can be the protective layer being additionally arranged or utilization
The solid electrolyte 61 extends and is formed.
Referring to Fig. 7, the eighth embodiment of the present invention provides the preparation method S10 of a lithium battery electric core, when the lithium electricity
Included solid electrolyte is Li in the battery core of pond2B12FxH12-xWhen, then the lithium battery electric core the preparation method is as follows:
Step S11 provides the boron-containing compound with face-centered cubic crystal structure, is replaced using the part F or is all replaced
H in the boron-containing compound, thus solid electrolyte raw material needed for obtaining；
Step S12 provides an anode layer, needed for being coated with the solid electrolyte raw material in the one side of anode layer to be formed
Solid-state electrolyte layer；
Plus plate current-collecting body is arranged in the anode layer one side opposite with solid-state electrolyte layer is formed in step S13；
Step S14 sets gradually negative electrode layer, negative pole currect collecting in one side of the solid electrolyte layer far from the anode layer
Body.
Specifically, in above-mentioned steps S11, the boron-containing compound with stereochemical structure can be specially face-centered cubic crystal
Structure, wherein boron atom is set at six vertex of face-centred cubic structure and the center in six faces.
In the present invention, the mode of coating includes but is not limited to extrusion coated, slot coated etc..It is coated with the solid-state formed
Electrolyte layer with a thickness of 200nm-20 μm.
In above-mentioned steps S13, the negative electrode layer can be bonded by way of hot pressing with solid-state electrolyte layer.
It, can also be in one side of the negative electrode layer towards the anode layer in some specific implementations of the present embodiment
Form above-mentioned solid-state electrolyte layer.Or it can also be formed respectively in the negative electrode layer with the surface that the anode layer is oppositely arranged above-mentioned
Solid-state electrolyte layer.
When the solid electrolyte is LiaMbFxH12-xOther specific ingredients and when structure, when such as M being Ga or Al, then on
State step S11 and can correspond to and adjust, here shown in content only as an example, not as the limitation of the invention.
The present invention further detects the performance of provided solid electrolyte, specific experimental group and comparative experiments
It is as follows:
Experimental group 1: solid electrolyte Li2B12F2H10。
Experimental group 2: solid electrolyte Li2B12F12。
Experimental group 3: solid electrolyte Li2Al12F10H2。
Contrast groups: its solid electrolyte is the solid polyelectrolyte of PEO base.
Above-mentioned experimental group 1-3 and documents 1 are subjected to electrochemical window detection respectively and lithium ion conductivity detects,
It is specific as follows:
(1) electrochemical window detects: being consolidated using cyclic voltammetry to prepared by above-mentioned experimental group 1-3 and contrast groups
State electrolyte carries out linear scan test, and scanning speed 0.1-5mV/s obtains experimental group 1-3 and the corresponding electricity of contrast groups
Chemical window test result.
Testing result: the electrochemical window of experimental group 1-3 is all larger than 5V, and contrast groups electrochemical window is then lower than 4.5V.
Comparative analysis: solid electrolyte provided in above-mentioned experimental group 1-3, in microstructure, due to its forming face
Include a variety of crystal phases being composed of B atom and F atom or Al atom and F atom in heart cubic crystal structure, therefore tests
Solid electrolyte provided in group 1-3 can have biggish electrochemical window.Further, due in above-mentioned experimental group 1-3
Provided solid electrolyte has B-F key or Al-F key, and structure is relatively stable, and therefore, the solid electrolyte can have
Higher stability, therefore, solid electrolyte provided in experimental group 1-3 can bear the voltage of 5V or more.
(2) lithium ion conduction test: the solid electrolyte material obtained using experimental group 1-3 and contrast groups, measure its
Lithium ion conductivity at 25 DEG C.
Testing result: in experimental group 1-3, lithium ion conductivity can reach 10-3S/cm, and the lithium ion conductivity of contrast groups
Only 5 × 10-7S/cm。
Comparative analysis: in experimental group 1-3 solid electrolyte obtained, since it forms face-centered cubic crystal structure and tool
There are B-F key or Al-F key, wherein F has biggish volume compared with H, therefore bigger space can be provided for the lithium ion mobility,
Therefore, solid electrolyte provided by the present invention be fast-ionic conductor, therefore, can lithium ion conductivity with higher, lithium
Ionic conductivity can reach 10-3S/cm.And the Li ionic conductivity of contrast groups is only 5 × 10-7S/cm。
Compared with prior art, solid electrolyte and its lithium battery electric core provided by the present invention, lithium battery have as follows
The utility model has the advantages that
One solid electrolyte and lithium battery electric core, lithium battery including the solid electrolyte are provided in the present invention, wherein
The solid electrolyte includes LiaMbFxH12-x, wherein M includes combination one or more of in B, Ga or Al, and a, b and x are indicated
For positive number.Since the structure of F atom is big compared with H atom, compared to the solid-state electricity for containing only Li atom, B atom and H atom
Xie Zhi, the compound with F atom can have bigger molecular volume, therefore can be the Li+Bigger space is provided, thus
Improve the transfer ability of lithium ion.
Further, using one of B-F key, Ga-F key or Al-F key or combinations thereof, rock-steady structure can be formed, because
This, the solid electrolyte can electrochemical window with higher, electrochemical window can reach 5V or more.The solid state electrolysis
Matter further comprises face-centered cubic crystal structure, in conjunction with one of B-F key, Ga-F key or Al-F key or combinations thereof, can be made
The solid electrolyte stable structure, therefore modulus of shearing with higher and higher Young's modulus.Specifically, the present embodiment
Provided in the modulus of shearing of solid electrolyte can reach 2-4Gpa, Young's modulus can reach 6-8Gpa.
In conjunction with one of B-F key, Ga-F key or Al-F key or combinations thereof, it can further make the solid electrolyte molecule
Framework flexibility with higher, thus can guarantee lithium ion in solid electrolyte when fast transferring, LiaMbFxH12-xPoint
Subrack structure can keep stable, to improve the cycle performance and service life of the solid electrolyte.
Further, there is B-B key etc. in solid electrolyte provided by the present invention, due to compound there is stickiness and soft
Property, therefore, the solid electrolyte can be soft material, and with preferable interfacial adhesion and and electrode interface infiltration
Property, therefore, the solid electrolyte contacts well with the surface of electrode.
The present invention also provides a kind of lithium battery electric core and lithium batteries comprising solid electrolyte as described above, wherein collecting
Fluid includes two opposite main surfaces, and column crystal anode layer is formed in one of main surface, using as a lithium battery
The anode structure of core forms negative electrode layer in another main surface, using the negative pole structure as another lithium battery electric core.By in afflux
Positive and negative anodes are set on two faces of body, to form the collector of positive and negative copolar, it can be achieved that prepared by multiple lithium battery electric core laminations, from
And realize the preparation of large area solid lithium battery.
The integral thickness of lithium battery electric core, lithium battery can be also reduced using the collector of positive and negative copolar.Further, it utilizes
The collector of positive and negative copolar between multiple lithium battery electric cores, it can be achieved that be connected in series.When lithium battery electric core series connection connects in lithium battery
It, can be directly using collector as the electrode of lithium battery, to simplify the encapsulating structure of the lithium battery when connecing.
In addition, in the present invention using the positive electrode including column crystal as anode layer, so as to be lithium ion
There is provided smooth diffusion and migrating channels during charge and discharge, the purpose of column crystal is that the high performance cathode of matching is realized just
The maximum of pole material utilizes, and improves the efficiency of lithium insertion and abjection.
Solid lithium battery provided in the present invention, by using the encapsulating structure of the above-mentioned solid lithium battery of the present invention
Packaging electric core has the advantages that encapsulation is close, so as to effective protection battery core, and then makes all solid lithium provided in the present invention
Battery has high service life.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in original of the invention
Made any modification within then, equivalent replacement and improvement etc. should all be comprising within protection scope of the present invention.
Claims (10)
1. a kind of solid electrolyte, it is characterised in that: it includes LiaMbFxH12-x, wherein M includes a kind of or several in B, Ga or Al
The combination of kind, numerical value a, b and x are expressed as positive number.
2. solid electrolyte as described in the appended claim 1, it is characterised in that: the solid electrolyte includes Li2B12FxH12-x,
Middle x is expressed as 1-12.
3. solid electrolyte as described in the appended claim 1, it is characterised in that: the solid electrolyte includes Li2B12F12。
4. a kind of lithium battery electric core, it is characterised in that: have the solid electrolyte as described in any one of claim 1-3.
5. lithium battery electric core as claimed in claim 4, it is characterised in that: the solid electrolyte with a thickness of 200nm-20 μ
m。
6. lithium battery electric core as claimed in claim 4, it is characterised in that: the lithium battery electric core includes anode layer, described solid
State electrolyte is formed in the one side of the anode layer, and cathode is arranged in the one side far from the anode layer in the solid electrolyte
Layer.
7. lithium battery electric core as recited in claim 6, it is characterised in that: the anode layer includes column crystal positive electrode,
The negative electrode layer includes lithium metal or lithium silicon-carbon composite cathode material.
8. the lithium battery electric core as described in claim 6 or 7, it is characterised in that: the lithium battery electric core further includes two affluxs
Body, the collector include two opposite main surfaces, form the anode layer in one of main surface, using as the lithium electricity
The anode structure of pond battery core；Negative electrode layer is formed in another main surface, using the negative pole structure as another lithium battery electric core.
9. a kind of lithium battery, it is characterised in that: it includes at least two continuous lamination settings lithium battery as claimed in claim 8
Battery core shares a positive and negative copolar collector, the positive and negative copolar afflux between at least two lithium battery electric cores being directly superposed
Body includes two opposite main surfaces, forms the anode layer in one of main surface, using as a wherein lithium battery electric core
Anode structure, negative electrode layer is formed in another main surface, using the negative pole structure as another lithium battery electric core.
10. lithium battery as described in claim 9, it is characterised in that: share two lithium batteries of a positive and negative copolar collector
It is series connection between battery core；The lithium battery further includes encapsulating structure, is defined and the side of superposition of multiple lithium battery electric cores
It is side to the surface of parallel lithium battery electric core, the encapsulating structure is disposed around the side of the lithium battery electric core.
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