CN207993959U - Negative electrode layer and its lithium battery electric core, lithium battery - Google Patents
Negative electrode layer and its lithium battery electric core, lithium battery Download PDFInfo
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- CN207993959U CN207993959U CN201721776952.8U CN201721776952U CN207993959U CN 207993959 U CN207993959 U CN 207993959U CN 201721776952 U CN201721776952 U CN 201721776952U CN 207993959 U CN207993959 U CN 207993959U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The utility model is related to field of lithium, more particularly to negative electrode layer and its lithium battery electric core, lithium battery.The negative electrode layer includes metal porous structure and melts the lithium metal being filled in the hole of metal porous structure, and the metal porous structure is formed by the metal or metallic compound of one or more combination in Al, Cu or Ni element.The uniformity that lithium metal is distributed in the negative electrode layer can be improved in above-mentioned metal porous structure.The negative electrode layer is formed on one surface of the collector, and metal porous structure described in the negative electrode layer can provide support frame for the lithium metal in the negative electrode layer.Lithium battery with above-mentioned negative electrode layer can avoid the structure of negative electrode layer from changing or cave in during lithium ion mobility, so as to extend the cycle life of lithium battery.
Description
【Technical field】
The utility model is related to field of lithium, more particularly to a kind of negative electrode layer and its lithium battery electric core, lithium battery.
【Background technology】
Compared with traditional electrode, lithium an- ode has higher theoretical capacity (3680mAh/g) and lower electrochemistry
Gesture (- 3.04V).However existing metal lithium electrode easily reacts with existing electrolyte, and growth lithium is easy in cyclic process
Dendrite, volume change are larger, safety and cycle performance existing defects.
Common metal cathode of lithium is all made of the mode of cladding to protect lithium an- ode, but this method can not solve lithium
Volume change is larger in use and leads to the problem of the areas Si Li for metal.The utility model provides a kind of with charge and discharge
The lithium metal that volume change is small in the process, ionic conductivity and electronic conductivity are higher, stability is preferable, has extended cycle life is negative
Pole.
【Utility model content】
To overcome the problems, such as that cathode performance is bad in existing lithium battery, the utility model provides a kind of negative electrode layer and its lithium
Battery battery core, lithium battery.
It is as follows that the utility model provides a technical solution to solve above-mentioned technical problem：A kind of negative electrode layer comprising metal
Porous structure and melting are filled in the lithium metal in the hole of metal porous structure, and the metal porous structure is by Al, Cu or Ni
The metal or metallic compound of one or more combination are formed in element.
Preferably, the metal porous structure includes metallic particles and/or metal compound particles, the metal porous knot
Structure further includes the hole formed between metallic particles and/or metal compound particles, and the lithium metal of melting is filled in the hole
In.
Preferably, the volume of the hole of the negative electrode layer accounts for the 20%-90% of the total volume of the negative electrode layer；The lithium gold
The quality of category accounts for the 10%-90% of the gross mass of the negative electrode layer.
Preferably, the pore size of the metal porous structure is 10nm-1 μm, porosity in the metal porous structure
For 10%-90%.
Preferably, the thickness of the negative electrode layer is 5-10 μm.
It is as follows that the utility model provides a technical solution to solve above-mentioned technical problem：A kind of lithium battery electric core comprising
Negative pole structure, the negative pole structure include collector and negative electrode layer as described above, and the negative electrode layer is formed in the collector
On one main surface.
Preferably, the lithium battery electric core further includes anode structure and is arranged between the anode structure and negative pole structure
Solid-state electrolyte layer；The anode structure includes anode layer, and the anode layer includes column crystal positive electrode.
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 utility model provides a technical solution to solve above-mentioned technical problem：A kind of lithium battery comprising at least
Lithium battery electric core as described above is arranged in two continuous laminations, and one is shared between at least two lithium battery electric cores being directly superposed
Positive and negative copolar collector, the positive and negative copolar collector plate include two opposite main surfaces, formed in one of main surface described in
Anode layer forms negative electrode layer using the anode structure as a wherein lithium battery electric core in another main surface, using as another lithium electricity
The negative pole structure of pond battery core.
Preferably, it is to be connected in series between two lithium battery electric cores of a shared positive and negative copolar collector；The lithium battery
Further include encapsulating structure, the surface for defining the lithium battery electric core parallel with multiple Direction of superposition of the lithium battery electric core 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 utility model, lithium battery, have
Following advantageous effect：
In the negative electrode layer that utility model is provided comprising collector substrate and the negative electrode layer for being formed in its surface, institute
It includes that metal porous structure and melting are filled in lithium metal in the hole of metal porous structure to state negative electrode layer.In above-mentioned structure
In, metal porous structure described in the negative electrode layer can be used as the skeleton that the lithium metal is depended on or supported, so as to golden with lithium
Belong to and form the alloy with 3D network structures, in battery charging and discharging, during lithium ion mobility, to avoid the knot of negative electrode layer
Structure changes or caves in, so as to extend the cycle life of lithium battery electric core and battery.
Further, in negative electrode layer provided by the utility model, due to lithium metal be filled in metal porous structure it
In, therefore, the specific surface area on lithium metal surface greatly increases, and local current reduces, and can further reduce the enrichment of lithium ion
Degree is conducive to dendrite inhibition growth, therefore safe.
In some other embodiments of utility model, in the negative electrode layer provided, including mixed metal skeleton, it is described mixed
It includes the hole formed by the metal of one or more combination in Al, Cu or Ni element to close metallic framework, and the negative electrode layer also wraps
Include the lithium metal that melting is filled in the hole.In such a configuration, metal mixture layer can described in the negative electrode layer
3D structures are formed so as to form the alloy with network structure with lithium metal as the support frame of the negative electrode layer, with
In battery charging and discharging, during lithium ion mobility, the structure of negative electrode layer is avoided to change or cave in, so as to extend lithium
The cycle life of battery battery core and battery.
Further, in negative electrode layer provided by the utility model, one or more of groups in containing Al, Cu or Ni element
It is formed among hole between the metallic particles or metal compound particles of conjunction, the molten metal lithium is filled in the hole.
Based on above structure, the specific surface area on lithium metal surface greatly increases, and local current reduces, and can further reduce lithium ion
Enrichment degree is conducive to dendrite inhibition growth, therefore safe.
The utility model also provides a kind of lithium battery electric core and lithium battery comprising negative electrode layer as described above.Wherein collect
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.
【Description of the drawings】
Fig. 1 is the structural schematic diagram for the negative electrode layer that the utility model first embodiment provides.
Fig. 2 is the structural schematic diagram of the variation of negative electrode layer shown in Fig. 1.
Fig. 3 is the structural schematic diagram for the negative electrode layer that the utility model second embodiment provides.
Fig. 4 is the schematic diagram of a layer structure for the lithium battery electric core that the utility model 3rd embodiment is provided.
Fig. 5 is the schematic diagram of a layer structure for the lithium battery electric core that the utility model fourth embodiment is provided.
Fig. 6 is the laminated construction schematic diagram for the lithium battery that the 5th embodiment of the utility model is provided.
Fig. 7 is the laminated construction schematic diagram for the lithium battery that the utility model sixth embodiment is provided.
Fig. 8 is the laminated construction schematic diagram for the lithium battery that the 7th embodiment of the utility model is provided.
Fig. 9 is the laminated construction signal for the lithium battery with encapsulating structure that the 8th embodiment of the utility model is provided
Figure.
Figure 10 is the flow diagram for the lithium battery electric core preparation method that the 9th embodiment of the utility model is provided.
【Specific implementation mode】
In order to make the purpose of this utility model, technical solution and advantage be more clearly understood, below in conjunction with attached drawing and implementation
Example, the present invention will be further described in detail.It should be appreciated that specific embodiment described herein is only used to solve
The utility model is released, is not used to limit the utility model.
It please refers to Fig.1 and Fig. 2, the utility model first embodiment provides a kind of novel negative electrode layer 62, provide an afflux
Body substrate 61 and be formed in the collector substrate 61 a surface negative electrode layer 62, collector 61 combines formation with negative electrode layer 62
One negative pole structure 60.
The negative electrode layer 62 includes containing one or more combination metal porous structure 621 in Cu, Ni or Al element and melting
Melt the lithium metal 622 being filled in the hole 6211 of metal porous structure 621.
When the metal porous structure 621 includes two or more metallic element, the quality between different metal element
Than as follows：
When the metal porous structure 621 is Al, Ni alloy, Al:The mass ratio of Ni is (1-10)：(1-10), specifically
Ground, Al:The mass ratio of Ni is 1:1、 1:3、2:3：5:1、7:1、10:1、1:6 or 1:10.
When the metal porous structure 621 is Cu, Al, Ni alloy, Cu:Al:The mass ratio of Ni is (1-5)：(2-5)：
(1-5), specifically, Cu:Al:The mass ratio of Ni is 1:3:3、1:1:3 or 2:3:3.
As shown in fig. 1, in the metal porous structure, the hole 6211 can arrange for rule, and the hole
6211 it is equal in magnitude.As shown in Figure 5, in the metal porous structure 621, the hole 6211 can be irregular arrangement,
And the size of the hole 6211 differs.
The pore size of the metal porous structure 621 is 10nm-1 μm, specifically, the metal porous structure 621
The size in aperture be 10nm, 20nm, 40nm, 52nm, 70nm, 81nm, 100nm, 205nm, 324nm, 541nm, 650nm,
756nm, 878nm, 921nm or 1 μm.
Porosity is 10%-90% in the metal porous structure 621, and specifically, the metal porous structure 621 can wrap
Include 10%, 15%, 17%, 25%, 31%, 42%, 48%, 57%, 68%, 76%, 80% or 90%.
In order to allow the negative electrode layer 62 to form a relatively stable network structure, the thickness of the negative electrode layer 62 is
5-10 μm, specifically, the thickness of the negative electrode layer 62 is 5 μm, 5.2 μm, 6 μm, 7.1 μm, 8.5 μm, 8.7 μm, 9.1 μm, 9.7 μ
M or 10 μm.
Referring to Fig. 3, the utility model second embodiment provides a kind of novel negative electrode layer 52, a collector substrate is provided
51 and be formed in the collector substrate 51 a surface negative electrode layer 52, it is one negative that collector 51 combines formation with negative electrode layer 52
Pole structure 50.
As shown in Figure 3, the negative electrode layer 52 further comprises mixed metal skeleton 521, the mixed metal skeleton 521
It is formed by the metal or metallic compound of one or more combination in Al, Cu or Ni element, in the mixed metal skeleton 521
Hole 522 is formed between metallic particles and/or the metal compound particles.The negative electrode layer 52 further includes that melting is filled in
Lithium metal 523 in the hole 522.
In such a configuration, mixed metal skeleton 521 described in the negative electrode layer 52 can be used as the negative electrode layer 52
Support, so as to form the alloy with 3D network structures with lithium metal.And then during battery charging and discharging, the cathode
After lithium metal in layer 52 forms the lithium ion of migration under the function of current, it also can guarantee that the structure of negative electrode layer 52 does not change or collapses
It collapses, so that it is guaranteed that the constancy of volume of the negative electrode layer 52, to extend the cycle life of the negative pole structure 50.
When the mixed metal skeleton 521 includes two or more metallic element, the quality between different metal element
Than as follows：
When the mixed metal skeleton 521 is Cu, Al alloy, Cu:The mass ratio of Al is (1-10)：(1-10), specifically
Ground, Cu:The mass ratio of Al is 1:1、 1:3、2:3：5:1、7:1、10:1、1:6 or 1:10.
When the mixed metal skeleton 521 is Cu, Al, Ni alloy, Cu:Al:The mass ratio of Ni is (1-5)：(2-5)：
(1-5), specifically, Cu:Al:The mass ratio of Ni is 1:3:3、1:1:3 or 2:3:3.
In the present embodiment, in order to make the specific volume metric density bigger of the negative electrode layer 52, then the quality of the lithium metal can
Account for the 10%-90% of the gross mass of the negative electrode layer 52.Specifically, the lithium metal accounts for the gross mass of the negative electrode layer 52
50-70%.
Further, in utility model, the volume of hole accounts for 52 total volume of the negative electrode layer in the negative electrode layer 52
20%-90%, ratio can also be 20%, 25%, 27%, 45%, 41%, 45%, 48%, 57%, 68%, 76%,
79%, 80% or 90%.
Referring to Fig. 4, the 3rd embodiment of the utility model provides a kind of lithium battery electric core 10 comprising implement such as first
Negative electrode layer 13 described in example, the lithium battery electric core 10 further includes anode layer 12 and solid electrolyte 11, the solid electrolyte
11 wherein one side, the solid electrolytes 11 for being formed in the anode layer 12 are arranged in the one side far from the anode layer 12
Negative electrode layer 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 being connect with external circuits for the lithium battery electric core 10.
In the present embodiment, the thickness of the negative electrode layer 13 is 1nm-100 μm.Specifically, the thickness of the negative electrode layer 13
It is 1 μm, 2.5 μm, 4.1 μm, 5.3 μm, 6.1 μm, 8.2 μm, 11.2 μm, 25 μm, 37 μm, 59 μm, 70 μm, 80 μm or 100 μm.
In the present embodiment, the negative electrode layer 52 can be negative electrode layer 13 described in first embodiment as described above.
In the present embodiment some specific embodiments, the anode layer 12 includes column crystal positive electrode.Specifically
The material on ground, the column crystal positive electrode is specially MOxOxide specifically may include but be not only restricted to：
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. 5, the fourth embodiment of the utility model provides a kind of lithium battery electric core 20, the present embodiment and above-mentioned the
Three embodiments difference lies in：The lithium battery electric core 20 further includes the first collector 291 and the second collector 292, wherein institute
It includes two opposite main surfaces 209 to state the first collector 291 and the second collector 292, wherein the one of the first collector 291
Anode layer 22 is formed in a main surface 2911, shape in a main surface 2921 of second collector 292 towards the anode layer 22
At negative electrode layer 23.Solid electrolyte 24 is arranged between the anode layer 22 and the negative electrode layer 23.Wherein, related negative electrode layer 23
Definitions relevant it is identical as the definitions relevant of negative electrode layer 13 described in above-mentioned first embodiment, details are not described herein.
The anode layer 22 and first collector 291 form anode structure 20 1, the negative electrode layer 22 and described the
Two collectors 292 form negative pole structure 202.
Another main surface of anode layer 22 is not arranged in first collector 291 can form negative electrode layer 281, using as another
The negative pole structure of one lithium battery electric core.
Be not arranged in second collector 292 negative electrode layer 23 another side main surface can be formed anode layer 282 using as
The anode structure of another lithium battery electric core.
As shown in Figure 5, in the utility model some specific implementation modes, the anode layer 22 is splashed using magnetic control
Penetrate, the PVD techniques such as electron beam evaporation, pulsed laser deposition and atomic layer deposition the first collector 291 wherein one main table
It deposits and is formed on face.
Similarly, similarly mode the column to form another lithium battery electric core can also be deposited on the second collector 292
The anode layer 282 of shape crystal.
Referring to Fig. 6, the 5th embodiment of the utility model provides a kind of lithium battery 30, the lithium battery 30 may include two
The first lithium battery electric core 301 and the second lithium battery electric core 302 of a continuous lamination setting.First lithium battery electric core 3 01,
Second lithium battery electric core 302 is lithium battery electric core described in above-mentioned second embodiment and 3rd embodiment comprising such as the
Negative electrode layer 13 described in one embodiment.
As shown in Figure 6, one is shared between first lithium battery electric core 301 and second lithium battery electric core 302 just
Negative copolar collector 31, the positive and negative copolar collector 31 include two opposite main surfaces 310, in one of main surface 31 0
Anode layer 311 is formed, using the anode structure as the first lithium battery electric core 301, negative electrode layer 312 is formed in another main surface 310,
Using the negative pole structure as the second lithium battery electric core 302.
Continue as shown in Figure 6, 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 with towards 311 side of the anode layer on negative current collector 32
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 3rd embodiment and fourth embodiment, and details are not described herein.
Referring specifically to Fig. 7, the sixth embodiment of the utility model provides a lithium battery 40, and the lithium battery 40 includes more
A lithium battery electric core 10, the lithium battery 40 can be made by way of being successively superimposed, the overlapping of specific lithium battery electric core 10
Quantity 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.Above-mentioned negative electrode layer 45 specifically limits the definitions relevant phase with negative electrode layer 13 described in above-mentioned first embodiment
Together, it no longer limits herein.
As shown in Figure 7, 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 7, be arranged on 42 two faces being oppositely arranged of the second collector is respectively anode layer 44 and cathode
Layer 45.
Continue as shown in Figure 7, can be to be connected in series between multiple lithium battery electric cores 10 with shared collector.Work as lithium
It, can be directly using the collector positioned at 40 both sides of the 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. 8, the 7th embodiment in the utility model provides a lithium battery 50, in the present embodiment, the lithium
Battery 50 includes 5 lithium battery electric cores, respectively successively lamination setting the first lithium battery electric core 501, the second lithium battery
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 8, with
Above-mentioned multiple lithium battery electric cores may each comprise：First collector 51, anode layer 54, solid-state electrolyte layer 53, negative electrode layer 55 and
Two collectors 52.
As shown in Figure 8, the second collector is shared between the first lithium battery electric core 501 and the second lithium battery electric core 502
52.In the present embodiment, the material of second collector 52 is aluminium copper AlxCu1-x, wherein 0.1≤x≤0.9.
It is respectively provided with negative electrode layer 55 in two opposite main surfaces of second collector 52, it is seen then that the first lithium battery
Can be to be connected in parallel between core 501 and the second lithium battery electric core 50 2.
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
Can be to be connected in series 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
Parallel connectivity can be formed with the 4th lithium battery electric core 504 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. 8, in actual lithium battery 50, specific connection type can be according to practical lithium battery
Performance requirement adjusts, and is not intended to limit the present utility model herein.
Referring to Fig. 9, the utility model the 8th embodiment provide a lithium battery 60, the present embodiment with the above-mentioned 5th to
Lithium battery provided in 7th embodiment difference lies in：The lithium battery 60 further includes encapsulating structure 69, definition with it is multiple
The surface of the parallel lithium battery electric core 601 of Direction of superposition of the lithium battery electric core 61 is side 611, the encapsulating structure 69
It is disposed around the side 611 of the lithium battery electric core 601.
As shown in Figure 9, the lithium battery electric core 601 includes the first collection successively 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
The lithium battery electric core 601 and the positive and negative anodes of another lithium battery electric core 601 share collector.
In the present embodiment, the restriction limit related to negative electrode layer 13 described in above-mentioned first embodiment in relation to negative electrode layer 63
Fixed identical, details are not described herein.
As shown in Figure 9, the encapsulating structure 69, which encloses, sets the process of the side 611 and may 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 the present embodiment some particular embodiments, the encapsulating structure 69 can be the protective layer being additionally arranged or profit
Extended with the solid electrolyte 61 and is formed.
Referring to Fig. 10, the 9th embodiment of the utility model provides the preparation method S10 of a lithium battery electric core：
Step S11 provides an anode layer, and solid electrolyte raw material is coated in the one side of anode layer to form required 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 S12；
Step S13 forms the negative pole structure in one side of the solid-state electrolyte layer far from the anode layer.
In above-mentioned steps S13, the preparation method of the negative pole structure is as described in above-mentioned second embodiment, herein no longer
It repeats.Specifically, 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 the present embodiment some specific implementations
Form above-mentioned solid-state electrolyte layer.Or it can also be formed respectively with the surface that the anode layer is oppositely arranged in the negative electrode layer above-mentioned
Solid-state electrolyte layer.
Compared with prior art, negative electrode layer and its lithium battery electric core and lithium battery provided by the utility model have such as
Under advantageous effect：
In the negative electrode layer that utility model is provided comprising metal porous structure and melting are filled in metal porous structure
Hole in lithium metal.In such a configuration, metal porous structure described in the negative electrode layer can be used as the lithium metal
The skeleton for depending on or supporting, so as to form the alloy with 3D network structures with lithium metal, in battery charging and discharging, lithium from
During son migration, the structure of negative electrode layer is avoided to change or cave in, so as to extend following for lithium battery electric core and battery
The ring service life.
Further, in negative electrode layer provided by the utility model, due to lithium metal be filled in metal porous structure it
In, therefore, the specific surface area on lithium metal surface greatly increases, and local current reduces, and can further reduce the enrichment of lithium ion
Degree is conducive to dendrite inhibition growth, therefore safe.
In the negative electrode layer that utility model is provided, it may also include mixed metal skeleton, the mixed metal skeleton packet
The hole formed by the metal of one or more combination in Al, Cu or Ni element is included, the negative electrode layer further includes that melting is filled in
Lithium metal in the hole.In such a configuration, metal mixture layer described in the negative electrode layer can be used as the cathode
The support frame of layer forms 3D structures, in battery charging and discharging so as to form the alloy with network structure with lithium metal
When, during lithium ion mobility, avoid the structure of negative electrode layer from changing or cave in, so as to extend lithium battery electric core and electricity
The cycle life in pond.
Further, in negative electrode layer provided by the utility model, since lithium metal is among being filled in hole,
The specific surface area on lithium metal surface greatly increases, and local current reduces, and can further reduce the enrichment degree of lithium ion, favorably
It is grown in dendrite inhibition, therefore safe.
The utility model also provides a kind of lithium battery electric core and lithium battery comprising negative electrode layer as described above.Wherein collect
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 with.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
The purpose of ion provides unimpeded diffusion and migrating channels during charge and discharge, column crystal is that the high performance cathode of matching is real
The maximum of existing positive electrode utilizes, and improves the efficiency of lithium insertion and abjection.
The solid lithium battery provided in the utility model, by using the above-mentioned solid lithium battery of the utility model
Encapsulating structure packaging electric core has the advantages that encapsulation is close, so as to effective protection battery core, and then makes to carry in the utility model
The solid lithium battery of confession has high service life.
The above is only the preferred embodiment of the utility model only, is not intended to limit the utility model, all at this
Any modification made by within the principle of utility model, equivalent replacement and improvement etc. should all include the scope of protection of the utility model
Within.
Claims (10)
1. a kind of negative electrode layer, it is characterised in that：The negative electrode layer includes that metal porous structure and melting are filled in metal porous knot
Lithium metal in the hole of structure, the metal porous structure by one or more combination in Al, Cu or Ni element metal or gold
Belong to compound to be formed.
2. negative electrode layer as described in the appended claim 1, it is characterised in that：The metal porous structure includes metallic particles and/or gold
Belong to compound particle, the metal porous structure includes the hole formed between metallic particles and/or metal compound particles, is melted
The lithium metal melted is filled in the hole.
3. negative electrode layer as stated in claim 2, it is characterised in that：Hole in the metal porous structure of the negative electrode layer
Volume accounts for the 20%-90% of the total volume of the negative electrode layer；The quality of the lithium metal accounts for the gross mass of the negative electrode layer
10%-90%.
4. negative electrode layer as described in the appended claim 1, it is characterised in that：The pore size of the metal porous structure is 10nm-1 μ
M, porosity is 10%-90% in the metal porous structure.
5. the negative electrode layer as described in any one of claim 1-4, it is characterised in that：The thickness of the negative electrode layer is 5-10 μm.
6. a kind of lithium battery electric core, it is characterised in that：It includes negative pole structure, and the negative pole structure includes collector and such as right
It is required that any one of 1-4 negative electrode layers, the negative electrode layer are formed on a main surface of the collector.
7. lithium battery electric core as recited in claim 6, it is characterised in that：The lithium battery electric core further includes anode structure and sets
Set the solid-state electrolyte layer between the anode structure and negative pole structure；The anode structure includes anode layer, the anode
Layer includes column crystal positive electrode.
8. lithium battery electric core as recited in claim 7, it is characterised in that：The lithium battery electric core further includes two collectors,
The collector includes two opposite main surfaces, and the anode layer is formed in one of main surface, using as the lithium battery
The anode structure of 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 setting lithiums as described in claim 7 or 8
Battery battery core shares a positive and negative copolar collector, the positive and negative copolar between at least two lithium battery electric cores being directly superposed
Collector plate includes two opposite main surfaces, and the anode layer is formed in one of main surface, using as a wherein lithium battery
The anode structure of battery core forms negative electrode layer 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 to be connected in series between battery core；The lithium battery further includes encapsulating structure, definition 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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109494351A (en) * | 2018-11-22 | 2019-03-19 | 罗伯特·博世有限公司 | Solid lithium battery, cathode and their preparation method for solid lithium battery |
| CN111162265A (en) * | 2020-01-17 | 2020-05-15 | 中国人民解放军国防科技大学 | Preparation method of metal lithium composite negative electrode for solid-state battery |
| CN112133955A (en) * | 2020-09-28 | 2020-12-25 | 蜂巢能源科技有限公司 | Cell structure of solid-state battery and preparation method thereof |
| CN117810365A (en) * | 2023-12-27 | 2024-04-02 | 蜂巢能源科技股份有限公司 | Negative plate and preparation method and application thereof |
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2017
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109494351A (en) * | 2018-11-22 | 2019-03-19 | 罗伯特·博世有限公司 | Solid lithium battery, cathode and their preparation method for solid lithium battery |
| CN111162265A (en) * | 2020-01-17 | 2020-05-15 | 中国人民解放军国防科技大学 | Preparation method of metal lithium composite negative electrode for solid-state battery |
| CN111162265B (en) * | 2020-01-17 | 2022-04-12 | 中国人民解放军国防科技大学 | Preparation method of metal lithium composite negative electrode for solid-state battery |
| CN112133955A (en) * | 2020-09-28 | 2020-12-25 | 蜂巢能源科技有限公司 | Cell structure of solid-state battery and preparation method thereof |
| CN112133955B (en) * | 2020-09-28 | 2021-12-07 | 蜂巢能源科技有限公司 | Cell structure of solid-state battery and preparation method thereof |
| CN117810365A (en) * | 2023-12-27 | 2024-04-02 | 蜂巢能源科技股份有限公司 | Negative plate and preparation method and application thereof |
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