CN110752347A - Flexible electrode of lithium ion battery and preparation method thereof - Google Patents

Flexible electrode of lithium ion battery and preparation method thereof Download PDF

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CN110752347A
CN110752347A CN201910858497.3A CN201910858497A CN110752347A CN 110752347 A CN110752347 A CN 110752347A CN 201910858497 A CN201910858497 A CN 201910858497A CN 110752347 A CN110752347 A CN 110752347A
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membrane
flexible
filter membrane
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flexible substrate
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CN110752347B (en
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不公告发明人
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Wuhan Ruikomei New Energy 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
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a preparation method of a flexible electrode of a lithium ion battery, which comprises the following steps: s100: firstly, carrying out dispersion treatment on a flexible substrate a and a surfactant a, and pouring the flexible substrate a and the surfactant a into a device with a filter membrane for suction filtration to form a first membrane on the filter membrane; s200: dispersing the flexible substrate b, the active substance, the surfactant b and the filler, pouring the mixture into an instrument in S100, and performing suction filtration to form a second membrane on the first membrane; s300: and drying, shaping and stripping the filter membrane in the S200 to obtain the flexible electrode. The invention has the beneficial effects that: the preparation of the flexible electrode by a simple suction filtration method is realized; the flexible electrode can be prepared without a current collector, complex post-treatment work is avoided, the preparation method is simple, and the success rate of experiments is high; the preparation method is flexible; the prepared flexible electrode has good flexibility and does not have the powder dropping phenomenon caused by the traditional coating method.

Description

Flexible electrode of lithium ion battery and preparation method thereof
Technical Field
The invention relates to the technical field of preparation of flexible lithium ion batteries, in particular to a flexible electrode of a lithium ion battery and a preparation method thereof.
Background
In recent years, flexible wearable electronic devices such as smartwatches, flexible screens, wearable sensors, and knitted wristbands have attracted a great deal of interest and provide promising guidance for future life styles.
The flexible electrode is an essential component of a flexible battery, and is generally prepared in a planar or fibrous shape by adding an active material on a flexible conductive substrate. The positive active material of a common lithium ion battery comprises LiCO2、LiFePO4、LiMnO4And ternary materials (NCM and NCA), and the negative active material includes graphite, silicon powder, graphene, and the like. In the battery construction, the flexible lithium ion battery can be designed into a two-dimensional sheet shape or a one-dimensional fiber shape. In a conventional planar flexible lithium ion battery, an active material is prepared into slurry, and then the slurry is coated on a metal foil (copper foil or aluminum foil) to serve as a flexible electrode, a positive active material is coated on the aluminum foil to serve as a flexible positive electrode, and a negative active material is coated on the copper foil to serve as a flexible negative electrode.
However, since the conventional flexible lithium ion battery is limited by the flexibility of the planar structure, the electrochemical performance of the battery is seriously degraded after being greatly deformed, and although the thin film structure has good flexibility, the conventional thin film electrode is easily perforated and cracked, and is difficult to be in close contact with an irregular substrate, which may cause the electrochemical performance of the thin film battery to be greatly degraded.
In the prior art, the powder falling is serious in a coating method, the deformation is also limited by the mechanical property of the material, and meanwhile, the electrochemical property is also greatly reduced after the material is greatly deformed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a flexible electrode of a lithium ion battery and a preparation method thereof, so as to overcome the defects in the prior art.
The technical scheme for solving the technical problems is as follows: a preparation method of a flexible electrode of a lithium ion battery comprises the following steps:
s100: firstly, carrying out dispersion treatment on a flexible substrate a and a surfactant a, and pouring the flexible substrate a and the surfactant a into a device with a filter membrane for suction filtration to form a first membrane on the filter membrane;
s200: dispersing the flexible substrate b, the active substance, the surfactant b and the filler, pouring the mixture into an instrument in S100, and performing suction filtration to form a second membrane on the first membrane;
s300: and drying, shaping and stripping the filter membrane in the S200 to obtain the flexible electrode.
Further, the dispersing treatment of the flexible substrate a and the surfactant a in S100 includes:
s110, fully mixing a flexible substrate a and a surfactant a in a container filled with deionized water to obtain a mixed solution a, wherein the concentration of the flexible substrate a in the formed mixed solution a is 3-5 g/L;
and S120, placing the container containing the mixed solution a in an ultrasonic crusher for ultrasonic dispersion treatment for 1-3 hours.
Further, in the step S100,
the flexible substrate a is one or two of carbon nano tube, graphene and graphene oxide;
the surfactant a is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium octadecyl sulfate or sodium stearate.
Further, the dispersing the flexible substrate b, the active material, the surfactant b, and the filler in S200 includes:
s210, fully mixing the flexible substrate b and the surfactant b in a container filled with deionized water to obtain a mixed solution b;
s220, placing the container containing the mixed solution b in an ultrasonic crusher for ultrasonic dispersion treatment;
s230, adding an active substance and a filling agent into a container containing the mixed solution b in the step S220 to obtain a mixed solution c, and then continuing to perform ultrasonic dispersion treatment, wherein the mass ratio of the flexible substrate b to the surfactant b in the formed mixed solution c is as follows: 1 (3-5), the mass ratio of the flexible substrate b to the active substance is 1 (0.3-1.5), and the mass ratio of the flexible substrate b to the filler is 1 (0.5-1.5).
Further, the flexible substrate b is one or two of carbon nanotubes, graphene and graphene oxide;
the active substance is one of lithium iron phosphate, lithium cobaltate, ternary materials, lithium titanate or graphite;
the surfactant b is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium octadecyl sulfate or sodium stearate;
the filler is one of lignin and cellulose.
Further, the specific step of S300 is as follows:
naturally airing the filter membrane in the S200 until no obvious water drops exist on the surface, and then transferring the filter membrane into an oven for shaping;
and transferring the processed filter membrane onto a substrate, and peeling the filter membrane with the surfaces of the first membrane and the second membrane facing downwards to obtain the flexible electrode.
Further, the temperature of the oven is 60-80 ℃, and the drying time is 2-5 h.
Further, the setting treatment comprises placing substrates on the upper side and the lower side of the filter membrane, and clamping the substrates by a clip, or placing an object on the upper filter paper and placing the objects in an oven together.
Further, the substrate is one of A4 paper, filter paper or weighing paper.
The invention has the beneficial effects that: the preparation method of the flexible electrode of the lithium ion battery provided by the invention realizes the preparation of the flexible electrode by a simple suction filtration method, and the preparation method is novel; the flexible electrode can be prepared without a current collector, complex post-treatment work is avoided, the preparation method is simple, and the success rate of experiments is high; the preparation method is flexible, and can be used for preparing a flexible anode and a flexible cathode; the prepared flexible electrode has good flexibility and does not have the powder dropping phenomenon caused by the traditional coating method; the electrochemical performance is excellent, and particularly the rate performance and the cycle performance are greatly improved compared with those of the traditional coating method using a current collector; compared with the traditional electrode preparation, the preparation process does not need to use organic volatile solvents such as NMP and the like, and does not use any conductive agent and binder, thereby not only reducing the cost, but also avoiding the pollution to the environment, and having important significance for the development and popularization of the preparation method of the flexible electrode.
A flexible electrode for a lithium ion battery is prepared by the method.
The adoption of the further beneficial effects is as follows: the electrochemical performance is excellent, and particularly the rate performance and the cycle performance are greatly improved compared with the traditional coating method using a current collector.
Drawings
FIG. 1 is a flow chart of a method for preparing a flexible electrode of a lithium ion battery according to the present invention;
FIG. 2 is a scanning electron microscope photograph of a flexible electrode provided in example 1 of the present invention;
fig. 3 is a picture of magnification performance of the flexible electrode provided in embodiment 2 of the present invention;
FIG. 4 is a scanning electron microscope photograph of a flexible electrode provided in example 3 of the present invention;
FIG. 5 is a general photograph of a flexible electrode provided in example 4 of the present invention;
fig. 6 is a graph of cycle performance of the flexible electrode provided in example 5 of the present invention.
Detailed Description
The embodiment of the invention provides the preparation method of the flexible electrode of the lithium ion battery, which realizes the preparation of the flexible electrode by a simple suction filtration method, can prepare the flexible electrode without a current collector, does not use any organic solvent such as a conductive agent, a binder and NMP (N-methyl pyrrolidone), not only reduces the preparation cost, but also avoids pollution to the environment, has simple preparation method, has good flexibility, does not have the powder falling phenomenon caused by the traditional coating method, and has excellent electrochemical performance.
In order to better understand the technical solutions, the technical solutions will be described in detail below with reference to the drawings and the specific embodiments of the specification, and it should be understood that the embodiments and specific features of the embodiments of the present invention are detailed descriptions of the technical solutions of the present application, and are not limitations of the technical solutions of the present application, and the technical features of the embodiments and examples of the present application may be combined with each other without conflict.
As shown in fig. 1, a method for preparing a flexible electrode of a lithium ion battery includes the following steps:
s100: firstly, carrying out dispersion treatment on a flexible substrate a and a surfactant a, and pouring the flexible substrate a and the surfactant a into a device with a filter membrane for suction filtration to form a first membrane on the filter membrane;
generally, the flexible substrate a is one or two of carbon nanotube, graphene and graphene oxide;
the surfactant a is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium octadecyl sulfate or sodium stearate;
the filter membrane is one of a PTFE filter membrane, a PVDF filter membrane, a nylon filter membrane and a PP filter membrane;
the dispersion treatment of the flexible substrate a and the surfactant a comprises the following steps:
s110, fully mixing a flexible substrate a and a surfactant a in a container filled with deionized water to obtain a mixed solution a, wherein the concentration of the flexible substrate a in the formed mixed solution a is 3-5 g/L;
s120, placing the container containing the mixed solution a in an ultrasonic pulverizer for ultrasonic dispersion treatment for 1-3 hours;
the apparatus can be a sand core funnel in the prior art, the container can be a beaker in the prior art, and the ultrasonic cell crusher can be an ultrasonic cell crusher in the prior art;
s200: dispersing the flexible substrate b, the active substance, the surfactant b and the filler, pouring the mixture into an instrument in S100, and performing suction filtration to form a second membrane on the first membrane;
the dispersion treatment of the flexible substrate b, the active material, the surfactant b and the filler includes:
s210, fully mixing the flexible substrate b and the surfactant b in a container filled with deionized water to obtain a mixed solution b;
s220, placing the container containing the mixed solution b in an ultrasonic crusher for ultrasonic dispersion treatment;
s230, adding an active substance and a filling agent into a container containing the mixed solution b in the step S220 to obtain a mixed solution c, and then continuing to perform ultrasonic dispersion treatment, wherein the mass ratio of the flexible substrate b to the surfactant b in the formed mixed solution c is as follows: 1, (3) to 5), wherein the mass ratio of the flexible substrate b to the active substance is 1, (0.3 to 1.5), and the mass ratio of the flexible substrate b to the filler is 1, (0.5 to 1.5);
the flexible substrate b is one or two of carbon nano tube, graphene and graphene oxide;
the active substance is one of lithium iron phosphate, lithium cobaltate, ternary material, lithium titanate or graphite;
the surfactant b is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium octadecyl sulfate or sodium stearate;
the filler is one of lignin and cellulose;
s300: drying, shaping and stripping the filter membrane in the S200 to obtain a flexible electrode;
the method comprises the following specific steps:
naturally airing the filter membrane in the S200 until no obvious water drops exist on the surface, transferring the filter membrane into an oven and carrying out shaping treatment, wherein the temperature of the oven is 60-80 ℃, and the drying time is 2-5 h;
transferring the processed filter membrane onto a substrate, wherein the substrate is one of A4 paper, filter paper or weighing paper, and the filter membrane is stripped with the surfaces of the first membrane and the second membrane facing downwards to obtain a flexible electrode;
the shaping treatment comprises placing substrates on the upper and lower sides of the filter membrane, and clamping with a clip, or placing an object on the upper filter paper, and placing them into an oven.
A flexible electrode for a lithium ion battery is prepared by the method.
Specific examples will be provided below:
example 1
Taking 20mg of carbon nanotubes in a beaker filled with 50mL of deionized water, adding 0.05g of sodium dodecyl sulfate into the beaker, dispersing the mixture for 30min by using an ultrasonic cell crusher, pouring the solution into a sand core funnel paved with a PTFE filter membrane for suction filtration after the dispersion is finished, leaching the solution for three times by using the deionized water after the suction filtration is finished, and forming a first membrane on the filter membrane;
putting 60mg of carbon nano tube into a beaker filled with 100mL of deionized water, adding 0.25g of sodium dodecyl sulfate, dispersing for 30min by using an ultrasonic cell crusher, adding 60mg of lignin and 20mg of lithium iron phosphate into the beaker, continuing to disperse for 1h by ultrasonic, pouring the solution into a sand core funnel paved with a first membrane after the dispersion is finished, carrying out suction filtration, leaching with deionized water for three times after the suction filtration is finished, and finishing the second membrane;
standing the filter membrane which is subjected to suction filtration and provided with the first membrane and the second membrane for 6h until no obvious water drops exist on the surface, transferring the filter membrane into an oven, respectively placing a piece of filter paper above and below the filter membrane, pressing the upper part of the filter membrane by using a beaker, drying the filter membrane for 5h at 60 ℃, taking out the filter membrane and placing the filter membrane on clean A4 paper, wherein the surface of the filter membrane provided with the first membrane and the second membrane is downward and is opposite to the A4 paper, and stripping the flexible electrode, wherein the composite of the first membrane and the second membrane is the flexible electrode, and the specific capacity of the flexible electrode obtained by the process under the condition of 0.1A/g current density is 120 mAh/g.
Referring to fig. 2, a Scanning Electron Microscope (SEM) photograph of this scheme shows that the carbon nanotubes of the dense hemp are interlaced with each other to form a huge network structure, as shown in fig. 2.
Example 2
Putting 30mg of graphene into a beaker filled with 100mL of deionized water, adding 0.065g of sodium octadecyl sulfate, dispersing for 45min by using an ultrasonic cell crusher, pouring the solution into a sand core funnel paved with a PVDF filter membrane for suction filtration after the dispersion is finished, leaching for three times by using the deionized water after the suction filtration is finished, and forming a first membrane on the filter membrane;
and (2) putting 80mg of graphene into a beaker filled with 100mL of deionized water, adding 0.25g of sodium octadecyl sulfate, dispersing for 45min by using an ultrasonic cell crusher, adding 60mg of cellulose and 20mg of ternary cathode powder (NCM523) into the beaker, and continuing to perform ultrasonic dispersion for 1 h. After dispersion is finished, pouring the solution into a sand core funnel paved with a first layer of flexible substrate, carrying out suction filtration, leaching with deionized water for three times after the suction filtration is finished, and finishing a second layer of film;
standing the filter membrane which is subjected to suction filtration and provided with the first membrane and the second membrane for 6h until no obvious water drops exist on the surface, transferring the filter membrane into an oven, placing a piece of filter paper above and below the filter membrane respectively, fixing the filter membrane by using a clip, drying the filter membrane for 2h at 80 ℃, taking out the filter membrane and placing the filter membrane on clean A4 paper, enabling the surfaces of the filter membrane, which are provided with the first membrane and the second membrane, to face downwards to the A4 paper, and stripping the flexible electrode, wherein the composite of the first membrane and the second membrane is the flexible electrode, and the specific capacity of the flexible electrode obtained by the process under the condition of 0.1A/g current density is 165 mAh/g.
Referring to fig. 3, a graph of rate capability under the scheme, it can be known from fig. 3 that the flexible electrode prepared by the method has excellent rate capability, and the capacity is 115mAh/g under the large rate of 2A/g.
Example 3
Taking 10mg of graphene and 10mg of carbon nanotubes in a beaker filled with 50mL of deionized water, adding 0.03g of sodium dodecyl benzene sulfonate into the beaker, dispersing the mixture for 40min by using an ultrasonic cell crusher, and pouring the solution into a sand core funnel paved with a nylon filter membrane for suction filtration after the dispersion is finished. After the suction filtration is finished, leaching with deionized water for three times to form a first membrane on the filter membrane;
and (2) putting 30mg of graphene and 30mg of carbon nanotubes into a beaker filled with 100mL of deionized water, adding 0.2g of sodium dodecyl benzene sulfonate, dispersing for 40min by using an ultrasonic cell crusher, adding 60mg of cellulose and 30mg of lithium titanate powder into the beaker, and continuing to perform ultrasonic dispersion for 1 h. And after the dispersion is finished, pouring the solution into a sand core funnel paved with the first layer of flexible substrate, and performing suction filtration. After the suction filtration is finished, leaching with deionized water for three times, and finishing the second layer of film;
standing the filter membrane which is subjected to suction filtration and provided with the first membrane and the second membrane for 6h until no obvious water drops exist on the surface, transferring the filter membrane into an oven, placing a piece of filter paper on the upper side and the lower side of the filter membrane respectively, fixing the filter membrane by using a clip, drying the filter membrane for 3h at 70 ℃, taking out the filter membrane and placing the filter membrane on clean weighing paper, wherein the surfaces of the filter membrane, which are provided with the first membrane and the second membrane, face down and face towards the weighing paper, stripping the flexible electrode, and obtaining the composite of the first membrane and the second membrane, namely the flexible electrode, wherein the specific capacity of the flexible electrode obtained by the process under the condition of 0.1A/g current density is 180.
Referring to fig. 4, a Scanning Electron Microscope (SEM) photograph of this scheme shows that the carbon nanotubes and graphene in the dense hemp are interlaced with each other to form a huge network structure, as shown in fig. 4.
Example 4
And (3) putting 30mg of graphene oxide in a beaker filled with 70mL of deionized water, adding 0.04g of sodium stearate, dispersing for 50 hours by using an ultrasonic cell crusher, and pouring the solution into a sand core funnel paved with a PP filter membrane for suction filtration after the dispersion is finished. After the suction filtration is finished, leaching with deionized water for three times to form a first membrane on the filter membrane;
50mg of graphene is put into a beaker filled with 100mL of deionized water, 0.2g of sodium stearate is added into the graphene, after the graphene is dispersed for 1 hour by an ultrasonic cell crusher, 80mg of cellulose and 20mg of graphite powder are added into the beaker, and the ultrasonic dispersion is continued for 1 hour. After dispersion, pouring the solution into a sand core funnel paved with a first layer of flexible substrate, carrying out suction filtration, leaching with deionized water for three times after the suction filtration is finished, and finishing the second layer of film;
standing the filter membrane which is subjected to suction filtration and provided with the first membrane and the second membrane for 6h until no obvious water drops exist on the surface, transferring the filter membrane into an oven, placing a piece of filter paper on the upper side and the lower side of the filter membrane respectively, fixing the filter membrane by using a clip, drying the filter membrane for 3h at 75 ℃, taking out the filter membrane and placing the filter membrane on clean filter paper, wherein the surfaces of the filter membrane provided with the first membrane and the second membrane face the filter paper downwards, stripping the flexible electrode, and the composite of the first membrane and the second membrane is the flexible electrode, and the specific capacity of the flexible electrode obtained by the process under the condition of 0.1A/g current density is 330 mAh/g.
Referring to fig. 5, a general photograph of the scheme, it can be seen from fig. 5 that the flexible electrode prepared by the scheme has good flexibility.
Example 5
And (3) putting 10mg of graphene oxide and 20mg of carbon nanotubes into a beaker filled with 80mL of deionized water, adding 0.04g of sodium octadecyl sulfate into the beaker, dispersing the mixture for 45min by using an ultrasonic cell crusher, and pouring the solution into a sand core funnel paved with a PTFE filter membrane for suction filtration after the dispersion is finished. After the suction filtration is finished, leaching with deionized water for three times to form a first membrane on the filter membrane;
and (2) putting 80mg of graphene oxide into a beaker filled with 100mL of deionized water, adding 0.2g of sodium octadecyl sulfate, dispersing for 1h by using an ultrasonic cell crusher, adding 60mg of lignin and 20mg of lithium cobaltate powder into the beaker, and continuing to perform ultrasonic dispersion for 1 h. After dispersion is finished, pouring the solution into a sand core funnel paved with a first layer of flexible substrate, carrying out suction filtration, leaching with deionized water for three times after the suction filtration is finished, and finishing a second layer of film;
standing the filter membrane which is subjected to suction filtration and provided with the first membrane and the second membrane for 6h until no obvious water drops exist on the surface, transferring the filter membrane into an oven, placing a piece of filter paper on the upper side and the lower side of the filter membrane respectively, fixing the filter membrane by using a clip, drying the filter membrane for 5h at 70 ℃, taking out the filter membrane and placing the filter membrane on clean filter paper, wherein the surfaces of the filter membrane provided with the first membrane and the second membrane face the filter paper downwards, stripping the flexible electrode, and the composite of the first membrane and the second membrane is the flexible electrode, and the specific capacity of the flexible electrode obtained by the process under the condition of 2A/g high current density is 95 mAh/g.
Referring to fig. 6, a large-rate cycle performance picture under the scheme shows that the flexible electrode prepared by the scheme still has good cycle performance under the large-rate charge and discharge condition, and the capacity is still maintained above 90mAh/g after 250 cycles of charge and discharge.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
the preparation method of the flexible electrode of the lithium ion battery provided by the embodiment of the application realizes the preparation of the flexible electrode by a simple suction filtration method, and the preparation method is novel; the flexible electrode can be prepared without a current collector, complex post-treatment work is avoided, the preparation method is simple, and the success rate of experiments is high; the preparation method is flexible, and can be used for preparing a flexible anode and a flexible cathode; the prepared flexible electrode has good flexibility and does not have the powder dropping phenomenon caused by the traditional coating method; the electrochemical performance is excellent, and particularly the rate performance and the cycle performance are greatly improved compared with those of the traditional coating method using a current collector; compared with the traditional electrode preparation, the preparation process does not need to use organic volatile solvents such as NMP and the like, and does not use any conductive agent and binder, thereby not only reducing the cost, but also avoiding the pollution to the environment, and having important significance for the development and popularization of the preparation method of the flexible electrode.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. A preparation method of a flexible electrode of a lithium ion battery is characterized by comprising the following steps:
s100: firstly, carrying out dispersion treatment on a flexible substrate a and a surfactant a, and pouring the flexible substrate a and the surfactant a into a device with a filter membrane for suction filtration to form a first membrane on the filter membrane;
s200: dispersing the flexible substrate b, the active substance, the surfactant b and the filler, pouring the mixture into an instrument in S100, and performing suction filtration to form a second membrane on the first membrane;
s300: and drying, shaping and stripping the filter membrane in the S200 to obtain the flexible electrode.
2. The method according to claim 1, wherein the step S100 of dispersing the flexible substrate a and the surfactant a comprises:
s110, fully mixing a flexible substrate a and a surfactant a in a container filled with deionized water to obtain a mixed solution a, wherein the concentration of the flexible substrate a in the formed mixed solution a is 3-5 g/L;
and S120, placing the container containing the mixed solution a in an ultrasonic crusher for ultrasonic dispersion treatment for 1-3 hours.
3. The method for preparing the flexible electrode of the lithium ion battery according to claim 1, wherein in S100,
the flexible substrate a is one or two of carbon nano tube, graphene and graphene oxide;
the surfactant a is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium octadecyl sulfate or sodium stearate.
4. The method of claim 1, wherein the step S200 of dispersing the flexible substrate b, the active material, the surfactant b and the filler comprises:
s210, fully mixing the flexible substrate b and the surfactant b in a container filled with deionized water to obtain a mixed solution b;
s220, placing the container containing the mixed solution b in an ultrasonic crusher for ultrasonic dispersion treatment;
s230, adding an active substance and a filling agent into a container containing the mixed solution b in the step S220 to obtain a mixed solution c, and then continuing to perform ultrasonic dispersion treatment, wherein the mass ratio of the flexible substrate b to the surfactant b in the formed mixed solution c is as follows: 1 (3-5), the mass ratio of the flexible substrate b to the active substance is 1 (0.3-1.5), and the mass ratio of the flexible substrate b to the filler is 1 (0.5-1.5).
5. The method for preparing the flexible electrode of the lithium ion battery according to claim 4,
the flexible substrate b is one or two of a carbon nano tube, graphene and graphene oxide;
the active substance is one of lithium iron phosphate, lithium cobaltate, ternary materials, lithium titanate or graphite;
the surfactant b is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium octadecyl sulfate or sodium stearate;
the filler is one of lignin and cellulose.
6. The method for preparing the flexible electrode of the lithium ion battery according to claim 1, wherein the S300 comprises the following steps:
naturally airing the filter membrane in the S200 until no obvious water drops exist on the surface, and then transferring the filter membrane into an oven for shaping;
and transferring the processed filter membrane onto a substrate, and peeling the filter membrane with the surfaces of the first membrane and the second membrane facing downwards to obtain the flexible electrode.
7. The preparation method of the flexible electrode of the lithium ion battery according to claim 6, wherein the temperature of the oven is 60-80 ℃, and the drying time is 2-5 h.
8. The method of claim 6, wherein the shaping process comprises placing a substrate on each of the top and bottom of the filter membrane and clamping the substrate with a paper clip, or placing an object on the top filter paper and placing the object in an oven.
9. The method for preparing the flexible electrode of the lithium ion battery according to claim 8, wherein the substrate is one of A4 paper, filter paper or weighing paper.
10. A flexible electrode for a lithium ion battery, prepared by the method of any one of claims 1 to 9.
CN201910858497.3A 2019-09-11 2019-09-11 Flexible electrode of lithium ion battery and preparation method thereof Active CN110752347B (en)

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CN111812176A (en) * 2020-07-09 2020-10-23 哈尔滨工业大学（深圳） Flexible bioelectrode based on liquid metal nano ink and preparation method thereof

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CN105633343A (en) * 2015-12-31 2016-06-01 武汉艾特米克超能新材料科技有限公司 Flexible lithium ion battery electrode plate with self supporting capability and preparation method thereof

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