CN108574114B - Heat treatment method of solid electrolyte film and lithium battery cell structure - Google Patents

Heat treatment method of solid electrolyte film and lithium battery cell structure Download PDF

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CN108574114B
CN108574114B CN201810260554.3A CN201810260554A CN108574114B CN 108574114 B CN108574114 B CN 108574114B CN 201810260554 A CN201810260554 A CN 201810260554A CN 108574114 B CN108574114 B CN 108574114B
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solid electrolyte
electrolyte film
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heat treatment
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CN108574114A (en
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张晓琨
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Chengdu Dachao Technology 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract

The invention relates to the technical field of lithium batteries, in particular to a heat treatment method of a solid electrolyte film and a lithium battery core structure. A heat treatment method of a solid electrolyte film, comprising the steps of: providing a solid electrolyte film to be treated with a certain thickness, wherein the solid electrolyte film to be treated is formed on the electrode structure; performing heat treatment on the solid electrolyte film to be treated for a preset time by adopting a pulse light source with specific pulse parameters; cooling the solid electrolyte film after the heat treatment. The method adopts the pulse light source with specific pulse parameters to carry out heat treatment on the solid electrolyte film to be treated, the solid electrolyte film to be treated has better absorption performance on photons emitted by the pulse light source, and the temperature of the solid electrolyte film to be treated is improved, so that the crystal phase structure of the solid electrolyte film to be treated is changed, the phase and grain boundary impedance of the solid electrolyte film to be treated is further changed, the conductivity of conductive ions in the solid electrolyte film after heat treatment is improved, and the conductivity is improved.

Description

Heat treatment method of solid electrolyte film and lithium battery cell structure
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of lithium batteries, in particular to a heat treatment method of a solid electrolyte film and a lithium battery core structure.
[ background of the invention ]
In the process of preparing the lithium battery, the solid electrolyte film needs to be processed according to actual needs. Wherein the heat treatment technique can change the characteristics of the solid electrolyte film to reduce the grain boundary resistance of the solid electrolyte film, thereby improving the conduction of the conductive lithium ions; secondly, the heat treatment technology can also improve the interface contact performance between the solid electrolyte film and the electrode, reduce the interface impedance and further improve the battery performance.
In the prior art, a heater is mainly used for heating a solid electrolyte film, and due to uncontrollable heating process, the structure of an electrode material is easily affected greatly, so that the capacity retention rate and the structural stability of the electrode material are reduced. Therefore, a new heating technique for solid electrolyte is needed to solve the above problems.
[ summary of the invention ]
In order to solve the problem that the capacity retention rate and the structural stability of an electrode material are reduced when the solid electrolyte film is heated at present, the invention provides a heat treatment method of the solid electrolyte film of the lithium battery, which can realize the rapid heat treatment of the solid electrolyte film and well maintain the conductive performance of the electrode material.
In order to solve the above technical problems, the present invention provides a technical solution as follows: a heat treatment method of a solid electrolyte film, comprising the steps of:
providing a solid electrolyte film to be treated with a certain thickness, wherein the solid electrolyte film to be treated is formed on the electrode structure;
carrying out heat treatment on the solid electrolyte film to be treated for a preset time by adopting a pulse light source with specific pulse parameters to change the crystal phase structure of the solid electrolyte film, wherein the pulse parameters comprise: the pulse width is: 10-100 mus;
cooling the solid electrolyte film after the heat treatment.
Preferably, the pulse parameters are specifically: the pulse width is: 10-100 mus, the pulse current density is: 1-40mA/cm2The pulse frequency is: 10-1000HZ, and the heat treatment time is as follows: 1-10 h.
Preferably, the heat-treating the solid electrolyte membrane to be treated with the pulsed light source of the specific pulse parameter for the predetermined time includes setting at least two different ranges of pulse parameters for the staged heat-treatment of the solid electrolyte membrane to be treated.
Preferably, the staged heat treatment comprises the following three stages:
the first stage is as follows: the pulse current density was: 1-10mA/cm2The pulse frequency is: 10-100HZ, and the heating time is as follows: 1-2 h;
and a second stage: the pulse current density was: 20-40mA/cm2The pulse frequency is: 200-1000HZ, wherein the heating time is as follows: 2-3 h; and
and a third stage: the pulse current density was: 1-10mA/cm2The pulse frequency is: 10-100HZ, and the heating time is as follows: 1-1.5 h.
Preferably, the absorptivity of the solid electrolyte film to be treated to photons emitted by the pulse light source with the specific pulse parameters is more than 80%.
Preferably, the pulsed light source comprises: any one or combination of several of ultraviolet lamp, infrared lamp, high pressure sodium lamp or halogen tungsten lamp.
Preferably, the solid electrolyte thin film comprises an inorganic type solid electrolyte comprising a Li-La-Zr-O type material or a material obtained by element doping of a Li-La-Zr-O type material, and the conductivity of the solid electrolyte thin film after cooling treatment is: 4-8 mS/cm-1。
In order to solve the above technical problems, the present invention provides another technical solution: a lithium battery cell structure comprising an electrode structure and a solid electrolyte film formed on the electrode structure, the solid electrolyte film comprising a solid electrolyte film material, the electrode structure comprising an electrode sheet and an electrode material formed on the electrode sheet, the solid electrolyte film being formed on a side of the electrode material remote from the electrode sheet, wherein: the solid electrolyte film is prepared by the following method:
depositing the solid electrolyte film material on the electrode structure by a PVD deposition technique to form a solid electrolyte film to be processed having a certain thickness;
carrying out heat treatment on the solid electrolyte film to be treated for a preset time by adopting a pulse light source with specific pulse parameters to change the crystal phase structure of the solid electrolyte film, wherein the pulse parameters comprise: the pulse width is: 10-100 mus;
cooling the solid electrolyte film after the heat treatment.
Preferably, the electrode plate includes a positive electrode plate and/or a negative electrode plate, the electrode material includes a positive electrode material formed on the positive electrode plate and/or a negative electrode material formed on the negative electrode plate, and the solid electrolyte film is formed on the positive electrode material and/or the negative electrode material.
Preferably, the positive electrode material includes LiCoO2，LiMnO2，LiNiO2，LiVO2，LiNi1/3Co1/3Mn1/3O2，LiMn2O4，LiFePO4，LiMnPO4，LiNiPO4，Li2FeSiO4Any one or any combination of the above, and the negative electrode material is selected from any one of graphite, lithium metal and silicon.
Compared with the prior art, the heat treatment method of the solid electrolyte film and the lithium battery cell structure provided by the invention have the following beneficial effects:
the method comprises the steps of carrying out heat treatment on a solid electrolyte film to be treated for a preset time by adopting a pulse light source with specific pulse parameters, setting the specific pulse parameters, wherein the solid electrolyte film to be treated has better absorption performance on photons emitted by the pulse light source, and can effectively improve the temperature of the solid electrolyte film to be treated, so that the crystal phase structure of the solid electrolyte film to be treated can be effectively controlled and changed, and further the bulk phase and grain boundary impedance of the solid electrolyte film to be treated are changed, so that the conductivity of the solid electrolyte film after heat treatment of conductive ions is improved, and the conductivity is improved.
The pulse width is: 10-100 mus, the pulse duration of the pulse light source under the pulse width is shorter than the heat conduction time, therefore, the energy of the light pulse is stored in the solid electrolyte film to be processed for a very short time, and almost no heat conduction occurs in the period, namely, the instant heating of the electrolyte can be realized based on the setting and selection of the pulse width, therefore, the temperature difference between the solid electrolyte film to be processed and the electrode structure after the absorption of photons can be well avoided, the heat is reduced to be transferred from one side of the solid electrolyte film to be processed with high temperature to one side of the electrode structure, the damage of the high temperature to the electrode structure is further reduced, and the grain boundary impedance of the solid electrolyte film to be processed is well changed. The pulse current density is set to: 1-40mA/cm2The pulse frequency is: 10-1000 HZ; the pulse parameters are limited, so that the heating efficiency of the pulse light source on the solid electrolyte film to be processed can be well controlled, the heating degree of the solid electrolyte film to be processed can be well controlled, and the grain boundary impedance of the solid electrolyte film to be processed can be well changed.
The heat treatment of the solid electrolyte film to be treated by adopting the pulse light source with preset pulse parameters for preset time at least comprises the step-by-step heat treatment of the solid electrolyte film to be treated by setting two pulse parameters in different ranges, the pulse parameters in different stages are different, the heat treatment effect on the solid electrolyte film to be treated is also different, and the grain boundary impedance of the solid electrolyte film to be treated can be better changed by combining the multi-stage heat treatment with different parameters.
In order to solve the above technical problems, the present invention provides another technical solution: a lithium battery cell structure, the lithium battery cell comprising an electrode structure and a solid electrolyte film formed on the electrode structure, the solid electrolyte film comprising a solid electrolyte material, the electrode structure comprising an electrode sheet and an electrode material formed on the electrode sheet, the solid electrolyte film being formed on a side of the electrode material away from the electrode sheet, the solid electrolyte film being prepared by:
depositing the solid electrolyte film material on the electrode structure by a PVD deposition technique to form a solid electrolyte film to be processed having a certain thickness;
performing heat treatment on the solid electrolyte film to be treated for a preset time by adopting a pulse light source with specific pulse parameters;
cooling the solid electrolyte film after the heat treatment.
Under the set specific pulse parameters, photons emitted by the pulse light source are better absorbed by the solid electrolyte film to be processed relative to the electrode structure, so that the pulse light source is utilized to heat the solid electrolyte film to be processed, the solid electrolyte film to be processed has a better heating effect, the crystal phase structure of the solid electrolyte film to be processed can be well changed, the grain boundary impedance of the solid electrolyte film to be processed is further well reduced, and the conduction rate of conductive ions on the solid electrolyte film is improved.
Secondly, the electrode structure absorbs less photons emitted by the pulse light source, so that the temperature of the electrode structure is increased less, the influence of the pulse light source on the stability of the electrode structure is further well reduced, and the electrode structure still has higher specific capacity and charge-discharge cycle performance.
Furthermore, the pulse light source has a heat treatment effect on the solid electrolyte film to be treated and the electrode structure at the same time, so that the solid electrolyte film and the electrode structure are further jointed, the interface impedance between the solid electrolyte film and the electrode structure is better reduced, the conductivity of conductive ions between the solid electrolyte film and the electrode structure is improved, and the conductivity is improved.
[ description of the drawings ]
Fig. 1 is a process flow diagram of a solid electrolyte membrane to be processed in a first embodiment of the invention;
fig. 2 is a flow chart for obtaining the solid electrolyte membrane to be treated in the first embodiment of the present invention;
fig. 3A is a schematic structural view of a solid electrolyte thin film to be treated formed on a positive electrode structure in the first embodiment of the present invention;
fig. 3B is a schematic structural view of a solid electrolyte film to be treated formed on a negative electrode structure in the first embodiment of the present invention;
FIG. 4 is a schematic view of a pulsed light source irradiating on the solid electrolyte film to be treated in the first embodiment of the present invention;
FIG. 5 is a graph of the pulsed current control of a pulsed light source according to a first embodiment of the present invention;
FIG. 6 is a schematic view showing a thermal conduction curve of a solid electrolyte film to be treated in the first embodiment of the present invention;
FIG. 7 is a schematic thermal conductivity curve of an electrode structure according to a first embodiment of the present invention;
fig. 8 is a schematic structural view of a lithium battery cell according to a second embodiment of the present invention;
fig. 9 is a schematic structural view of a lithium battery cell when an electrode sheet is a positive electrode sheet according to a second embodiment of the present invention;
fig. 10 is a schematic structural view of a lithium battery cell when the electrode sheet is a negative electrode sheet according to a second embodiment of the present invention.
[ detailed description ] embodiments
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, a first embodiment of the present invention provides a heat treatment method of a solid electrolyte film, including the steps of:
s1: providing a solid electrolyte film to be treated with a certain thickness, wherein the solid electrolyte film to be treated is formed on the electrode structure;
s2: performing heat treatment on the solid electrolyte film to be treated for a preset time by adopting a pulse light source with specific pulse parameters;
s3: cooling the solid electrolyte film after the heat treatment.
In the step S1, the to-be-treated solid electrolyte thin film includes a solid electrolyte thin film material, where the solid electrolyte thin film material includes a mixed solution additive, a composite lithium salt, and a Li-La-Zr-O type material or an inorganic type solid electrolyte material obtained by doping an element thereof.
Referring to fig. 2, 3A and 3B, in the step S1, the solid electrolyte film material is deposited on the electrode structure 10 to form the solid electrolyte film 20 to be processed with a certain thickness by PVD deposition, wherein the PVD deposition includes the following steps:
s11: placing the electrode structure 10 as a substrate on a substrate table;
s12: putting a solid electrolyte film material into a tantalum crucible (or a molybdenum crucible or a tungsten crucible);
s13: adjust the air pressure of the cavity to 10-6Torr, and ensuring that the oxygen content of the cavity is less than 0.01ppm and the moisture content is less than 0.01 ppm;
s14: and (3) adjusting the deposition power to be 50-130W and the deposition time to be 0.5-1.0h, and depositing the solid electrolyte film material on the electrode structure 10 to obtain the solid electrolyte film 20 to be treated.
In step S11, the electrode structure 10 includes a positive electrode structure 101 and/or a negative electrode structure 102, the positive electrode structure 101 includes a positive electrode current collector 1011 and a positive electrode material layer 1012 formed on the positive electrode current collector 1011, and the negative electrode structure 102 includes a negative electrode current collector 1021 and a negative electrode material layer 1022 formed on the negative electrode current collector 1021.
In the above step S14, the solid electrolyte film material is deposited on the electrode structure 10 to obtain the solid electrolyte film 20 to be processed, specifically, the solid electrolyte film material is deposited on the positive electrode structure 101 and/or the negative electrode structure 102, more specifically, on the side of the positive electrode material layer 1012 away from the positive electrode current collector 1011 and/or coated on the side of the negative electrode material 1022 away from the negative electrode current collector 1021. The thickness of the to-be-treated solid electrolyte thin film 20 obtained after the end of deposition was: 5nm-10 μm.
Referring to fig. 4, in the step S2, the method specifically includes fixing the solid electrolyte film 20 to be processed, so that the pulse light source 30 faces the solid electrolyte film 20 to be processed, and photons emitted from the pulse light source 30 are better absorbed by the solid electrolyte film 20 to be processed, so as to better change a crystal phase structure of the solid electrolyte film 20 to be processed, thereby reducing grain boundary resistance of the solid electrolyte film 20 to be processed, and increasing a conduction rate of conductive ions in the solid electrolyte film after heat treatment, thereby improving conductivity.
In some embodiments of the present embodiment, the pulsed light source 30 is used to heat treat the solid electrolyte membrane 20 to be treated more efficiently. Specifically, in step S2, the pulse parameters are specifically: the pulse width is: 10-100 mus, the pulse current density is: 1-40mA/cm2The pulse frequency is: 10-1000HZ, and the heat treatment time is as follows: 1-10 h.
In some embodiments of the present invention, in the step S2, the pulse parameters of the pulse light source 30 can be adjusted according to the thickness of the solid electrolyte film 20 to be processed and the heat conduction rate thereof. The pulse current density and the pulse frequency of the pulse light source 30 can be set to be in positive correlation with the thickness of the solid electrolyte film 20 to be processed, that is, when the thickness of the solid electrolyte film 20 to be processed is thicker, the pulse current density and the pulse frequency of the pulse light source 30 can be set to be larger, so that the heat treatment efficiency of the pulse light source 30 on the solid electrolyte film 20 to be processed is improved. When the thickness of the to-be-treated solid electrolyte film 20 is relatively thin, the pulse current density and the pulse frequency can be set to be relatively small, so that the pulse light source 30 can effectively heat the to-be-treated solid electrolyte film 20, and can also reduce damage to the electrode structure 10, maintain the stability of the electrode structure 10, and ensure the capacity retention rate and the charge-discharge cycle performance of the electrode structure.
Further, the pulse parameters may also be adjusted according to the heat conduction rate of the to-be-treated solid electrolyte thin film 20. The high-low ratio of the heat conduction rate of the to-be-treated solid electrolyte thin film 20 is largely determined by the properties of the solid electrolyte material itself included in the to-be-treated solid electrolyte thin film 20. Similarly, the heat conduction of the electrode structure 10 is also determined by the positive electrode current collector 1011 included in the electrode structure 10 and the positive electrode material layer 1012 formed on the positive electrode current collector 1011 or by the negative electrode current collector 102 and the negative electrode material layer 1022 formed on the negative electrode current collector 1021.
Therefore, in some specific embodiments, after the determined solid state electrolyte material, positive electrode current collector 1011, positive electrode material layer 1012, negative electrode current collector 1021, and negative electrode material layer 1022 are selected, the photons emitted by the pulse light source have a certain heat conduction rate in the solid state electrolyte film 20 to be processed and the electrode structure 10, and at this time, the heat conduction rate of the photons in the solid state electrolyte film 20 to be processed and the electrode structure 10 can be measured respectively, and the pulse width can be adjusted to be an appropriate pulse width, so that the absorption rate of the photons of the pulse light source 30 by the solid state electrolyte film 20 to be processed is far larger than that of the electrode structure 10. Specifically, the pulse parameters are modulated so that the absorption rate of photons by the solid electrolyte thin film 20 to be treated is 80% or more. The appropriate pulse parameters are modulated to ensure that the photons emitted by the pulse light source 30 can better reduce the grain boundary impedance of the solid electrolyte film 20 to be processed, and simultaneously, the damage of the heat treatment to the electrode structure 10 can be well avoided.
Referring to fig. 5, 6 and 7, in fig. 5, an abscissa t represents time, and an ordinate I represents current intensity; in fig. 6 and 7, the abscissa T represents time and the ordinate T represents a thermal parameter. The heat absorbed by the solid electrolyte film 20 to be treated is different from that absorbed by the electrode structure 10 under irradiation of the pulse light source 30 of the set pulse parameters. Specifically, in the interval of time a-b (as shown in fig. 5), the corresponding solid electrolyte thin film 20 to be treated (as shown in fig. 6) absorbs much more heat than the electrode structure 10 (as shown in fig. 7), so that the solid electrolyte thin film 20 to be treated is heated by the pulsed light source, which has a good heating effect on the solid electrolyte thin film 20 to be treated, and a relatively small heating effect on the electrode structure 10. Based on this, it can be seen that the pulse light source 30 with preset pulse parameters is used for heating the solid electrolyte film 20 to be processed, so that the crystal phase structure of the solid electrolyte film 20 to be processed can be well changed, the crystal boundary resistance of the solid electrolyte film 20 to be processed is further well reduced, and the conduction rate of the solid electrolyte film after the heat treatment of conductive ions is improved.
Secondly, the electrode structure 10 absorbs less photons emitted by the pulse light source 30, so that the temperature of the electrode structure 10 is raised less, the influence of the pulse light source 30 on the stability of the electrode structure 10 is further reduced, and the electrode structure 10 still has high specific capacity and charge-discharge cycle performance.
Furthermore, the pulsed light source 30 has a heat treatment effect on the solid electrolyte film 20 to be treated and the electrode structure 10 at the same time, so that the solid electrolyte film 20 to be treated and the electrode structure 10 are further attached to each other, thereby better reducing the interfacial resistance between the solid electrolyte film after heat treatment and the electrode structure 10, improving the conductivity of the conductive ions between the solid electrolyte film after heat treatment and the electrode structure 10, and improving the conductivity.
In some specific embodiments, the heat-treating the to-be-treated solid electrolyte membrane 20 with the pulsed light source of a specific pulse parameter for a predetermined time includes setting at least two different ranges of pulse parameters for the staged heat-treatment of the to-be-treated solid electrolyte membrane 20.
The staged heat treatment comprises the following three stages:
the first stage is as follows: the pulse current density was: 1-10mA/cm2The pulse frequency is: 10-100HZ, and the heating time is as follows: 1-2 h;
and a second stage: the pulse current density was: 20-40mA/cm2The pulse frequency is: 200-1000HZ, wherein the heating time is as follows: 2-3 h;
and a third stage: the pulse current density was: 1-10mA/cm2The pulse frequency is: 10-100HZ, and the heating time is as follows: 1-1.5 h.
The solid electrolyte film 20 to be treated is treated in different stages with different pulse parameters, so that a better heat treatment effect can be achieved, and the conductivity of the solid electrolyte film after heat treatment can be better improved. The specific analysis of the above three phases is as follows:
in the first stage, the current density is small, the pulse frequency is low, and the heating time is short, and it can be seen that the heat treatment effect in the first stage is mild to the solid electrolyte membrane 20 to be treated. The purpose of this stage is to perform a certain temperature raising process on the to-be-treated solid electrolyte thin film 20, so that each atom of the solid electrolyte material contained in the to-be-treated solid electrolyte thin film 20 is in a heated state.
The current density and the pulse frequency of the second stage are both larger than those of the first stage, and the heating time is also longer than that of the first stage, and the main purpose of the second stage is to perform faster and deeper heating treatment on the solid electrolyte film 20 to be treated after the primary heating treatment is performed on the solid electrolyte film 20 to be treated through the first stage, so that the molecular structure of the solid electrolyte material is better changed, and the grain boundary resistance of the solid electrolyte 20 to be treated is better changed.
The pulse parameter of the third stage is close to the pulse parameter setting of the first stage. After the heating treatment in the second stage, the crystal phase structure of the solid electrolyte film 20 to be treated is improved well, and the crystal phase structure of the solid electrolyte film 20 to be treated after the heating treatment in the second stage has better stability by performing a mild heat treatment on the solid electrolyte film 20 to be treated after the heating treatment in the third stage.
The solid electrolyte film after the cooling heat treatment is carried out in an inert atmosphere, and the cooling time is 1-5 h.
And cooling the solid electrolyte film after the heat treatment under the inert gas condition, so that the moisture and oxygen in the air can be well prevented from being absorbed by the solid electrolyte film after the heat treatment to influence the structural stability of the solid electrolyte film after the heat treatment.
After the solid electrolyte membrane 20 to be processed is subjected to the cooling process in step S3, the obtained conductivity of the solid electrolyte membrane after the heat treatment is: 4-8 mS/cm-1And the interfacial resistance between the solid electrolyte thin film and the electrode structure after the heat treatment is significantly reduced. And the electrode structure 10 still has a high specific capacity and charge-discharge cycle performance.
To further verify the interfacial impedance between the solid electrolyte membrane and the electrode structure 10 and the stability of the electrode structure after the heat treatment with specific pulse parameters modulated in the present invention, the present invention provides the following experimental groups:
experimental group 1:
the solid electrolyte material is: li7La3Zr2O12The electrode material is as follows: LiCoO2The thickness of the solid electrolyte thin film 20 to be processed is: 5 μm, pulse width: 50 μ s, pulse current density: 20/mA/cm2The pulse frequency is: 100HZ, heating time is as follows: and 2 h.
Experimental group 2:
the solid electrolyte material is: li7La3Zr2O12The electrode material is as follows: LiCoO2The thickness of the solid electrolyte thin film 20 to be processed is: 10 μm, pulse width: 80 μ s, pulse current density: 40/mA/cm2The pulse frequency is: 300HZ, heating time is as follows: and 3 h.
Experimental group 3:
the solid electrolyte material is: li7La3Zr2O12The electrode material is as follows: LiMnO2The thickness of the solid electrolyte thin film 20 to be processed is: 5 μm, pulse width: 20 μ s, pulse current density: 50/mA/cm2The pulse frequency is: 400HZ, heating time is as follows: and 2 h.
Experimental group 4:
the solid electrolyte material is: li6La3ZrTaO12The electrode material is as follows: LiMnO2The thickness of the solid electrolyte thin film 20 to be processed is: 5 μm, pulse width: 80 μ s, pulse current density: 20mA/cm2The pulse frequency is: 500HZ, heating time is as follows: and 2 h.
TABLE 1 conductivity tabulation of experimental groups 1-4
Figure GDA0002633725000000121
And (3) analyzing an experimental result:
as can be seen from Table 1, the solid electrolyte thin films obtained by the methods provided by the experimental groups 1 to 4 of the present invention after heat treatment have high electrical conductivity.
TABLE 2 tabulated capacity retention rates for experimental groups 1-4
Test object Capacity retention rate
Experimental group 1 92.3％
Experimental group 2 94.7％
Experimental group 3 95.8％
Experimental group 4 94.5％
And (3) analyzing an experimental result:
as can be seen from table 2, the capacity retention rates of the electrode structures 10 after the solid electrolyte thin films obtained by the experimental groups 1 to 4 are processed are detected, and it can be known that the electrode structures 10 obtained by the experimental groups 1 to 4 have higher capacity retention rates.
The pulsed light source 30 includes: any one or combination of several of ultraviolet lamp, infrared lamp, high pressure sodium lamp or halogen tungsten lamp.
Referring to fig. 8, a second embodiment of the present invention provides a lithium battery cell structure 40, where the lithium battery cell structure 40 includes an electrode structure 50 and a solid electrolyte thin film 60 formed on the electrode structure 50, the solid electrolyte thin film 60 includes a solid electrolyte material, the electrode structure 50 includes an electrode sheet 501 and an electrode material layer 502 formed on the electrode sheet 501, the solid electrolyte thin film 60 is formed on a side of the electrode material layer 502 away from the electrode sheet 501, and the solid electrolyte thin film 60 is prepared by:
v1: depositing the solid electrolyte thin film material over the electrode structure 50 by PVD deposition technique as described in the first embodiment to form a solid electrolyte thin film to be treated having a certain thickness;
v2: performing heat treatment on the solid electrolyte film to be treated for a preset time by adopting a pulse light source with specific pulse parameters;
v3: cooling the solid electrolyte film after the heat treatment.
In this embodiment, the heat treatment of the to-be-treated solid electrolyte thin film of the lithium cell structure 40 in the step V3 is the same as that in the first embodiment, and will not be described in detail here.
Referring to fig. 9 and 10, the electrode sheet 501 includes a positive electrode sheet 5011 and/or a negative electrode sheet 5012, and the electrode material layer 502 includes a positive electrode material 5021 formed on the positive electrode sheet 5011 and/or a negative electrode material 5022 formed on the negative electrode sheet 5012.
The positive electrode material 5021 comprises LiCoO2，LiMnO2，LiNiO2，LiVO2，LiNi1/3Co1/3Mn1/3O2，LiMn2O4，LiFePO4，LiMnPO4，LiNiPO4，Li2FeSiO4Any one or any combination of the above, the negative electrode material 5022 is selected from any one of graphite, lithium metal and silicon.
Under the set specific pulse parameters, photons emitted by the pulse light source are better absorbed by the solid electrolyte film to be processed than the electrode structure 50, so that the pulse light source is utilized to heat the solid electrolyte film to be processed, the solid electrolyte film to be processed has a better heating effect, the crystal phase structure of the solid electrolyte film to be processed can be well changed, the grain boundary impedance of the solid electrolyte film to be processed is further well reduced, and the conduction rate of conductive ions in the solid electrolyte film 60 is improved.
Secondly, the electrode structure 50 absorbs less photons emitted by the pulse light source, so that the temperature of the electrode structure 50 is raised less, the influence of the pulse light source on the stability of the electrode structure 50 is further reduced, and the electrode structure 50 still has high specific capacity and charge-discharge cycle performance.
Furthermore, the pulsed light source has a heat treatment effect on the solid electrolyte film to be treated and the electrode structure 50 at the same time, so that the solid electrolyte film to be treated and the electrode structure 50 are further attached to each other, the interfacial resistance between the solid electrolyte film 60 and the electrode structure 50 is better reduced, the conductivity of conductive ions between the solid electrolyte film 60 and the electrode structure 50 is improved, and the conductivity is improved.
Compared with the prior art, the heat treatment method of the solid electrolyte film and the lithium battery cell structure provided by the invention have the following beneficial effects:
the method comprises the steps of carrying out heat treatment on a solid electrolyte film to be treated for a preset time by adopting a pulse light source with specific pulse parameters, setting the specific pulse parameters, wherein the solid electrolyte film to be treated has better absorption performance on photons emitted by the pulse light source, and can effectively improve the temperature of the solid electrolyte film to be treated, so that the crystal phase structure of the solid electrolyte film to be treated can be effectively controlled and changed, further the grain boundary impedance of the solid electrolyte film to be treated is changed, the conductivity of the solid electrolyte film subjected to heat treatment by conductive ions is improved, and the conductivity is improved.
The pulse width is: 10-100 mus, the pulse duration of the pulse light source under the pulse width is shorter than the heat conduction time, therefore, the energy of the light pulse is stored in the solid electrolyte film to be processed for a very short time, and almost no heat conduction occurs in the period, namely, the instant heating of the electrolyte can be realized based on the setting and selection of the pulse width, therefore, the temperature difference between the solid electrolyte film to be processed and the electrode structure after the absorption of photons can be well avoided, the heat is reduced to be transferred from one side of the solid electrolyte film to be processed with high temperature to one side of the electrode structure, the damage of the high temperature to the electrode structure is further reduced, and the grain boundary impedance of the solid electrolyte film to be processed is well changed.The pulse current density is set to: 1-40mA/cm2The pulse frequency is: 10-1000 HZ; the pulse parameters are limited, so that the heating efficiency of the pulse light source on the solid electrolyte film to be processed can be well controlled, the heating degree of the solid electrolyte film to be processed can be well controlled, and the grain boundary impedance of the solid electrolyte film to be processed can be well changed.
The heat treatment of the solid electrolyte film to be treated by adopting the pulse light source with preset pulse parameters for preset time at least comprises the step-by-step heat treatment of the solid electrolyte film to be treated by setting two pulse parameters in different ranges, the pulse parameters in different stages are different, the heat treatment effect on the solid electrolyte film to be treated is also different, and the grain boundary impedance of the solid electrolyte film to be treated can be better changed by combining the multi-stage heat treatment with different parameters.
In order to solve the above technical problems, the present invention provides another technical solution: a lithium battery cell structure, the lithium battery cell comprising an electrode structure and a solid electrolyte film formed on the electrode structure, the solid electrolyte film comprising a solid electrolyte material, the electrode structure comprising an electrode sheet and an electrode material formed on the electrode sheet, the solid electrolyte film being formed on a side of the electrode material away from the electrode sheet, the solid electrolyte film being prepared by:
depositing the solid electrolyte film material on the electrode structure by a PVD deposition technique to form a solid electrolyte film to be processed having a certain thickness;
performing heat treatment on the solid electrolyte film to be treated for a preset time by adopting a pulse light source with specific pulse parameters;
cooling the solid electrolyte film after the heat treatment.
Under the set specific pulse parameters, photons emitted by the pulse light source are better absorbed by the solid electrolyte film to be processed relative to the electrode structure, so that the pulse light source is utilized to heat the solid electrolyte film to be processed, the solid electrolyte film to be processed has a better heating effect, the crystal phase structure of the solid electrolyte film to be processed can be well changed, the grain boundary impedance of the solid electrolyte film to be processed is further well reduced, and the conduction rate of conductive ions on the solid electrolyte film is improved.
Secondly, the electrode structure absorbs less photons emitted by the pulse light source, so that the temperature of the electrode structure is increased less, the influence of the pulse light source on the stability of the electrode structure is further well reduced, and the electrode structure still has higher specific capacity and charge-discharge cycle performance.
Furthermore, the pulse light source has a heat treatment effect on the solid electrolyte film to be treated and the electrode structure at the same time, so that the solid electrolyte film and the electrode structure are further jointed, the interface impedance between the solid electrolyte film and the electrode structure is better reduced, the conductivity of conductive ions between the solid electrolyte film and the electrode structure is improved, and the conductivity is improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A method for heat-treating a solid electrolyte film, comprising the steps of:
providing a solid electrolyte film to be treated with a certain thickness, wherein the solid electrolyte film to be treated is formed on the electrode structure;
carrying out heat treatment on the solid electrolyte film to be treated for a preset time by adopting a pulse light source with specific pulse parameters to change the crystal phase structure of the solid electrolyte film, wherein the pulse parameters comprise: the pulse width is: 10-100 mus;
cooling the solid electrolyte film after the heat treatment.
2. The solid electrolyte membrane of claim 1A method of heat treating a film, characterized by: the pulse parameters are specifically as follows: the pulse current density was: 1-40mA/cm2The pulse frequency is: 10-1000HZ, and the heat treatment time is as follows: 1-10 h.
3. The method for heat-treating a solid electrolyte membrane according to claim 2, characterized in that: the heat treatment of the solid electrolyte film to be treated for a predetermined time by adopting a pulse light source with specific pulse parameters comprises the step of setting at least two pulse parameters with different ranges for the heat treatment of the solid electrolyte film to be treated in stages.
4. The method for heat-treating a solid electrolyte membrane according to claim 3, characterized in that: the staged heat treatment comprises the following three stages:
the first stage is as follows: the pulse current density was: 1-10mA/cm2The pulse frequency is: 10-100HZ, and the heating time is as follows: 1-2 h;
and a second stage: the pulse current density was: 20-40mA/cm2The pulse frequency is: 200-1000HZ, wherein the heating time is as follows: 2-3 h;
and a third stage: the pulse current density was: 1-10mA/cm2The pulse frequency is: 10-100HZ, and the heating time is as follows: 1-1.5 h.
5. The method for heat-treating a solid electrolyte membrane according to claim 1, characterized in that: the absorptivity of the solid electrolyte film to be processed to photons emitted by the pulse light source with the specific pulse parameters is more than 80%.
6. The method for heat-treating a solid electrolyte membrane according to claim 1, characterized in that: the pulsed light source includes: any one or combination of several of ultraviolet lamp, infrared lamp, high pressure sodium lamp or halogen tungsten lamp.
7. The method for heat-treating a solid electrolyte membrane according to any one of claims 1 to 6, characterized in that: the solid electrolyte film to be treated comprises an inorganic solid electrolyte, the inorganic solid electrolyte comprises a Li-La-Zr-O type material or a material obtained by doping elements thereof, and the conductivity of the solid electrolyte film after cooling heat treatment is as follows: 4-8 mS/cm.
8. A lithium battery cell structure comprising an electrode structure and a solid electrolyte film formed on the electrode structure, the solid electrolyte film comprising a solid electrolyte film material, the electrode structure comprising an electrode sheet and an electrode material formed on the electrode sheet, the solid electrolyte film being formed on a side of the electrode material remote from the electrode sheet, wherein: the solid electrolyte film is prepared by the following method:
depositing the solid electrolyte film material on the electrode structure by a PVD deposition technique to form a solid electrolyte film to be processed having a certain thickness;
carrying out heat treatment on the solid electrolyte film to be treated for a preset time by adopting a pulse light source with specific pulse parameters to change the crystal phase structure of the solid electrolyte film, wherein the pulse parameters comprise: the pulse width is: 10-100 mus;
cooling the solid electrolyte film after the heat treatment.
9. The lithium battery cell structure of claim 8, wherein: the electrode plate comprises a positive electrode plate and/or a negative electrode plate, the electrode material comprises a positive electrode material formed on the positive electrode plate and/or a negative electrode material formed on the negative electrode plate, and the solid electrolyte film is formed on the positive electrode material and/or the negative electrode material.
10. The lithium battery cell structure of claim 9, wherein: the positive electrode material comprises LiCoO2，LiMnO2，LiNiO2，LiVO2，LiNi1/3Co1/3Mn1/3O2，LiMn2O4，LiFePO4，LiMnPO4，LiNiPO4，Li2FeSiO4Any one or any combination of the above, and the negative electrode material is selected from any one of graphite, lithium metal and silicon.
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