CN109935892A - 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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- CN109935892A CN109935892A CN201711370955.6A CN201711370955A CN109935892A CN 109935892 A CN109935892 A CN 109935892A CN 201711370955 A CN201711370955 A CN 201711370955A CN 109935892 A CN109935892 A CN 109935892A
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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
Abstract
The present invention relates to field of lithium, in particular to solid electrolyte and its lithium battery electric core, lithium battery, the solid electrolyte includes organic metal framework and filling and the electrolyte in the organic metal framework, the organic metal framework includes one or more of X-MOFs, X-BTTri or X-dobdc, the X includes one or more of Cu, Mg or Zn, the s includes one or more of 5,177 or 210, and the mass mixing mass ratio of the electrolyte and the organic backbone is (10:1)-(1:10).Above-mentioned solid electrolyte stable structure has the advantages that electrochemical window greater than 5V, preferably stickiness, flexibility, interface wellability, interfacial adhesion, high Li ionic conductivity, high tolerance, high shear modulus, Young's modulus and can inhibit lithium dendrite growth.
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, and sulfide solid state electrolysis confrontation water, air are very sensitive, and all solid state electrolysises registered now
There is biggish interface resistance after material and positive and negative electrode material, causes cycle life shorter.
And inorganic powder or thin-film material that general solid electrolyte material uses, it is polycrystalline material, there are lithium ions
Conductivity is low, and operating voltage is low, poor with interface wellability.
[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, the solid-state electricity
Solution matter includes organic metal framework and filling and the electrolyte in the organic metal framework, and the organic metal framework includes X-
One or more of MOFs, X-BTTri or X-dobdc, the X include one or more of Cu, Mg or Zn, the s
Including one or more of 5,177 or 210, the mass mixing mass ratio of the electrolyte and the organic backbone be (10:
1)-(1:10)。
Preferably, the electrolyte includes Li3Sn2(PO4)3Or Li3Ge2(PO4)3Any one of or two kinds.
Preferably, lithium ion conductivity is (0.05-11) × 10 in the solid electrolyte-2S/cm。
It is as follows that the present invention provides another technical solution to solve above-mentioned technical problem: a kind of lithium battery electric core, including as above
The 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 negative
Pole material.
Preferably, the lithium battery electric core further includes two collectors, and the collector includes two opposite main surfaces,
The anode layer or the negative electrode layer are formed in one of main surface, using the anode structure or cathode as the lithium battery electric core
Structure；Negative electrode layer or anode layer are formed in another main surface, using the negative pole structure or anode structure as another lithium battery electric core.
It is as follows that the present invention provides another 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 a continuous lamination, and one is being shared between at least two lithium battery electric cores being directly superposed just
Negative copolar collector, the positive and negative copolar collector include two opposite main surfaces, formed in one of main surface it is described just
Pole 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 battery 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
In the present invention, electrolyte includes Li in the solid electrolyte3Sn2(PO4)3Or Li3Ge2(PO4)3In any
Kind or two kinds, upper electrolyte have good stable type and ion compatibility, therefore, have greater than 5V electrochemical window.Institute
Se and Ge are stated in the structure of solid electrolyte to Li+Fetter weaker, therefore Li ion is easier to migrate, therefore, can get compared with
Excellent conductivity is good, more excellent with that can have when preferably stickiness and flexibility and the solid electrolyte are contacted with electrode layer
Interface wellability and interfacial adhesion；Further, the solid electrolyte further includes organometallic skeletal, is solid-state electricity
Solving matter has porosity abundant, is that lithium ion is easier to migrate, solid electrolyte molecular framework is also made to have preferably tolerance
Property and cycle performance.The characteristics of based on the solid electrolyte structure, can also have modulus of shearing (6Gpa) and high Young mould
The advantages of measuring (10-11Gpa), in turn, solid electrolyte provided by the present invention can also effectively inhibit the growth of Li dendrite.
Lithium battery provided by the present invention, wherein collector includes two opposite main surfaces, in one of main surface
Form column crystal anode layer and negative electrode layer formed in another main surface using the anode structure as a lithium battery electric core, using as
The negative pole structure of another lithium battery electric core.By the way that positive and negative anodes are arranged on two faces of collector, to form the collection of positive and negative copolar
Fluid is, it can be achieved that prepared by multiple lithium battery electric core laminations, to 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 encapsulation close, can effective protection battery core, and then make solid lithium battery provided in the present invention that there is pole
High service life.
[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, the solid electrolyte include organic metal framework and
Filling and the electrolyte in the organic metal framework, the organic metal framework includes X-MOFs, X-BTTri or X-dobdc
One or more of, the X includes one or more of Cu, Mg or Zn, and the s includes one of 5,177 or 210
Or it is several.The electrolyte includes Li3Sn2(PO4)3Or Li3Ge2(PO4)3Any one of or two kinds.
It is appreciated that the organometallic skeletal include Mg-MOF-5, Zn-MOF-5, Cu-MOF-5, Mg-MOF-177,
Zn-MOF-177Cu-MOF-177、Mg-MOF-210、Zn-MOF-210、Cu-MOF-210、Mg-BTTri、Zn-BTTri、Cu-
One or more of BTTri, Mg-dobdc, Zn-dobdc or Cu-dobdc；The electrolyte and the organometallic skeletal
It is mutually mixed, and then obtains the solid electrolyte.The mixing quality ratio of the electrolyte and organometallic skeletal be (10:
1)-(1:10)；Further, the mixing quality ratio of the electrolyte and organometallic skeletal is (8:3)-(3:8)；Specifically
, the mixing quality ratio of the electrolyte and organometallic skeletal is 10:1,1:10,8:1,8:2,3:8,7:1,5:1 or 5:
5。
Further, the electrolyte is preferably Li3Sn2(PO4)3；The organometallic skeletal is preferably Cu-MOF-
177, Cu-BTTri or Cu-dobdc；The mixing quality ratio of the electrolyte and organometallic skeletal is 8:2.
Further, lithium ion conductivity is (0.5-11) × 10 in above-mentioned solid electrolyte-2S/cm；The solid state electrolysis
Lithium ion conductivity is (3-10) × 10 in matter-2S/cm；Specifically, lithium-ion electrolyte 0.5 × 10 in the solid electrolyte-2S/cm、3×10-2S/cm、5×10-2S/cm、7×10-2S/cm、9×10-2S/cm、10×10-2S/cm or 11 × 10-2S/cm；
Meanwhile the solid electrolyte can greater than 5V or more electrochemical window on steady operation.
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 contact point 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 cathode material.
Specifically, the material of column crystal positive electrode as shown in Figure 1 is specially MOxOxide specifically may include
But it is not only restricted to:
1) oxide electrolyte, such as Li1+xAlxTi2-x(PO4)3(LATP)、Li7La3Zr2O12(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、CaCO3、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 uses magnetron sputtering, electronics
The PVD techniques such as beam evaporation, pulse laser deposition and atomic layer deposition deposit in a wherein main surface for the first collector 291
It 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 and described
Second lithium battery electric core 302 is lithium battery electric core described in above-mentioned second embodiment and 3rd embodiment comprising in fact such as first
Apply solid electrolyte 34 described in example.
As shown in Figure 3, one is shared between first lithium battery electric core 301 and second lithium battery electric core 302 just
Negative copolar collector 31, which includes two opposite main surfaces 310, in one of main surface 310
Anode layer 311 is formed, using the anode structure as the first lithium battery electric core 301, forms negative electrode layer 312 in another main surface 310,
Using the negative pole structure as the second lithium battery electric core 302.
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
Pass negative electrode layer 321 and the definitions relevant of anode layer 351 are no longer superfluous herein as shown in above-mentioned second embodiment and 3rd embodiment
It states.
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 coincidence number of specific lithium ion list battery core 10
It measures unrestricted.
The lithium ion list battery core 10 include overlapping setting the first collector 41, anode layer 44, solid-state electrolyte layer 43,
Negative electrode layer 45 and the second collector 42.The lithium ion list battery core 10 being disposed adjacent is by sharing a plus plate current-collecting body 41 or cathode
Collector 42 is superimposed together.Specifically restriction is identical with above-mentioned first embodiment for above-mentioned solid-state electrolyte layer 43, herein no longer
It limits.
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 4,42 two sides of the second collector are arranged in is respectively anode layer 44 and negative electrode layer 45.
As shown in Figure 4, having between the multiple lithium battery electric cores 10 for sharing collector to be series connection.Work as lithium battery
It, can be directly using the collector positioned at 40 two sides of lithium battery as the electricity of lithium battery when middle lithium battery electric core 10 is connected in series
Pole, 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 with it is another
One lithium battery electric core 61 is that positive and negative anodes share collector.Wherein, restriction and above-mentioned first in relation to solid electrolyte 61 are implemented
The definitions relevant of solid electrolyte 10 described in example is identical, and 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 61.
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 610 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, the lithium battery
Battery core includes solid-state electrolyte layer described in first embodiment comprising following steps:
Step S11 provides an anode layer, and coating forms solid electrolyte in the one side of anode layer, with a thickness of 1 μm -100
μm；
Plus plate current-collecting body is arranged in the anode layer one side opposite with solid electrolyte is formed in step S12；
Step S13, the prefabricated negative electrode layer of hot pressing compound one, makes in one side of the solid electrolyte far from the anode layer
Solid electrolyte is with a thickness of 200nm-20 μm of negative current collector.
Step S14 forms negative current collector far from the surface of the solid-state electrolyte layer in the negative electrode layer.
Specifically, in above-mentioned steps S11, the mode of coating includes but is not limited to extrusion coated, slot coated etc..
The performance of provided solid electrolyte and its lithium battery is detected in ninth embodiment of the invention, specifically
Experimental group and comparative experiments are as follows:
Experimental group 10: solid electrolyte Li3Se(PO4)3(Cu-MOF-177), the electrolyte and organometallic skeletal
Mixing quality ratio is 8:2, and the solid electrolyte is adopted respectively with a thickness of 800nm, plus plate current-collecting body and negative current collector
With aluminium, copper product, anode layer LiAlO2Column crystal positive electrode, negative electrode layer is lithium silicon-carbon cathode material, by its group
Dress up lithium battery electric core.
Experimental group 20: the difference of itself and above-mentioned experimental group 10 is: solid electrolyte Li3Se(PO4)3-(Cu-MOF-
210)。
Contrast groups 30: the difference of itself and above-mentioned experimental group 10 is: solid electrolyte Li3Se(PO4)3-(Cu-MOF-
5)。
Control experiment: solid electrolyte surface adhesive, wellability, modulus of shearing and Young's modulus, electrochemical window are directed to
The dependence test experiment of mouth and its test result
Comparative analysis: above-mentioned experimental group 10-20 relative contrast group 30 is compared, solid state electrolysis provided by experimental group 10-20
Matter surface adhesive, wellability, modulus of shearing and Young's modulus, lithium ion conductivity are superior to contrast groups 30；And the experiment
Group 10-20 and contrast groups 30, the electrochemical window of provided solid electrolyte are all larger than 5V.
Its reason is: Se is to Li in the electrolyte+Fetter it is weak, so Li3Se(PO4) in solid electrolyte, lithium ion compared with
It is easy migration, therefore is fast-ionic conductor；The specific surface area of Cu-MOF-177 and Cu-MOF-210 in the organometallic skeletal
It is better than Cu-MOF-5 with porosity.
Experimental group 11: solid electrolyte Li3Se(PO4)3(Cu-MOF-177), the electrolyte and organometallic skeletal
Mixing quality ratio is 8:2, and the solid electrolyte is adopted respectively with a thickness of 800nm, plus plate current-collecting body and negative current collector
With aluminium, copper product, anode layer LiAlO2Column crystal positive electrode, negative electrode layer is lithium silicon-carbon cathode material, by its group
Dress up lithium battery electric core.
Contrast groups 21: the difference of itself and above-mentioned experimental group 10 is: solid electrolyte Li3Ge(PO4)3-(Cu-MOF-
177)。
Comparative analysis: above-mentioned 11 relative contrast of experimental group group 21 is compared, solid electrolyte surface provided by experimental group 11
Adhesiveness, wellability, modulus of shearing and Young's modulus are close with above-mentioned parameter in the contrast groups 21, but experimental group 11 is mentioned
The solid electrolyte lithium ion conductivity of confession is better than this parameter similar in contrast groups 21；And the experimental group 11 and contrast groups 21
The electrochemical window of provided solid electrolyte is all larger than 5V.
Its reason is: the Sn is weaker than the constraint of lithium ion, and Ge is to the binding force of lithium ion, and then lithium ion is containing
It is easier to migrate in the solid electrolyte of Sn.
Experimental group 12: solid electrolyte Li3Se(PO4)3(Cu-MOF-177), the electrolyte and organometallic skeletal
Mixing quality ratio is 8:2, and the solid electrolyte is adopted respectively with a thickness of 800nm, plus plate current-collecting body and negative current collector
With aluminium, copper product, anode layer LiAlO2Column crystal positive electrode, negative electrode layer is lithium silicon-carbon cathode material, by its group
Dress up lithium battery electric core.
Contrast groups 22: the difference of itself and above-mentioned experimental group 10 is: solid electrolyte Li3Ge(PO4)3-(Mg-MOF-
177)。
Contrast groups 32: the difference of itself and above-mentioned experimental group 10 is: solid electrolyte Li3Ge(PO4)3-(Zn-MOF-
177)。
Comparative analysis: above-mentioned 11 relative contrast of experimental group organizes 21-31 and compares, solid electrolyte table provided by experimental group 11
Face adhesiveness, wellability, modulus of shearing, Young's modulus and lithium ion conductivity are superior to above-mentioned parameter in contrast groups 21-31；And
The electrochemical window of solid electrolyte provided by the experimental group 11 and contrast groups 21 is all larger than 5V.
Its reason is: porosity in the organometallic skeletal that the Cu is constituted, organic better than what the Mg and Zn was constituted
Porosity in porosity in metallic framework.
Further, in 11 experimental groups of the experimental group and contrast groups solid electrolyte organometallic skeletal, can also
To replace with BTTri simultaneously-2Or dobdc-2.Result in corresponding comparative analysis is still identical as the comparing result of experimental group 11,
The analysis of causes is also identical.
Experimental group 13: solid electrolyte Li3Se(PO4)3(Cu-MOF-177), the electrolyte and organometallic skeletal
Mixing quality ratio is 8:2, and the solid electrolyte is adopted respectively with a thickness of 800nm, plus plate current-collecting body and negative current collector
With aluminium, copper product, anode layer LiAlO2Column crystal positive electrode, negative electrode layer is lithium silicon-carbon cathode material, by its group
Dress up lithium battery electric core.
Contrast groups 23: the difference of itself and above-mentioned experimental group 10 is: the electrolyte and organometallic skeletal mixing quality
Ratio is 8:1.
Contrast groups 33: the difference of itself and above-mentioned experimental group 10 is: the electrolyte and organometallic skeletal mixing quality
Ratio is 3:1.
Control experiment: solid electrolyte surface adhesive, wellability, modulus of shearing and Young's modulus, electrochemical window are directed to
The dependence test experiment of mouth and its test result
Comparative analysis: above-mentioned 13 relative contrast of experimental group organizes 23-33 and compares, solid electrolyte table provided by experimental group 13
Face adhesiveness, wellability, modulus of shearing and Young's modulus, lithium ion conductivity are superior to contrast groups 30；And the experimental group 13
5V is all larger than with the electrochemical window of contrast groups 23-33, provided solid electrolyte.
Its reason is: when the electrolyte and organometallic skeletal mixing quality ratio are 8:2, the solid dielectric
In organometallic skeletal in porosity it is best, meanwhile, electrolyte occupied state in organometallic skeletal is best.
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
In the present invention, electrolyte includes Li in the solid electrolyte3Sn2(PO4)3Or Li3Ge2(PO4)3In any
Kind or two kinds, upper electrolyte have good stable type and ion compatibility, therefore, have greater than 5V electrochemical window.Institute
Se and Ge are stated in the structure of solid electrolyte to Li+Fetter weaker, therefore Li ion is easier to migrate, therefore, can get compared with
Excellent conductivity is good, more excellent with that can have when preferably stickiness and flexibility and the solid electrolyte are contacted with electrode layer
Interface wellability and interfacial adhesion；Further, the solid electrolyte further includes organometallic skeletal, is solid-state electricity
Solving matter has porosity abundant, is that lithium ion is easier to migrate, solid electrolyte molecular framework is also made to have preferably tolerance
Property and cycle performance.The characteristics of based on the solid electrolyte structure, can also have modulus of shearing (6Gpa) and high Young mould
The advantages of measuring (10-11Gpa), in turn, solid electrolyte provided by the present invention can also effectively inhibit the growth of Li dendrite.
Lithium battery provided by the present invention, wherein collector includes two opposite main surfaces, in one of main surface
Form column crystal anode layer and negative electrode layer formed in another main surface using the anode structure as a lithium battery electric core, using as
The negative pole structure of another lithium battery electric core.By the way that positive and negative anodes are arranged on two faces of collector, to form the collection of positive and negative copolar
Fluid is, it can be achieved that prepared by multiple lithium battery electric core laminations, to 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 encapsulation close, can effective protection battery core, and then make solid lithium battery provided in the present invention that there is pole
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: the solid electrolyte includes that organic metal framework and filling have with described
Electrolyte in machine metal framework, the organic metal framework include one of X-MOFs, X-BTTri or X-dobdc or several
Kind, the X includes one or more of Cu, Mg or Zn, and the s includes one or more of 5,177 or 210, the electricity
The mass mixing mass ratio of organic backbone described in Xie Zhiyu is (10:1)-(1:10).
2. solid electrolyte as described in the appended claim 1, it is characterised in that: the electrolyte includes Li3Sn2(PO4)3Or Li3Ge2
(PO4)3Any one of or two kinds.
3. solid electrolyte as described in the appended claim 1, it is characterised in that: lithium ion conductivity is in the solid electrolyte
(0.05-11)×10-2S/cm。
4. a kind of lithium battery electric core, it is characterised in that: including 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 cathode material.
8. the lithium battery electric core as described in any one of claim 5-7, it is characterised in that: the lithium battery electric core further includes two
Collector, the collector include two opposite main surfaces, and the anode layer or described negative is formed in one of main surface
Pole layer, using the anode structure or negative pole structure as the lithium battery electric core；Negative electrode layer or anode layer are formed in another main surface, with
Negative pole structure or anode 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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