CN108376763A - A kind of composite negative pole structure, solid lithium battery battery core, solid lithium battery and preparation method thereof - Google Patents
A kind of composite negative pole structure, solid lithium battery battery core, solid lithium battery and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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
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Abstract
The present invention relates to field of lithium more particularly to a kind of composite negative pole structure, solid lithium battery battery core, solid lithium battery and preparation method thereof.The composite negative pole structure includes a negative electrode layer and the passivation film for being formed in one surface of the negative electrode layer, and the negative electrode layer includes metal gridding skeleton and is compound in the lithium metal in the metal gridding skeleton by hot pressing；The solid lithium battery battery core includes composite negative pole structure as described above；The solid lithium battery includes one or more solid lithium battery battery cores as mentioned, connects and/or is connected in parallel between multiple solid lithium battery battery cores；The solid lithium battery that above-mentioned technical proposal provided by the present invention is provided has the advantages that lithium an- ode volume change is small, electro-deposition is uniform in charge and discharge process, and it can effectively inhibit the formation of Li dendrite, and then the effective cycle life and service life for improving solid lithium battery.
Description
【Technical field】
The present invention relates to field of lithium more particularly to a kind of composite negative pole structure solid lithium battery battery cores, all solid state
Lithium battery and preparation method thereof.
【Background technology】
Since 90 annual commercial lithium battery of last century comes out, 3C Product, battery-operated motor cycle, low speed electricity have been widely used in it
The fields such as motor-car and electric vehicle.
But the point that existing lithium battery Presence of an interface impedance is big, energy density is low；Meanwhile existing lithium battery is negative in lithium metal
Pole volume in charge and discharge process change it is larger, and then destroy lithium battery structure；Meanwhile existing lithium battery is in charge and discharge
Electro-deposition Density inhomogeneity in journey, the growth in turn resulting in Li dendrite further destroys lithium battery structure, and then reduces lithium battery
Cycle performance and service life.
【Invention content】
To overcome current lithium battery poor circulation and the low disadvantage of physical life, the present invention provides a kind of all solid lithiums
Battery battery core, solid lithium battery and preparation method thereof.
The present invention is in order to solve the above technical problems, one technical solution of offer is as follows：A kind of composite negative pole structure comprising one
Negative electrode layer and the passivation film for being formed in one surface of the negative electrode layer, the negative electrode layer include metal gridding skeleton and pass through hot pressing
The lithium metal being compound in the metal gridding skeleton.
Preferably, the passivation film includes LiCl and/or LiF films, and the metal gridding skeleton is that Ni and/or Cu is closed
Gold.
The present invention is in order to solve the above technical problems, to provide another technical solution as follows：A kind of preparation of composite negative pole structure
Method comprising following steps：Prepare the negative electrode layer containing lithium metal and metal gridding skeleton；Cathode is placed on solution or fluorine
In the gas of Leon, to form passivation film in cathode layer surface；The wherein described solution includes carbonic acid lipid electrolyte, ethers electrolysis
One or more of liquid, lithium salt electrolyte and thionyl chloride solution.
Preferably, the preparation of the negative electrode layer includes providing a prefabricated metal grid frame and lithium metal or one base of offer
Bottom prepares metal gridding skeleton in substrate；Under vacuum or under Ar compression rings border, metal gridding skeleton and lithium metal are heated
Set 170 DEG C -220 DEG C；
Preferably, the preparation of the passivation film includes providing a preformed solution；The negative electrode layer is soaked in described molten
In liquid, so that the lithium metal in negative electrode layer and solution reaction, LiCl and/or LiF films are formed in negative electrode layer and solution contact surface
Layer.
Preferably, the preparation of the passivation film can also be to provide a sealable container, and the negative electrode layer is fixed on
In the container；Container is extracted into vacuum, and is filled with Freon gas to 0.4atm-3atm；Container and negative electrode layer are added
Heat makes the lithium metal in negative electrode layer and freon gas precursor reactant, and then formation LiF is thin in cathode layer surface to 90 DEG C -190 DEG C
Film layer.
The present invention is in order to solve the above technical problems, to provide another technical solution as follows：A kind of solid lithium battery battery core,
Including composite negative pole structure as described above.
Preferably, the solid lithium battery battery core further includes electrolyte layer, positive decorative layer, anode layer and afflux
Body, the composite negative pole structure, electrolyte layer, positive decorative layer and anode layer stack gradually setting, and the collector is set to
On the face of the anode layer and composite negative pole structure far from the electrolyte layer.
Preferably, the anode layer includes LiNixCoyMzO2, wherein
The numerical value of x+y+z=1, the x include 0-0.8, and the numerical value of the y includes 0-0.4, and the numerical value of the z is 1-x-y
Difference, wherein M includes Mn and/or Al metallic elements, and the electrolyte layer includes nanoscale SiO2And/or Al2O3, the anode
Decorative layer is sulfide and/or oxide solid electrolyte.
The present invention is in order to solve the above technical problems, to provide another technical solution as follows：A kind of solid lithium battery comprising
One or more solid lithium battery battery cores as described above.
Compared with prior art, composite negative pole structure provided by the present invention, by by lithium metal hot pressing and nickel and/or
In the metal gridding skeleton that the metals such as copper are constituted, since the metal gridding skeleton that the metals such as the nickel and/or copper are constituted has pole
High intensity, and then effectively reduce volume of the lithium an- ode in the charge and discharge process of solid lithium battery battery core and become
Change, and promote stability and uniformity of the battery core in reaction, and then protects the structural stability of composite negative pole structure,
Improve cycle life；The solid lithium battery battery core of offer of the present invention, it is described compound by using composite negative pole structure
Negative pole structure, by the metal gridding skeleton that constitutes the metals such as lithium metal hot pressing and nickel and/or copper, due to the nickel
And/or the metal gridding skeleton that the metals such as copper are constituted has high intensity, and then lithium an- ode is effectively reduced complete
Volume change in the charge and discharge process of solid state lithium battery battery core, and promote battery core reaction when stability and uniformly
Property, and then the structural stability of composite negative pole structure is protected, cycle life is improved, all-solid lithium battery battery core is extended
Service life；Further, the all-solid-state battery battery core restrained effectively by forming passivation film in cathode layer surface
The formation of Li dendrite, meanwhile, solid lithium battery battery core is also effectively promoted, the equal property of the electro-deposition in charge and discharge process,
Further suppress the volume change of the growth and lithium an- ode of Li dendrite in charge and discharge process.
Meanwhile the solid lithium battery battery core is by using LiNixCoyMzO2Positive electrode effectively provides complete solid
The energy density of state lithium battery electric core；Comprising nano-filled object include nanoscale SiO by practicality2And/or Al2O3Etc. nanometers fill out
The PEO base polymer electrolytes for filling object have been effectively promoted the conduction velocity of lithium ion in the electrolyte；Further, pass through
Positive decorative layer is set between anode layer and electrolyte layer, significantly reduces the interface electricity between anode layer and electrolyte layer
Resistance.
Solid lithium battery provided in the present invention, by using one or more above-mentioned solid lithium battery electricity
Core, density can be connected and may be up to 400Wh/kg by so that the solid lithium battery is had, meanwhile, the solid lithium battery is in charge and discharge
Change small, cell deposition uniformly with negative electrode volume in the process and can effectively inhibit the formation of Li dendrite, and then is effective
Improve the cycle life and service life of solid lithium battery.
The present invention also provides composite negative pole structure preparation method, in this way, can quickly prepare described multiple
Close the structures such as negative pole structure, the passivation film of negative pole structure.The present invention also provides solid lithium battery battery core preparation method,
All solid state lithium battery electric core is fallen in this way, can quickly prepare.Solid lithium battery preparation side provided by the present invention
Method can prepare the solid lithium battery for including above-mentioned solid lithium battery battery core.
【Description of the drawings】
Figure 1A is a kind of composite negative pole structure schematic diagram of a layer structure provided in first embodiment of the invention.
Figure 1B is the variable condition schematic diagram of Figure 1A in the present invention.
Fig. 2A-Fig. 2 D are the flow signals of the composite negative pole structure preparation method provided in second embodiment of the invention
Figure.
Fig. 3 is a kind of solid lithium battery battery core schematic diagram of a layer structure provided in third embodiment of the invention.
Fig. 4 A are a kind of solid lithium battery schematic diagram of a layer structure provided in fourth embodiment of the invention.
Fig. 4 B are a kind of layer structural representations of solid lithium battery encapsulating structure provided in fourth embodiment of the invention
Figure.
Fig. 5 is a kind of solid lithium battery method for making electric core flow signal provided in eighth embodiment of the invention
Figure.
【Specific implementation mode】
In order to make the purpose of the present invention, technical solution and advantage be 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.
A and Figure 1B are please referred to Fig.1, a kind of composite negative pole structure 100 is provided in the first embodiment of the present invention comprising
Negative electrode layer 101 and passivation film 102, the passivation film 102 are formed on 101 surface of the negative electrode layer.The negative electrode layer 101
Further include metal gridding skeleton 1011 and lithium metal 1012, the lithium metal 1012 is compound in the metal grill bone by hot pressing
In frame 1011.The metal gridding skeleton 1011 mainly has the metals such as Cu and/or Ni；Preferably, the metal gridding skeleton
1011 be Cu.The passivation film 102 includes mainly LiCl and/or LiF films；Preferably, the passivation film 102 is LiF
Film layer.
A kind of preparation method S100 of composite negative pole structure, the negative pole structure are provided in the second embodiment of the present invention
For the negative pole structure 100 provided in first embodiment of the invention.Specifically, Fig. 2A is please referred to, the preparation of the negative pole structure
Method S100 includes：
Step S101：Prepare the negative electrode layer containing lithium metal and metal gridding skeleton；
Step S102：Cathode is placed in solution or Freon gas, so that the lithium metal in the negative electrode layer and institute
Solution or freon gas precursor reactant are stated, to form passivation film in cathode layer surface.
Fig. 2 B are please referred to, specifically, the step S101 includes：
Step S1011：One or more of metal gridding skeletons in lithium metal and prefabricated Al, Cu or a Ni are provided；
Step S1012：Under vacuum or under Ar compression rings border, by one or more of metal gridding skeletons in Al, Cu or Ni
170 DEG C -220 DEG C are set with lithium metal heating；
Step S1013：After lithium metal softening, by the lithium metal hot pressing after softening into a kind of or several in Al, Cu or Ni
In kind metal grill, negative electrode layer is formed.
Meanwhile the step S1011 can also be：Lithium metal and a matrix are provided, one surface of matrix formed Al, Cu or
One or more of metal gridding skeletons in Ni.
Fig. 2 C are please referred to, the step S102 includes：
Step S1021 provides a preformed solution；
The negative electrode layer is soaked in the solution by step S1022, so that the lithium metal in negative electrode layer and solution are anti-
It answers, LiCl and/or LiF film layers is formed in negative electrode layer and solution contact surface.
Above-mentioned solution includes in carbonic acid lipid electrolyte, ethers electrolyte, lithium salt electrolyte and thionyl chloride solution
It is any one or several；Further include additive in above-mentioned electrolyte, the additive includes mainly (C2H5)4NF(HF)4, LiF and fluorine
For ethylene carbonate, reduction chemical potential and Li+Close metal ions M+, lithium polysulfide and LiNO3.In the negative electrode layer
Lithium metal after contacting above-mentioned solution, under the common effect of solution and additive, in the negative electrode layer and the electricity
LiCl and/or LiF film layers are formed on the contact surface of electrolyte solution.
In some embodiments, the step S102 includes：
Step S1021 provides a thionyl chloride solution；
Step S1022, the negative electrode layer is soaked in the thionyl chloride solution so that lithium metal in negative electrode layer with
Solution reacts 17-72h at 40-90 DEG C, to form LiCl in negative electrode layer and solution contact surface
Further, the cathode and thionyl chloride solution reaction temperature can also be 65-80 DEG C in the present embodiment,
Reaction time can also be 24-40 hours；Specifically, the cathode and thionyl chloride solution reaction temperature can also be 40 DEG C, 50
DEG C, 60 DEG C, 76 DEG C or 90 DEG C, the reaction time be specially 17h, for 24 hours, 30h, 50h, 65h or 70h；Preferably, the cathode and Asia
Chlorosulfuric acid solution reaction temperature can also be 76 DEG C, reaction time 30h.
Thionyl chloride solution in above-mentioned steps S1021, can also replace with thionyl chloride solution and lithium salt electrolyte is mixed
Close solution；The wherein described lithium salt electrolyte solubility is 1-5mol/L, the volume of the sulfonyl solutions of chlorine and lithium salt electrolyte solution
Than being (1:10)-(10:1).
Fig. 2 D are please referred to, step S102 can also be described in other embodiments of the present invention：
Step S1021` provides a sealable container, the negative electrode layer is fixed in the container；
Container is extracted vacuum by step S1022`, and it is 0.4atm-5atm to be filled with Freon gas to air pressure；
Step S1023` is heated to 90 DEG C -190 DEG C to container and negative electrode layer, makes the lithium metal in negative electrode layer and freon
Gas reaction, and then LiF film layers are formed in cathode layer surface.
In the step S1022`, described to be filled with Freon gas to air pressure be preferably 3.8atm-4.2atm；The step
In S1023`, container and negative electrode layer heating temperature are preferably 140 DEG C -160 DEG C.
Referring to Fig. 3, a kind of solid lithium battery battery core 10 is provided in the third embodiment of the present invention, it is described all solid state
Lithium battery electric core 10 includes composite negative pole structure 100, and the composite negative pole structure 100 is provided in first embodiment of the invention
Composite negative pole structure 100.Meanwhile the solid lithium battery battery core 10 further includes collector 11, anode layer 12, anode modification
Layer 13 and electrolyte layer 14.The collector 11 includes two the first collectors 111 and the second collector being oppositely arranged
112, first collector, 111 and second collector 112 all has that there are two the main surfaces that are oppositely arranged.
Specifically, the anode layer 12 is set in 111 1 main surface of the first collector, the anode layer 12 is far from institute
It states and is provided with positive decorative layer 13 on the face of the first collector 111,13 face far from the anode layer 12 of the anode decorative layer
On be provided with electrolyte layer 14, the electrolyte layer 14 is provided with passivation film 102 on the face far from the positive decorative layer 13,
The passivation film 102 is provided with negative electrode layer 101 on the face far from the electrolyte layer 14, the negative electrode layer 101 is far from described
The second collector 112 is provided on the face of electrolyte layer 14.
The coating of the anode layer 12 is formed in 111 1 main surface of the first collector comprising LiNixCoyMzO2Material
Material, wherein M includes AL and/or Mn, and the summation of x, y and z are 1；The x includes 0-0.8, specifically, x can be 0,0.3,
0.4, one or more of 0.5,0.6 or 0.8, the y includes 0-0.4, and specifically, y can be 0,0.1,0.2,0.3 or 4
One or more of, the z includes 0-0.3, and specifically, z can be one or more of 0,0.1,0.2 or 0.3.It can be with
Understand, the material of the anode layer 12 includes LiNiO2、LiCoO2、LiMnO2、LiNi0.4Co0.3Mn0.3O2、
LiNi0.4Co0.4Mn0.2O2、LiNi0.5Co0.3Mn0.2O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、
LiNi0.4Co0.3Al0.3O2、LiNi0.4Co0.4Al0.2O2、LiNi0.5Co0.3Al0.2O2、LiNi0.6Co0.2Al0.2O2Or
LiNi0.8Co0.1Al0.1O2；Preferably, the material of the anode layer 12 is preferably LiNi0.6Co0.2Mn0.2O2、
LiNi0.8Co0.1Mn0.1O2、LiNi0.6Co0.2Al0.2O2Or LiNi0.8Co0.1Al0.1O2。
Meanwhile the thickness of the anode layer 12 is 110nm-5 μm；Further, the thickness of the anode layer 12 is
100nm-10μm；Specifically, the thickness of the anode layer 12 is 5 μm, 10 μm, 20 μm, 40 μm, 50 μm, 60 μm, 90 μm, 100 μm
Or one or more of 110 μm.
On face of the anode layer 12 far from first collector 111, it is additionally provided with a positive decorative layer 13.It is main
Including oxide and/sulfide solid electrolyte；The oxide electrolyte includes MgO, CoO, Al2O3、ZrO2Or TiO2In
It is one or more of；The sulfide electrolyte includes Li2S、P2S5、SiS2、GeS2Or B2S3One or more of.
Meanwhile the thickness of the positive decorative layer 13 is 1-300nm；Specifically, the thickness of the positive decorative layer 13 can
Think one kind or several in 1nm, 10nm, 20nm, 50nm, 100nm, 150nm, 200nm, 250nm, 280nm, 290nm or 300nm
Kind.
The electrolyte layer 14 is all solid state electrolyte, and all solid state electrolyte is preferably PEO based polyalcohols solid-state electricity
Xie Zhi, the PEO based polyalcohols solid electrolyte further include having nano-filled object, and the nano-filled object is electrical conductivity materials,
It can be effectively promoted and accelerate conduction of the lithium ion in PEO base electrolytes, further, the high electricity of solid electrolyte of body
Conductance.The nano-filled object includes SiO2And/or Al2O3Deng.Further, the thickness of the electrolyte layer 14 is 1-60 μm；
Specifically, the thickness of the electrolyte layer 14 is 1 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 55 μm or 60 μm.
The negative electrode layer 101 includes that copper and/or nickel metal gridding skeleton and hot pressing are compound in the copper and/or nickel metal
The lithium metal is heated to 180 DEG C -220 DEG C by the lithium metal in grid frame, while by the copper and/or nickel metal grill
Skeleton is also heated at 180 DEG C -220 DEG C, then lithium metal pressurizes together in the metal gridding skeleton, tool is uniformly filled in institute
In the gap for stating grid frame.The copper and/or nickel metal gridding skeleton have good mechanical strength, and then lithium metal hot pressing is multiple
After in conjunction and the copper and/or nickel metal gridding skeleton, lithium an- ode can be effectively prevented from and existed, volume during charge point
It changes, and damages the structure of solid lithium battery, reduce its service life.
In addition, 101 surface of the negative electrode layer is additionally provided with a passivation film 102, the passivation film can effectively facilitate lithium
Ion is in 101 surface uniform deposition of negative electrode layer；Meanwhile the passivation film also has certain mechanical strength, can effectively keep away
Exempt from the generation of solid lithium battery Li dendrite.
Fig. 4 A and Fig. 4 B are please referred to, a kind of solid lithium battery 1 is provided in the fourth embodiment of the present invention, it is described complete solid
State lithium battery 1 only includes solid lithium battery battery core 10 and encapsulating structure 19 in one or more above-mentioned first embodiments.It is fixed
Justice 111 and second surface of the collector 112 far from the electrolyte layer 14 of the first collector is end face 107, both ends of the surface 107
Between 10 surface of solid lithium battery battery core be side 108, the encapsulating structure 19 is coated on the side 108 and end face
On 107.The encapsulating structure 19 includes mainly aluminum plastic film 191.The aluminum plastic film includes close lithium barrier layer 1911, aluminium film resistance successively
Interlayer 1912 and protective layer 1913, parent's lithium barrier layer hot pressing is together on the surface of the all-solid-state battery battery core 10.
Referring to Fig. 5, in the fifth embodiment of the present invention, a kind of preparation method of solid lithium battery battery core is provided
S10, the solid lithium battery battery core are the solid lithium battery battery core 10 provided described in the above-mentioned 3rd embodiment of the present invention,
Identical with 3rd embodiment to the restriction of the solid lithium battery battery core, details are not described herein.Described in the present embodiment
The preparation method S10 of solid lithium battery battery core its include mainly：
Step S11 provides anode layer, composite negative pole structure and two collectors, and the one of a collector wherein respectively
Face forms anode layer, and forms the composite negative pole structure in the one side of another collector；
Step S12 forms positive decorative layer on surface of the anode layer far from collector；
Step S13, on surface of the anode layer decorative layer far from the anode layer and/or in the composite negative pole structure
Coating forms electrolyte layer on face far from collector where it；
Electrolyte layer is pressed together on the positive decorative layer and the composite negative pole by step S14 by hot pressing complex method
Between structure.
Wherein, compound described in the preparation method and second embodiment of the invention of composite negative pole structure in the step S11
The preparation method S100 of negative pole structure is identical, and details are not described herein.
Further, be originally described offer in embodiment the preparation method S10 of solid lithium battery battery core in, described
An encapsulation step S15 can also be added after step S14, and then prepares all solid lithium in the present invention described in fourth embodiment
Battery.
Specifically, the step S15 includes providing a prefabricated encapsulating structure, and seal to the all-solid-state battery battery core
Dress, or directly form encapsulating structure on all-solid-state battery battery core surface.
Further, the encapsulating structure is the encapsulating structure provided in the fourth embodiment of the present invention, related encapsulation
The restriction of structure, details are not described herein.
Compared with prior art, composite negative pole structure provided by the present invention, by by lithium metal hot pressing and nickel and/or
In the metal gridding skeleton that the metals such as copper are constituted, since the metal gridding skeleton that the metals such as the nickel and/or copper are constituted has pole
High intensity, and then effectively reduce volume of the lithium an- ode in the charge and discharge process of solid lithium battery battery core and become
Change, and promote stability and uniformity of the battery core in reaction, and then protects the structural stability of composite negative pole structure,
Improve cycle life；The solid lithium battery battery core of offer of the present invention, it is described compound by using composite negative pole structure
Negative pole structure, by the metal gridding skeleton that constitutes the metals such as lithium metal hot pressing and nickel and/or copper, due to the nickel
And/or the metal gridding skeleton that the metals such as copper are constituted has high intensity, and then lithium an- ode is effectively reduced complete
Volume change in the charge and discharge process of solid state lithium battery battery core, and promote battery core reaction when stability and uniformly
Property, and then the structural stability of composite negative pole structure is protected, cycle life is improved, all-solid lithium battery battery core is extended
Service life；Further, the all-solid-state battery battery core restrained effectively by forming passivation film in cathode layer surface
The formation of Li dendrite, meanwhile, solid lithium battery battery core is also effectively promoted, the equal property of the electro-deposition in charge and discharge process,
Further suppress the volume change of the growth and lithium an- ode of Li dendrite in charge and discharge process.
Meanwhile the solid lithium battery battery core is by using LiNixCoyMzO2Positive electrode effectively provides complete solid
The energy density of state lithium battery electric core；Comprising nano-filled object include nanoscale SiO by practicality2And/or Al2O3Etc. nanometers fill out
The PEO base polymer electrolytes for filling object have been effectively promoted the conduction velocity of lithium ion in the electrolyte；Further, pass through
Positive decorative layer is set between anode layer and electrolyte layer, significantly reduces the interface electricity between anode layer and electrolyte layer
Resistance.
Solid lithium battery provided in the present invention, by using one or more above-mentioned solid lithium battery electricity
Core, density can be connected and may be up to 400Wh/kg by so that the solid lithium battery is had, meanwhile, the solid lithium battery is in charge and discharge
Change small, cell deposition uniformly with negative electrode volume in the process and can effectively inhibit the formation of Li dendrite, and then is effective
Improve the cycle life and service life of solid lithium battery.
The present invention also provides composite negative pole structure preparation method, in this way, can quickly prepare described multiple
Close the structures such as negative pole structure, the passivation film of negative pole structure.The present invention also provides solid lithium battery battery core preparation method,
All solid state lithium battery electric core is fallen in this way, can quickly prepare.Solid lithium battery preparation side provided by the present invention
Method can prepare the solid lithium battery for including above-mentioned solid lithium battery battery core.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all originals in the present invention
Any modification made by within then, equivalent replacement and improvement etc. should all include within protection scope of the present invention.
Claims (10)
1. a kind of composite negative pole structure, it is characterised in that：It includes a negative electrode layer and is formed in the blunt of one surface of the negative electrode layer
Change film layer, the negative electrode layer includes metal gridding skeleton and is compound in the lithium metal in the metal gridding skeleton by hot pressing.
2. composite negative pole structure as described in claim 1, it is characterised in that：The passivation film includes LiCl and/or LiF
Film, the metal gridding skeleton are Ni and/or Cu alloys.
3. a kind of preparation method of composite negative pole structure, it is characterised in that：It prepares negative containing lithium metal and metal gridding skeleton
Pole layer；
Cathode is placed in solution or Freon gas, to form passivation film in cathode layer surface；The wherein described solution packet
Include one or more of carbonic acid lipid electrolyte, ethers electrolyte, lithium salt electrolyte and thionyl chloride solution.
4. such as a kind of preparation method of composite negative pole structure in claim 3, it is characterised in that：The preparation packet of the negative electrode layer
It includes,
One prefabricated metal grid frame and lithium metal are provided or a substrate is provided, metal gridding skeleton is prepared in substrate；
Under vacuum or under Ar compression rings border, metal gridding skeleton and lithium metal heating are set 170 DEG C -220 DEG C；
After lithium metal softening, by the lithium metal hot pressing of softening into metal gridding skeleton.
5. such as a kind of preparation method of composite negative pole structure in claim 3, it is characterised in that：The preparation packet of the passivation film
It includes,
One preformed solution is provided；
The negative electrode layer is soaked in the solution so that the lithium metal in negative electrode layer and solution reaction, negative electrode layer with it is molten
Liquid contact surface forms LiCl and/or LiF film layers.
6. such as a kind of preparation method of composite negative pole structure in claim 3, it is characterised in that：The preparation of the passivation film is also
Can be,
One sealable container is provided, the negative electrode layer is fixed in the container；
Container is extracted into vacuum, and is filled with Freon gas to 0.4atm-3atm；
Container and negative electrode layer are carried out being heated to 90 DEG C -190 DEG C, make the lithium metal in negative electrode layer and freon gas precursor reactant, into
And LiF film layers are formed in cathode layer surface.
7. a kind of solid lithium battery battery core, it is characterised in that：Including the composite negative pole knot as described in claim any one of 1-2
Structure.
8. a kind of solid lithium battery battery core as claimed in claim 7, it is characterised in that：The solid lithium battery battery core is also
Including electrolyte layer, positive decorative layer, anode layer and collector, the composite negative pole structure, electrolyte layer, anode modification
Layer and anode layer stack gradually setting, and the collector is set to the anode layer and composite negative pole structure far from the electrolysis
On the face of matter layer.
9. a kind of solid lithium battery battery core as claimed in claim 8, it is characterised in that：The anode layer includes
LiNixCoyMzO2, wherein the numerical value of x+y+z=1, the x include 0-0.8, and the numerical value of the y includes 0-0.4, the number of the z
Value is the difference of 1-x-y, and wherein M includes Mn and/or Al metallic elements, and the electrolyte layer includes nanoscale SiO2And/or Al2O3,
The anode decorative layer is sulfide and/or oxide solid electrolyte.
10. a kind of solid lithium battery, it is characterised in that：It includes one or more such as claim 8-9 any one of them
Solid lithium battery battery core.
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