CN110957471A - Method for improving interfacial wettability of electrode of quasi-solid battery - Google Patents

Method for improving interfacial wettability of electrode of quasi-solid battery Download PDF

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CN110957471A
CN110957471A CN201911302810.1A CN201911302810A CN110957471A CN 110957471 A CN110957471 A CN 110957471A CN 201911302810 A CN201911302810 A CN 201911302810A CN 110957471 A CN110957471 A CN 110957471A
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pole piece
electrolyte
solid
negative electrode
battery
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包大新
王国光
王占洲
蒋易晟
石程
夏阳
张俊
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Hengdian Group DMEGC Magnetics Co Ltd
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Hengdian Group DMEGC Magnetics Co Ltd
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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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
    • 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
    • H01M4/139—Processes of manufacture
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a method for improving the wettability of an electrode interface of a similar solid-state battery, which comprises the following steps: s1, soaking the positive pole piece and the negative pole piece in electrolyte; s2, freezing the soaked positive pole piece and negative pole piece to obtain a positive pole piece and a negative pole piece of pre-buried electrolyte; and S3, pressing and molding the positive pole piece and the negative pole piece of the pre-embedded electrolyte and the solid electrolyte membrane to obtain a similar solid battery, and heating to melt the pre-embedded electrolyte and wet the solid battery. The method for preparing the quasi-solid battery is fast and efficient, simple to operate and low in cost, and can solve the problem of electrode interface wetting in the assembling process of the quasi-solid battery.

Description

Method for improving interfacial wettability of electrode of quasi-solid battery
Technical Field
The invention belongs to the technical field of solid-state batteries, and relates to a method for improving the wettability of an electrode interface of a solid-state battery.
Background
Compared with the traditional liquid battery, the solid battery has high energy density, long cycle life, safety and reliability, and is the focus of attention of researchers at home and abroad. However, the problems of serious capacity attenuation and poor long-term cycling stability in the cycling process of the solid-state battery, battery short circuit caused by the growth of dendrites and the like are closely related to the physical and chemical contact of the solid-solid interface of the solid-state battery. Therefore, improving the interfacial wettability of the solid-state battery is an important factor that drives its development.
CN 109994783 a discloses a method for preparing an all-solid-state battery by in-situ solid stating, comprising the following steps: s1: uniformly stirring lithium salt, a small molecular monomer additive and a cross-linking agent to obtain a mixed solution; s2: injecting the mixed solution into a battery unit containing a positive electrode layer, a negative electrode layer and a solid electrolyte layer or a diaphragm layer, and fully infiltrating the positive electrode layer, the negative electrode layer and the solid electrolyte layer or the diaphragm layer; s3: and polymerizing the whole battery unit under the irradiation of electron beams, and carrying out in-situ polymerization and solidification on the mixed solution in a positive electrode layer, a negative electrode layer, a solid electrolyte layer or a diaphragm layer and layers in the battery unit to obtain the all-solid-state battery. According to the method, the liquid micromolecule monomers infiltrated into each interface in the cell unit are directly polymerized and solidified in situ to generate the solid electrolyte through an electron beam polymerization method, so that the compatibility of the solid-solid interface of the all-solid cell is greatly improved, but the method for preparing the all-solid cell is complex in operation and high in cost, and is not beneficial to industrial production.
CN 108933284a discloses a flexible all-solid-state lithium ion secondary battery and a preparation method thereof, the method comprises the following steps: 1) preparing a gellable system; 2) pressing a negative electrode current collector and a negative electrode material into a negative electrode, and then placing the negative electrode in a gellable system for infiltration; or the gel system can be coated on the surface of the negative electrode pressed by the negative electrode current collector and the negative electrode material; 3) pressing the positive current collector and the positive material into a positive electrode, and then placing the positive electrode in a gel system for infiltration; or the gellable system is coated on the surface of the positive electrode pressed by the positive electrode current collector and the positive electrode material; 4) pressing the soaked or coated negative electrode, optional diaphragm and positive electrode into a whole in a battery pressing mould to form a pre-liquid injection all-solid-state battery, namely the flexible all-solid-state lithium ion secondary battery; wherein the gellable system comprises the following components: lithium salt and ether compounds, wherein the ether compounds are selected from one of cyclic ether compounds or linear ether compounds; the mass percentage of the gellable polymer and/or the gellable prepolymer in the system is 1 wt% or less. The method can form solid electrolytes on the surfaces of the positive and negative pole pieces and in situ, and the obtained lithium ion secondary battery forms a conductive network in the whole battery, so that the internal resistance of the lithium ion secondary battery can be greatly reduced, the conductivity and the rate capability can be improved, the potential safety hazard brought by liquid electrolyte can be solved, but a gel system can possibly block partial lithium ion transmission, and lithium salt cannot be fully utilized.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a method for improving the wettability of an electrode interface of a solid-state-like battery, which has the advantages of high speed, high efficiency, low cost and simple operation and solves the problems of poor wettability of the electrode interface, unstable battery cycle and the like in the assembly process of the solid-state-like battery in the prior art.
The solid-state battery of the invention is characterized in that: the electrolyte content in the solid-state battery is less than or equal to 10 wt%.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for improving the wettability of an electrode interface of a solid-state battery, which comprises the following steps:
s1, soaking the positive pole piece and the negative pole piece in electrolyte;
s2, freezing the soaked positive pole piece and negative pole piece to obtain a positive pole piece and a negative pole piece of pre-buried electrolyte;
and S3, pressing and molding the positive pole piece and the negative pole piece of the pre-embedded electrolyte and the solid electrolyte membrane to obtain a similar solid battery, and heating to melt the pre-embedded electrolyte and wet the solid battery.
The invention soaks the electrode pole piece (positive pole piece and negative pole piece) in the electrolyte, and then uses the freezing method to embed a part of the electrolyte in the electrode pole piece, and adopts the solid electrolyte membrane and the electrode pole piece embedded with the electrolyte to be pressed into the similar solid battery, and the battery is heated after being formed to melt the embedded electrolyte and wet the similar solid battery.
The manner of immersing the positive electrode plate and the negative electrode plate in the electrolyte in step S1 is not limited in the present invention, and for example, the positive electrode plate and the negative electrode plate may be immersed in the same electrolyte at the same time or immersed in different electrolytes respectively, and those skilled in the art can select the immersion method according to the needs.
The preparation method or the obtaining way of the positive plate and the negative plate is not particularly limited, and the positive plate and the negative plate can be prepared by referring to the prior art in the field or can be directly purchased. Illustratively, the positive electrode tab and the negative electrode tab may be prepared in the following manner.
Preferably, the positive electrode sheet in step S1 is prepared by the following method: and uniformly mixing the positive electrode material, the binder and the conductive agent to prepare positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, and drying to obtain the positive electrode plate.
Preferably, the negative electrode sheet of step S1 is prepared by the following method: and uniformly mixing the negative electrode material, the binder and the conductive agent to prepare negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, and drying to obtain the negative electrode plate.
Preferably, the cathode material and the anode material independently include any one of a layered structure compound, a spinel structure compound, an olivine structure compound, a NASICON structure compound, a conversion type material, an insertion type material, and an alloy type material or a combination of at least two thereof, but are not limited to the above-listed types, and other cathode materials and anode materials commonly used in the art may be used in the present invention.
Preferably, the binder used to prepare the positive electrode slurry and the binder used to prepare the negative electrode slurry independently include any one of polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), Polyethylene (PE), sodium carboxymethyl cellulose (CMC), or Styrene Butadiene Rubber (SBR), or a combination of at least two thereof.
Preferably, the conductive agent used to prepare the positive electrode slurry and the conductive agent used to prepare the negative electrode slurry independently include any one of conductive carbon black, conductive graphite, or conductive carbon fiber or a combination of at least two thereof.
Preferably, the chemical formula of the cathode material comprises LiMO2、LiMPO4、LiMn2O4、LiCo2O4、LiV2O4、Li3V2(PO4)3、Li3Fe2(PO4)3、LiNix1A1-x1O2、LiNix2CoyB1-x2-yO2Any one or the combination of at least two of the above, wherein M comprises any one or the combination of at least two of Co, Ni or Mn, A comprises any one or the combination of at least two of Co or Mn, B comprises any one or the combination of at least two of Mn or Al, x1 is more than or equal to 0 and less than or equal to 1, x2 is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1.
Preferably, the chemical formula of the anode material comprises C, Si/C, Li3N、Li7MnN4、Li3FeN2、Li3-xCoxN、SnO、TiO2Or Li4Ti5O12Any one or a combination of at least two of them. The Si/C is a silicon-carbon composite negative electrode material.
In a preferred embodiment of the method of the present invention, the electrolyte includes an electrolyte prepared using any one or a combination of at least two of Ethylene Carbonate (EC), Vinylene Carbonate (VC), dimethyl carbonate (DMC) and fluoroethylene carbonate (FEC) as a solvent. Typical but non-limiting examples of such combinations are: combinations of ethylene carbonate and vinylene carbonate, combinations of ethylene carbonate and dimethyl carbonate, combinations of vinylene carbonate and fluoroethylene carbonate, combinations of ethylene carbonate, vinylene carbonate and dimethyl carbonate, and the like.
The invention relates to electrolysisThe other components in the solution are not limited and those skilled in the art can make composition selections with reference to the prior art electrolyte, for example, the lithium salt in the electrolyte may be LiPF6、LiFSI、LiTFSI、LiBF4Or a combination of any one or at least two of LiFOB.
As a preferable technical scheme of the method, the soaking temperature in the step S1 is 0-100 ℃, and the time is 0.1-48 h. Such as 0 ℃, 10 ℃, 20 ℃, 30 ℃, 35 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃ for a period of time such as 0.1h, 0.5h, 1h, 2h, 23h, 4h, 5h, 7h, 8h, 10h, 12.5h, 15h, 17h, 20h, 23h, 24h, 26h, 28h, 30h, 32h, 36h, 40h, 43h, 45h or 48h, and the like.
In order to obtain a better soaking effect, the soaking temperature in the step S1 is more preferably 20-50 ℃ and the time is 12-24 hours.
Preferably, the temperature of the freezing in the step S2 is-150 to-5 ℃, such as-150 ℃, -140 ℃, -130 ℃, -120 ℃, -110 ℃, -100 ℃, -90 ℃, -80 ℃, -65 ℃, -50 ℃, -40 ℃, -30 ℃, -20 ℃, -10 ℃, -8 ℃, or-5 ℃, etc., and if the freezing temperature is lower than-150 ℃, the cost is increased; if the freezing temperature is higher than-5 ℃, part of the electrolyte cannot be sufficiently solidified, and is preferably-50 to-5 ℃.
Preferably, the freezing time in step S2 is 0.1-48 h, such as 0.1h, 0.5h, 1h, 2h, 3h, 5h, 8h, 10h, 12h, 14h, 16h, 20h, 24h, 28h, 32h, 36h, 40h, 42h, 44h or 48 h.
Preferably, the pressure of the press forming in step S3 is 0.1 to 50MPa, such as 0.1MPa, 0.5MPa, 1MPa, 3MPa, 5MPa, 8MPa, 10MPa, 13MPa, 18MPa, 22MPa, 26MPa, 30MPa, 35MPa, 40MPa, 45MPa or 50MPa, and if the pressure is less than 0.1MPa, the material compaction density is insufficient, which affects the battery performance; if the pressure is more than 50MPa, the material can be cracked, and the battery performance is affected, preferably 10-20 MPa.
Preferably, the heating conditions in step S3 are: 20 to 100 ℃ (e.g., 20 ℃, 30 ℃, 35 ℃, 40 ℃, 50 ℃, 60 ℃, 65 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃) for 0.1 to 48 hours (e.g., 0.1 hour, 0.5 hour, 1 hour, 2 hours, 3 hours, 3.5 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours, 24 hours, 27 hours, 30 hours, 32 hours, 35 hours, 38 hours, 40 hours, 42 hours, 45 hours or 48 hours, etc.), and in order to obtain better wetting effect, the heating at 30 to 80 ℃ is more preferably performed for 1 to 24 hours.
Preferably, no electrolyte is added during the press forming in step S3.
As a further preferable technical solution of the method of the present invention, the method comprises the steps of:
s1, uniformly mixing the positive electrode material, the binder and the conductive agent to prepare positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, and drying to obtain a positive electrode plate;
uniformly mixing a negative electrode material, a binder and a conductive agent to prepare a negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, and drying to obtain a negative electrode plate;
s2, freezing the soaked positive pole piece and negative pole piece at-50 to-5 ℃ to obtain a positive pole piece and a negative pole piece of pre-buried electrolyte;
s3, pressing and forming the positive pole piece and the negative pole piece of the pre-buried electrolyte and the solid electrolyte membrane under the pressure of 10-20 MPa to obtain a similar solid battery, heating at 30-80 ℃ for 1-24 h to melt the pre-buried electrolyte, and wetting the solid battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) the electrode plate is soaked in the electrolyte, a part of the electrolyte is embedded in the electrode plate by a freezing method, the solid electrolyte membrane and the electrode plate with the embedded electrolyte are pressed into the similar solid battery, and the embedded electrolyte is melted by heating after the battery is molded to wet the similar solid battery.
(2) When the method is adopted to prepare the quasi-solid battery, no electrolyte is required to be dripped, so that the direct contact between metal lithium and the electrolyte is avoided, and the growth of lithium dendrite is effectively inhibited; in addition, in the heating process, the electrolyte pre-embedded in the electrode can be melted to wet a solid-solid interface, so that the interface wettability of the similar solid-state battery is improved, and the electrochemical performance of the similar solid-state battery is improved.
(3) The method does not need to add electrolyte in the process of preparing the quasi-solid battery, has simple process, simple and convenient operation, low cost, rapidness and high efficiency, and has the potential of large-scale production.
Drawings
FIG. 1 is a schematic diagram of a class 1 solid-state battery of example 1, 11-Al foil, 12-positive paste layer, 1-positive electrode tab; 2-a solid electrolyte membrane; 31-Cu foil, 32-negative slurry layer, 3-negative pole piece;
fig. 2 shows the cycle performance of the class 1 solid-state battery of example 1.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. However, the scope of the present invention is not limited thereto.
Example 1
The embodiment provides a method for improving the wettability of an electrode interface of a solid-state battery, which comprises the following steps:
the first step is as follows: positive pole piece and negative pole piece for preparing pre-buried electrolyte
S1, mixing LiNi0.6Co0.2Mn0.2O2Adding the conductive carbon black and the PVDF into NMP according to the mass ratio of 9:0.5:0.5, uniformly stirring, coating the anode slurry on an Al foil, drying at 80 ℃, and punching into an anode piece with the diameter of 12 mm; uniformly stirring Si/C, conductive carbon black, CMC and SBR in a mass ratio of 8:1:0.5:0.5, coating the negative electrode slurry on a Cu foil, drying at 80 ℃, and punching into a negative electrode piece with the diameter of 12 mm;
s2, respectively soaking the positive pole piece and the negative pole piece in LiPF (ethylene carbonate) (EC) which is used as a solvent6Electrolyte (LiPF) being lithium salt6Concentration of 1mol/L), the soaking temperature is 60 ℃, and the soaking time is 24 hours;
and S3, freezing the soaked positive pole piece and negative pole piece at-30 ℃ for 24h to obtain the positive pole piece and negative pole piece with the electrolyte pre-buried.
The second step is that: preparation-like solid-state battery
S4 use of PEO, LiTFSI、Al2O3The solid electrolyte membrane prepared from the raw materials, the positive pole piece and the negative pole piece of the pre-embedded electrolyte are pressed into a similar solid-state battery, the pressing pressure is 18MPa, and the battery is heated for 12 hours at 50 ℃ after being formed, so that the pre-embedded electrolyte is melted and the similar solid-state battery is wetted.
And (3) detection:
the prepared battery is subjected to cycle performance test by using an electrochemical workstation, the test voltage is 3.0-4.3V, the current density is 0.1C in the first 3 circles, and then 0.5C (1C is 200mA g)-1). The first-circle discharge capacity of the battery is 173mAh g-1And the discharge capacity after 50 cycles is 170mAh g-1The capacity retention rate was 98.3%. FIG. 1 is a schematic diagram of a solid-state battery of this example, 11-Al foil, 12-positive electrode paste layer, 1-positive electrode tab; 2-a solid electrolyte membrane; 31-Cu foil, 32-negative electrode paste layer, 3-negative electrode sheet.
Fig. 2 shows the cycle performance of the solid-state-like battery of this embodiment.
Example 2:
the embodiment provides a method for improving the wettability of an electrode interface of a solid-state battery, which comprises the following steps:
the first step is as follows: positive pole piece and negative pole piece for preparing pre-buried electrolyte
S1 LiFePO4Adding the conductive carbon fiber and PEO into NMP according to the mass ratio of 8:1:1, uniformly stirring, coating the anode slurry on Al foil, drying at 80 ℃, and punching into an anode piece with the diameter of 12 mm; adding TiO into the mixture2Uniformly stirring the conductive carbon fiber and the PEO in a mass ratio of 8:1:1, coating the negative electrode slurry on a Cu foil, drying at 80 ℃, and punching into a negative electrode piece with the diameter of 12 mm;
s2, soaking the positive pole piece and the negative pole piece in a LiBF solution using fluoroethylene carbonate (FEC)4Electrolyte being lithium salt (LiBF)4Concentration of 1.5mol/L), soaking temperature of 50 ℃ and soaking time of 24 h;
and S3, freezing the soaked positive pole piece and negative pole piece at-20 ℃ for 20h to obtain the positive pole piece and negative pole piece with the electrolyte pre-buried.
The second step is that: preparation of solid-state batteries
S4, adopting PEO, LiTFSI and Li6.4La3Zr1.4Ta0.6O12And (3) pressing the solid electrolyte membrane prepared from the raw materials, and the positive pole piece and the negative pole piece of the pre-embedded electrolyte into a similar solid-state battery, wherein the pressing pressure is 25MPa, and the battery is heated for 18 hours at 40 ℃ after being formed, so that the pre-embedded electrolyte is melted and the similar solid-state battery is wetted.
And (3) detection:
the prepared battery is subjected to cycle performance test by using an electrochemical workstation, the test voltage is 2.5-4.0V, the current density is 0.1C in the first 3 circles, and then 0.5C (1C is 170mA g)-1). The first circle discharge capacity of the battery is 142mAh g-1And the discharge capacity after 50 cycles is 136mAh g-1The capacity retention rate was 95.8%.
Example 3
The embodiment provides a method for improving the wettability of an electrode interface of a solid-state battery, which comprises the following steps:
the first step is as follows: positive pole piece and negative pole piece for preparing pre-buried electrolyte
S1, mixing LiNi0.6Co0.2Mn0.2O2Adding the conductive graphite and the PVDF into NMP according to the mass ratio of 8:1:1, uniformly stirring, coating the anode slurry on an Al foil, drying at 80 ℃, and punching into an anode piece with the diameter of 12 mm; adding Si/C, conductive graphite, CMC and SBR into deionized water according to the mass ratio of 8:1:0.5:0.5, uniformly stirring, coating the negative electrode slurry on a Cu foil, drying at 80 ℃, and punching into a negative electrode piece with the diameter of 12 mm;
s2, soaking the positive pole piece and the negative pole piece in an electrolyte (the concentration of LiFSI is 2mol/L) which takes dimethyl carbonate (DMC) as a solvent and LiFSI as a lithium salt, wherein the soaking temperature is 55 ℃, and the soaking time is 20 hours;
and S3, freezing the soaked electrode plate at-15 ℃ for 48 hours to obtain the positive electrode plate and the negative electrode plate with the electrolyte pre-buried.
The second step is that: preparation-like solid-state battery
S4, using PEO, LiTFSI and Li6.4La3Zr1.4Ta0.6O12The solid electrolyte membrane prepared from the raw materials and the positive pole piece and the negative pole piece of the pre-embedded electrolyte are pressed into the similar solid-state battery, the pressing pressure is 22MPa, and the battery is heated for 24 hours at 55 ℃ after being formed, so that the pre-embedded electrolyte is melted and the similar solid-state battery is wetted.
And (3) detection:
the prepared battery is subjected to cycle performance test by using an electrochemical workstation, the test voltage is 3.0-4.3V, the current density is 0.1C in the first 3 circles, and then 0.5C (1C is 200 mAg)-1). The first circle discharge capacity of the battery is 170mAh g-1And the discharge capacity after 50 cycles is 165mAh g-1The capacity retention rate was 97.1%.
Example 4
The embodiment provides a method for improving the wettability of an electrode interface of a solid-state battery, which comprises the following steps:
the first step is as follows: positive pole piece and negative pole piece for preparing pre-buried electrolyte
S1, mixing LiNi0.7Co0.2Al0.1O2Adding the carbon nano tube and the PVDF into NMP according to the mass ratio of 8:1:1, uniformly stirring, coating the anode slurry on an Al foil, drying at 70 ℃, and punching into an anode piece with the diameter of 12 mm; mixing Li4Ti5O12Uniformly stirring the conductive carbon black, the CMC and the SBR according to the mass ratio of 8:1:0.5:0.5, coating the negative electrode slurry on a Cu foil, drying at 75 ℃, and punching into a negative electrode piece with the diameter of 12 mm;
s2, respectively soaking the positive pole piece and the negative pole piece in an electrolyte (the LiFOB concentration is 1mol/L) which takes Ethylene Carbonate (EC) as a solvent and LiFOB as a lithium salt, wherein the soaking temperature is 30 ℃, and the soaking time is 32 h;
and S3, freezing the soaked positive pole piece and negative pole piece at-50 ℃ for 12h to obtain the positive pole piece and negative pole piece with the electrolyte pre-buried.
The second step is that: preparation-like solid-state battery
S4, adoptPEO、LiFSI、Al2O3The solid electrolyte membrane prepared from the raw materials, the positive pole piece and the negative pole piece of the pre-embedded electrolyte are pressed into a solid-state battery, the pressing pressure is 10MPa, and the battery is heated for 24 hours at 30 ℃ after being formed, so that the pre-embedded electrolyte is melted and the solid-state battery is wetted.
And (3) detection:
the prepared battery is subjected to cycle performance test by using an electrochemical workstation, the test voltage is 3.0-4.3V, the current density is 0.1C in the first 3 circles, and then 0.5C (1C is 200 mAg)-1). The first circle discharge capacity of the battery is 171mAh g-1And the discharge capacity after 50 cycles is 168mAh g-1The capacity retention rate was 98.2%.
Example 5
The embodiment provides a method for improving the wettability of an electrode interface of a solid-state battery, which comprises the following steps:
the first step is as follows: positive pole piece and negative pole piece for preparing pre-buried electrolyte
S1, mixing LiNi0.6Co0.2Mn0.2O2Adding the conductive carbon black and the PVDF into NMP according to the mass ratio of 9:0.5:0.5, uniformly stirring, coating the anode slurry on an Al foil, drying at 80 ℃, and punching into an anode piece with the diameter of 12 mm; uniformly stirring Si/C, conductive carbon black, CMC and SBR in a mass ratio of 8:1:0.5:0.5, coating the negative electrode slurry on a Cu foil, drying at 80 ℃, and punching into a negative electrode piece with the diameter of 12 mm;
s2, respectively soaking the positive pole piece and the negative pole piece in LiPF (ethylene carbonate) (EC) which is used as a solvent6Electrolyte (LiPF) being lithium salt6Concentration of 1mol/L), the soaking temperature is 60 ℃, and the soaking time is 24 hours;
and S3, freezing the soaked positive pole piece and negative pole piece at-80 ℃ for 24h to obtain the positive pole piece and negative pole piece with the electrolyte pre-buried.
The second step is that: preparation-like solid-state battery
S4, using PEO, LiTFSI and Al2O3Solid electrolyte membrane prepared from raw materials and anode of pre-buried electrolyteAnd pressing the sheet and the negative pole sheet into a similar solid-state battery, wherein the pressing pressure is 18MPa, and the battery is heated for 12 hours at 50 ℃ after being formed, so that the pre-embedded electrolyte is melted and the similar solid-state battery is wetted.
And (3) detection:
the prepared battery is subjected to cycle performance test by using an electrochemical workstation, the test voltage is 3.0-4.3V, the current density is 0.1C in the first 3 circles, and then 0.5C (1C is 200 mAg)-1). The first circle discharge capacity of the battery is 165mAh g-1And the discharge capacity after 50 cycles is 150mAh g-1The capacity retention rate was 90.9%.
Example 6
The embodiment provides a method for improving the wettability of an electrode interface of a solid-state battery, which comprises the following steps:
the first step is as follows: positive pole piece and negative pole piece for preparing pre-buried electrolyte
S1, mixing LiNi0.6Co0.2Mn0.2O2Adding the conductive carbon black and the PVDF into NMP according to the mass ratio of 9:0.5:0.5, uniformly stirring, coating the anode slurry on an Al foil, drying at 80 ℃, and punching into an anode piece with the diameter of 12 mm; uniformly stirring Si/C, conductive carbon black, CMC and SBR in a mass ratio of 8:1:0.5:0.5, coating the negative electrode slurry on a Cu foil, drying at 80 ℃, and punching into a negative electrode piece with the diameter of 12 mm;
s2, respectively soaking the positive pole piece and the negative pole piece in LiPF (ethylene carbonate) (EC) which is used as a solvent6Electrolyte (LiPF) being lithium salt6Concentration of 1mol/L), the soaking temperature is 60 ℃, and the soaking time is 24 hours;
and S3, freezing the soaked positive pole piece and negative pole piece at-30 ℃ for 24h to obtain the positive pole piece and negative pole piece with the electrolyte pre-buried.
The second step is that: preparation-like solid-state battery
S4, using PEO, LiTFSI and Al2O3Pressing a solid electrolyte membrane prepared from raw materials and a positive pole piece and a negative pole piece of pre-embedded electrolyte into a similar solid battery, wherein the pressing pressure is 3MPa, and the battery is heated for 12 hours at 50 ℃ after being formed so as to ensure that the electrolyte membrane is pre-pressed into the similar solid batteryThe buried electrolyte melts and wets the solid-state battery.
And (3) detection:
the prepared battery is subjected to cycle performance test by using an electrochemical workstation, the test voltage is 3.0-4.3V, the current density is 0.1C in the first 3 circles, and then 0.5C (1C is 200 mAg)-1). The first circle discharge capacity of the battery is 160mAh g-1And the discharge capacity after 50 cycles is 146mAh g-1The capacity retention rate was 91.3%. The battery of example 6 was slightly inferior to that of example 1 in performance because the cell was prepared under a lower pressure in example 6, resulting in a lower packing density of the cell, resulting in poor performance of the cell.
Example 7
The embodiment provides a method for improving the wettability of an electrode interface of a solid-state battery, which comprises the following steps:
the first step is as follows: positive pole piece and negative pole piece for preparing pre-buried electrolyte
S1, mixing LiNi0.6Co0.2Mn0.2O2Adding the conductive carbon black and the PVDF into NMP according to the mass ratio of 9:0.5:0.5, uniformly stirring, coating the anode slurry on an Al foil, drying at 80 ℃, and punching into an anode piece with the diameter of 12 mm; uniformly stirring Si/C, conductive carbon black, CMC and SBR in a mass ratio of 8:1:0.5:0.5, coating the negative electrode slurry on a Cu foil, drying at 80 ℃, and punching into a negative electrode piece with the diameter of 12 mm;
s2, respectively soaking the positive pole piece and the negative pole piece in LiPF (ethylene carbonate) (EC) which is used as a solvent6Electrolyte (LiPF) being lithium salt6Concentration of 1mol/L), the soaking temperature is 60 ℃, and the soaking time is 24 hours;
and S3, freezing the soaked positive pole piece and negative pole piece at-30 ℃ for 24h to obtain the positive pole piece and negative pole piece with the electrolyte pre-buried.
The second step is that: preparation-like solid-state battery
S4, using PEO, LiTFSI and Al2O3Solid electrolyte membrane prepared from raw materials, and solid electrolyte-like pressed positive pole piece and negative pole piece of pre-embedded electrolyteAnd (3) the pressing pressure of the battery is 40MPa, and the battery is heated for 12h at 50 ℃ after being formed, so that the pre-embedded electrolyte is melted and the solid-state battery is wetted.
And (3) detection:
the prepared battery is subjected to cycle performance test by using an electrochemical workstation, the test voltage is 3.0-4.3V, the current density is 0.1C in the first 3 circles, and then 0.5C (1C is 200 mAg)-1). The first-circle discharge capacity of the battery is 163mAh g-1And the discharge capacity after 50 cycles is 142mAh g-1The capacity retention rate was 87.1%. The battery performance of example 7 was slightly inferior to that of example 1 because the pressure at the time of preparing the battery of example 7 was large, resulting in the fragmentation of a part of the material, which affected the battery performance.
The preparation parameters and the performance results for the examples are shown in table 1.
TABLE 1
Figure BDA0002322286240000141
In conclusion, the solid-like battery obtained by the method improves the wettability of the solid-like interface, so that the electrochemical performance of the solid-like battery is further improved, and the method is simple and convenient to operate, rapid, efficient and remarkable in economic benefit.
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. A method for improving the wettability of an electrode interface of a solid-state-like battery is characterized by comprising the following steps:
s1, soaking the positive pole piece and the negative pole piece in electrolyte;
s2, freezing the soaked positive pole piece and negative pole piece to obtain a positive pole piece and a negative pole piece of pre-buried electrolyte;
and S3, pressing and molding the positive pole piece and the negative pole piece of the pre-embedded electrolyte and the solid electrolyte membrane to obtain a similar solid battery, and heating to melt the pre-embedded electrolyte and wet the solid battery.
2. The method according to claim 1, wherein the positive electrode sheet of step S1 is prepared by the following method: uniformly mixing a positive electrode material, a binder and a conductive agent to prepare positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, and drying to obtain a positive electrode plate;
preferably, the negative electrode sheet of step S1 is prepared by the following method: and uniformly mixing the negative electrode material, the binder and the conductive agent to prepare negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, and drying to obtain the negative electrode plate.
3. The method according to claim 2, wherein the positive electrode material and the negative electrode material independently include any one of a layered structure compound, a spinel structure compound, an olivine structure compound, a NASICON structure compound, a conversion type material, an insertion type material, and an alloy type material or a combination of at least two of them;
preferably, the binder used for preparing the positive electrode slurry and the binder used for preparing the negative electrode slurry independently comprise any one or a combination of at least two of polyethylene oxide, polymethyl methacrylate, polyvinylidene fluoride, polyethylene, sodium carboxymethyl cellulose or styrene butadiene rubber;
preferably, the conductive agent used for preparing the positive electrode slurry and the conductive agent used for preparing the negative electrode slurry independently comprise any one or a combination of at least two of conductive carbon black, conductive graphite or conductive carbon fiber;
preferably, the chemical formula of the cathode material comprises LiMO2、LiMPO4、LiMn2O4、LiCo2O4、LiV2O4、Li3V2(PO4)3、Li3Fe2(PO4)3、LiNix1A1-x1O2、LiNix2CoyB1-x2-yO2Any one or the combination of at least two of the above, wherein M comprises any one or the combination of at least two of Co, Ni or Mn, A comprises any one or the combination of two of Co or Mn, B comprises any one or the combination of two of Mn or Al, x1 is more than or equal to 0 and less than or equal to 1, x2 is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1;
preferably, the chemical formula of the anode material comprises C, Si/C, Li3N、Li7MnN4、Li3FeN2、Li3-xCoxN、SnO、TiO2Or Li4Ti5O12Any one or a combination of at least two of them.
4. The method according to any one of claims 1 to 3, wherein the electrolyte comprises an electrolyte prepared using any one of ethylene carbonate, vinylene carbonate, dimethyl carbonate, or fluoroethylene carbonate, or a combination of at least two thereof, as a solvent.
5. The method according to any one of claims 1 to 4, wherein the soaking in step S1 is performed at a temperature of 0 to 100 ℃ for 0.1 to 48 hours.
6. The method according to claim 5, wherein the soaking in step S1 is performed at 20-50 ℃ for 12-24 h.
7. The method according to any one of claims 1 to 6, wherein the temperature of the freezing in step S2 is-150 to-5 ℃, preferably-50 to-5 ℃;
preferably, the freezing time in the step S2 is 0.1-48 h.
8. The method according to any one of claims 1 to 7, wherein the pressure for the press forming in step S3 is 0.1 to 50MPa, preferably 10 to 20 MPa;
preferably, the heating conditions in step S3 are: heating at 20-100 ℃ for 0.1-48 h, preferably at 30-80 ℃ for 1-24 h.
9. The method according to any one of claims 1 to 8, wherein no electrolyte is added during the press forming in step S3.
10. A method according to any of claims 1-9, characterized in that the method comprises the steps of:
s1, uniformly mixing the positive electrode material, the binder and the conductive agent to prepare positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, and drying to obtain a positive electrode plate;
uniformly mixing a negative electrode material, a binder and a conductive agent to prepare a negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, and drying to obtain a negative electrode plate;
s2, freezing the soaked positive pole piece and negative pole piece at-50 to-5 ℃ to obtain a positive pole piece and a negative pole piece of pre-buried electrolyte;
s3, pressing and forming the positive pole piece and the negative pole piece of the pre-buried electrolyte and the solid electrolyte membrane under the pressure of 10-20 MPa to obtain a similar solid battery, heating at 30-80 ℃ for 1-24 h to melt the pre-buried electrolyte, and wetting the solid battery.
CN201911302810.1A 2019-12-17 2019-12-17 Method for improving interfacial wettability of electrode of quasi-solid battery Pending CN110957471A (en)

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