CN111916678A - High specific energy lithium battery electrode, dry preparation method thereof and lithium battery - Google Patents

High specific energy lithium battery electrode, dry preparation method thereof and lithium battery Download PDF

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Publication number
CN111916678A
CN111916678A CN202010966968.5A CN202010966968A CN111916678A CN 111916678 A CN111916678 A CN 111916678A CN 202010966968 A CN202010966968 A CN 202010966968A CN 111916678 A CN111916678 A CN 111916678A
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electrode
lithium battery
processing aid
poly
carbonate
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CN111916678B (en
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桂鲁哲
桂客
毛泽民
李泓
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Institute of Physics of CAS
Tianmu Lake Institute of Advanced Energy Storage Technologies Co Ltd
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Tianmu Lake Institute of Advanced Energy Storage Technologies 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
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • 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
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • 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

Abstract

The invention relates to a high specific energy lithium battery electrode, a dry preparation method thereof and a lithium battery. The method comprises the following steps: under the heating condition, uniformly mixing the electrode material and the processing aid according to the mass of the processing aid which accounts for 10-80% of the total mass of the electrode material and the processing aid to form a paste mixture; wherein the electrode material comprises: electrode active material, conductive agent, adhesive; the processing aid comprises: one or more combinations of poly (ethylene carbonate) PEC, poly (propylene carbonate) Poly (propylene carbonate), poly (butylene carbonate), poly (cyclohexene polycarbonate), or poly (trimethylene carbonate) PTMC; rolling and molding the paste mixture, and then hot-pressing the paste mixture on a current collector to obtain an electrode plate; and carrying out heat treatment on the electrode slice under a vacuum condition to obtain the high-specific-energy lithium battery electrode.

Description

High specific energy lithium battery electrode, dry preparation method thereof and lithium battery
Technical Field
The invention relates to the technical field of battery materials, in particular to a high-specific-energy lithium battery electrode, a dry preparation method thereof and a lithium battery.
Background
Due to rapid development of modern society economy and science and technology, the performance of the traditional lithium ion battery can not meet the current energy requirement. The fields of rapidly developing electric automobiles, intelligent consumer electronics and the like all urgently need lithium ion batteries with higher energy density, long cycle life, low cost and high safety. In the aspect of positive and negative electrodes, the requirements on material performance are higher and higher, and meanwhile, the preparation process of the positive and negative electrode plates also puts forward higher requirements.
At present, a lithium ion battery electrode is prepared by coating a mixed slurry consisting of an active material, a conductive agent, a binder and a solvent on a current collector by a wet method, in the wet method preparation process, drying is the step of consuming most energy in the electrode preparation process, an oil-soluble binder also needs to use N-methyl pyrrolidone (NMP) as the solvent, the solvent has high cost and toxicity, steam generated in the drying process can damage a human body, the electrode prepared by the wet method easily causes the solvent and the binder to form a binder layer, and the whole active material particle is surrounded by the binder layer, so that the contact between the active material particles and the conductive agent particle is hindered, and poor electrode conductivity is caused.
The dry method electrode preparation electrode does not use solvent in the process, so that the problems can be avoided. However, conventional dry techniques require a high amount of binder control due to the lack of dispersibility provided by the solvent. If the content of the binder is too low, layering can occur in the pulping process, the forming is difficult in the coating process, and meanwhile, the insufficient binder can cause that the pole piece can not form a perfect three-dimensional reticular structure, the conductivity is reduced, so that the problems of resistance increase, capacity attenuation and the like are caused; if the binder content is too large, it tends to result in a high proportion of inactive materials, resulting in a decrease in mass energy density, and particularly in dry-method electrodes, the amount of binder is required to be high due to lack of dispersibility provided by a solvent, and an excessively high binder amount results in an increase in internal resistance and a decrease in capacity exertion efficiency. In addition, since the powder needs to be directly extruded into a dry electrode film, the pure powder can cause difficulty in processing and forming thin materials, or powder coating or deposition equipment such as laser and static electricity is needed, the required process requirement is high, and the manufacturing cost is difficult to reduce.
Disclosure of Invention
In order to solve the technical problems, the embodiment of the invention provides a high-specific-energy lithium battery electrode, a dry-method preparation method thereof and a lithium battery. The method of preparing the electrode by a dry method without using a solvent is adopted, and a specific processing aid is added in the process of solvent-free mixing, so that the dispersing performance is enhanced, the active substance, the conductive agent and the binder are uniformly dispersed, and the electrode is easy to process and form; meanwhile, the demand of a material system on the adhesive is reduced, the internal resistance of an electrode material is also reduced, and the electrochemical performance of the battery is ensured; by introducing and using the processing aid, powder spraying in a conventional dry process is not needed in the process, and the processing process steps and cost are saved.
In a first aspect, an embodiment of the present invention provides a dry method for preparing a high specific energy lithium battery electrode: the dry preparation method comprises the following steps:
under the heating condition, uniformly mixing the electrode material and the processing aid according to the mass of the processing aid which accounts for 10-80% of the total mass of the electrode material and the processing aid to form a paste mixture; wherein the electrode material comprises: electrode active material, conductive agent, adhesive; the processing aid comprises: one or more combinations of poly (ethylene carbonate) PEC, poly (propylene carbonate) Poly (propylene carbonate), poly (butylene carbonate), poly (cyclohexene polycarbonate), or poly (trimethylene carbonate) PTMC;
rolling and molding the paste mixture, and then hot-pressing the paste mixture on a current collector to obtain an electrode plate;
and carrying out heat treatment on the electrode slice under a vacuum condition to obtain the high-specific-energy lithium battery electrode.
Preferably, the heating condition is 40-90 ℃;
the method for uniformly mixing specifically comprises the following steps: ball milling and mixing are carried out in a ball mill, or mechanical milling and mixing are carried out.
Preferably, the mass of the processing aid accounts for 25-50% of the total mass of the electrode material and the processing aid.
Preferably, the pressure of the rolling is 400psi-800 psi; the hot pressing temperature is 40-90 deg.C, and the pressure is 20-50 psi.
Preferably, the electrode active material includes a positive electrode active material or a negative electrode active material;
the positive electrode active material includes: one or more of nickel cobalt lithium manganate, lithium iron phosphate, lithium manganate, lithium cobaltate, lithium nickel cobalt aluminate and lithium-rich manganese-based materials;
the negative active material includes: one or more of nano silicon, silica, silicon carbon, graphite, soft carbon and hard carbon;
the conductive agent includes: one or a combination of more of conductive carbon black, carbon fiber, conductive graphite and carbon nano tube;
the adhesive includes: one or a combination of more of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, nitrile rubber, sodium carboxymethylcellulose, polyacrylic acids, polyacrylonitrile and sodium alginate.
Preferably, the current collector includes an aluminum foil or a copper foil.
Preferably, the heat treatment of the electrode sheet under a vacuum condition specifically includes:
and under the vacuum condition, heating the electrode plate to at least reach the decomposition temperature of the processing aid, and continuously vacuumizing the heat treatment environment to decompose the processing aid.
Preferably, the thickness of the obtained high specific energy lithium battery electrode is 1 μm to 200 μm.
In a second aspect, the embodiment of the present invention provides a high specific energy lithium battery electrode prepared by the preparation method described in the first aspect.
In a third aspect, embodiments of the present invention provide a lithium battery, including the electrode of the high specific energy lithium battery described in the second aspect.
The embodiment of the invention provides a dry preparation method of a high-specific energy lithium battery electrode, wherein a specific processing aid is added in the solvent-free mixing process to enhance the dispersing performance, so that an active substance, a conductive agent and a binder are uniformly dispersed and are easy to process and form; meanwhile, the demand of a material system on the adhesive is reduced, the internal resistance of the electrode material is also reduced, the specific energy of the material is improved, and the electrochemical performance of the battery is ensured; by introducing and using the processing aid, powder spraying in a conventional dry process is not needed in the process, and an expensive solvent is not needed, so that a drying process for the solvent is not needed, the processing process steps are saved, and the production cost is reduced. The processing aid is decomposed by heat treatment, and is convenient to recover and recycle. The electrode prepared by the dry preparation method provided by the invention has good cycle stability, storage life, high temperature performance, safety performance and rate capability.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
FIG. 1 is a flow chart of a dry method for preparing an electrode of a lithium battery with high specific energy according to an embodiment of the present invention;
FIG. 2 is a comparison graph of 100-cycle performance at 0.1C when the negative electrode sheets provided in example 1 and comparative example 1 of the present invention are applied to lithium batteries;
fig. 3 is a comparison graph of rate performance of the negative electrode plate applied to the lithium battery provided in example 1 and comparative example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following figures and specific examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as in any way limiting the present invention, i.e., as in no way limiting its scope.
The dry preparation method of the high specific energy lithium battery electrode is used for preparing the lithium battery electrode by a dry method, can be used for preparing a positive electrode and a negative electrode, and has the main preparation flow as shown in figure 1, and comprises the following steps:
step 110, under a heating condition, uniformly mixing the electrode material and the processing aid according to the mass of the processing aid which accounts for 10-80% of the total mass of the electrode material and the processing aid to form a paste-like mixture;
wherein the electrode material comprises: electrode active material, conductive agent, adhesive;
the electrode active material includes a positive electrode active material or a negative electrode active material;
the positive electrode active material includes: one or more of nickel cobalt lithium manganate, lithium iron phosphate, lithium manganate, lithium cobaltate, lithium nickel cobalt aluminate and lithium-rich manganese-based materials;
the negative active material includes: one or more of nano silicon, silica, silicon carbon, graphite, soft carbon and hard carbon;
the conductive agent includes: one or a combination of more of conductive carbon black, carbon fiber, conductive graphite and carbon nano tube;
the adhesive comprises: one or a combination of more of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, nitrile rubber, sodium carboxymethylcellulose, polyacrylic acids, polyacrylonitrile and sodium alginate.
The processing aid comprises: one or more combinations of polyethylene carbonate (PEC), polypropylene carbonate (poly (propylene carbonate)), polybutylene carbonate (poly (butylene carbonate)), Polycyclohexene carbonate (Polycyclohexene carbonate), or polytrimethylene carbonate (PTMC).
The heating condition for mixing the electrode material and the processing aid is 40-90 ℃; the method for uniformly mixing specifically comprises the following steps: ball-milling and mixing in a ball mill, or mechanical milling and mixing, etc.
More preferably, the mass ratio of the processing aid to the total mass of the electrode material and the processing aid is 25-50%.
Step 120, rolling and molding the paste mixture, and then hot-pressing the paste mixture on a current collector to obtain an electrode plate;
specifically, the rolling pressure is 400psi-800 psi;
after roll forming, the temperature of hot pressing on the current collector is between 40 and 90 ℃, and the pressure is between 20 and 50 psi. The current collector can be selected from aluminum foil, copper foil and the like.
And step 130, carrying out heat treatment on the electrode slice under a vacuum condition to obtain the high-specific-energy lithium battery electrode.
Specifically, the temperature of the heat treatment is at least as high as the decomposition temperature of the processing aid, so that the processing aid is decomposed; and in the heat treatment process, the environment where the electrode plate is located is continuously vacuumized.
The processing aid introduced in the preparation method of the embodiment of the invention can provide high-efficiency dispersibility, and the obtained mixture becomes a pasty substance through the addition and mixing of the processing aid, so that the processing and forming are easy. The pole piece is finally heated to the decomposition temperature of the processing aid and can be completely decomposed to generate H2O、CO2And the depolymerization product can be further recovered and used for re-synthesizing the processing aid, so that the cost is reduced by recycling.
The thickness of the lithium battery electrode with high specific energy prepared by the invention is 1-200 μm. The obtained electrode can be used in lithium batteries including liquid lithium ion batteries, mixed solid-liquid metal lithium batteries, all-solid lithium ion batteries and all-solid metal lithium batteries.
In order to better understand the technical solutions provided by the present invention, the following description respectively illustrates specific processes for preparing an electrode of a lithium battery by applying the method provided by the above embodiments of the present invention, and a method and characteristics for applying the same to a lithium battery by using a plurality of specific examples.
Example 1
The embodiment provides a solvent-free dry preparation process of a high-specific energy lithium battery electrode, which comprises the following steps of:
under the condition of 60 ℃, mixing artificial graphite, conductive carbon black, carbon nanofiber and styrene butadiene rubber according to the mass part ratio of 80: 10: 5: 5 simply mixing in a planetary ball mill at 2000rpm, adding 80 parts of polyethylene carbonate (PEC), keeping the same rotating speed, stirring for 1 hour, then rolling and molding the obtained homogeneous mixture under 600psi pressure, hot-pressing the rolled thin material on copper foil at 45 ℃ and 35psi pressure to obtain a negative plate, and finally gradually heating the negative plate to 230 ℃ under the vacuum condition to obtain the negative plate.
The processing aid used in this example, polyethylene carbonate (PEC), has a very low glass transition temperature (0-10 ℃) which reduces the temperature requirements during processing.
To better illustrate the effect of the present invention, the negative electrode plate prepared by the conventional wet slurry was used as comparative example 1 for comparison.
Comparative example 1
The composition of the negative electrode slurry in this comparative example was: the mass ratio of the artificial graphite to the conductive carbon black to the carbon nanofiber to the styrene butadiene rubber is 80: 10: 5: and 5, the solvent is water.
And (2) uniformly stirring the slurry, coating the slurry on a copper foil by using a scraper, putting the copper foil into an oven, firstly carrying out air blast drying on the negative current collector coated with the negative slurry with the thickness of 100 microns at 80 ℃ for 2 hours, then carrying out rapid air blast drying at 120 ℃ for 1 hour, finally carrying out deep vacuum drying at 110 ℃ for 1.5 hours, and rolling to obtain the negative pole piece of the comparative example 1.
The negative pole piece prepared by the dry method in the embodiment 1 and the negative pole piece prepared by the traditional wet method in the comparative example 1 are respectively tested, wherein the comparative results of the stripping test are shown in the table 1; the results of comparison of the sheet resistances measured by the four-probe method at-30 ℃ are shown in Table 2.
Electrode preparation method Peel strength (N/cm) Peel force (N)
Example 1: PEC dry process preparation 0.0075 0.1869
Comparative example 1: preparation by traditional wet method 0.0072 0.1790
TABLE 1
Electrode preparation method Surface resistance (m omega)
Example 1: PEC dry process preparation 5.87
Comparative example 1: preparation by traditional wet method 6.32
TABLE 2
Through test comparison, the negative plate prepared in the embodiment 1 of the invention has the bonding strength between the negative material and the current collector which is comparable to that of the negative plate prepared by the traditional wet method, and is even better, and meanwhile, the internal resistance of the electrode material is smaller.
The negative pole piece prepared by the dry method in the embodiment 1 and the negative pole piece prepared by the traditional wet method in the comparative example 1 are respectively manufactured into button cells, and the performances are compared. The battery adopts a Celgard2300 model diaphragm, metal lithium as a counter electrode, Ethylene Carbonate (EC)/dimethyl carbonate (DMC) +1MLiPF6Is an electrolyte. Through tests, the comparison graph of the 100-week cycle performance at 0.1 ℃ is shown in figure 2, the comparison graph of the rate performance is shown in figure 3, and the 100-week cycle performance at 0.1 ℃ of the electrode prepared by the dry method is shown in figure 3Compared with the traditional wet preparation method, the method improves the rate charge-discharge performance by 69 percent.
Example 2
The embodiment provides a solvent-free dry preparation process of a high-specific energy lithium battery electrode, which comprises the following steps of:
under the condition of 80 ℃, mixing an artificial graphite negative electrode material, conductive carbon black, carbon nanofiber and styrene butadiene rubber according to the mass part ratio of 72.5: 15: 5: 7.5 simply mixing in a planetary ball mill at 3000rpm, adding 90 parts of polyethylene carbonate (PEC), keeping the same rotating speed, stirring for 2 hours, then rolling and molding the obtained homogeneous mixture under 800psi pressure, hot-pressing the rolled thin material on copper foil at 45 ℃ and 35psi pressure to obtain a negative plate, and finally gradually heating the negative plate to 230 ℃ under the vacuum condition to obtain the negative plate.
Example 3
The embodiment provides a solvent-free dry preparation process of a high-specific energy lithium battery electrode, which comprises the following steps of:
under the condition of 40 ℃, mixing artificial graphite, conductive carbon black and styrene butadiene rubber according to the mass part ratio of 80: 10: 10 simply mixing the materials in a planetary ball mill at 1000rpm, adding 70 parts of polyethylene carbonate (PEC), keeping the same rotating speed, stirring for 0.5 hour, then rolling and molding the obtained homogeneous mixture under 400psi pressure, hot-pressing the rolled thin material on copper foil at 45 ℃ and 35psi pressure to obtain a negative plate, and finally gradually heating the negative plate to 230 ℃ under the vacuum condition to obtain the negative plate.
Example 4
The embodiment provides a solvent-free dry preparation process of a high-specific energy lithium battery electrode, which comprises the following steps of:
under the condition of 60 ℃, the high-nickel ternary lithium ion battery anode material NCM (the ratio of nickel to cobalt to manganese is 8:1:1), conductive carbon black, carbon nanofiber and polytetrafluoroethylene are mixed according to the mass part ratio of 80: 10: 5: 5 simply mixing in a planetary ball mill at 2000rpm, adding 80 parts of polyethylene carbonate (PEC), keeping the same rotating speed, stirring for 1 hour, rolling and molding the obtained homogeneous mixture under 600psi pressure, hot-pressing the rolled thin material on an aluminum foil at 45 ℃ and 35psi pressure to obtain a positive plate, and finally gradually heating the positive plate to 230 ℃ under the vacuum condition to obtain the positive plate.
Example 5
The embodiment provides a solvent-free dry preparation process of a high-specific energy lithium battery electrode, which comprises the following steps of:
under the condition of 80 ℃, NCA (the ratio of nickel to cobalt to aluminum is 8: 1.5: 0.5), conductive carbon black, carbon nanofiber and polytetrafluoroethylene are mixed according to the mass part ratio of 72.5: 15: 5: 7.5 simply mixing in a planetary ball mill at 3000rpm, adding 90 parts of polyethylene carbonate (PEC), keeping the same rotating speed, stirring for 2 hours, then rolling and molding the obtained homogeneous mixture under 800psi pressure, hot-pressing the rolled thin material on an aluminum foil at 45 ℃ and 35psi pressure to obtain a positive plate, and finally gradually heating the positive plate to 230 ℃ under the vacuum condition to obtain the positive plate.
Example 6
The embodiment provides a solvent-free dry preparation process of a high-specific energy lithium battery electrode, which comprises the following steps of:
at the temperature of 40 ℃, mixing Lithium Cobaltate (LCO), conductive carbon black and polytetrafluoroethylene according to the mass part ratio of 80: 10: 10 simply mixing the materials in a planetary ball mill at 1000rpm, adding 70 parts of polyethylene carbonate (PEC), keeping the same rotating speed, stirring for 0.5 hour, then rolling and molding the obtained homogeneous mixture under 400psi pressure, hot-pressing the rolled thin material on copper-aluminum foil at 45 ℃ and 35psi pressure to obtain a positive plate, and finally gradually heating the positive plate to 230 ℃ under the vacuum condition to obtain the positive plate.
Example 7
The embodiment provides a solvent-free dry preparation process of a high-specific energy lithium battery electrode, which comprises the following steps of:
under the condition of 80 ℃, mixing artificial graphite, conductive carbon black, carbon nanofiber and styrene butadiene rubber according to the mass part ratio of 72.5: 15: 5: 7.5 simply mixing the materials in a planetary ball mill at 3000rpm, adding 90 Parts of Polypropylene Carbonate (PPC), keeping the same rotating speed, stirring for 2 hours, then rolling and molding the obtained homogeneous mixture under 800psi, hot-pressing the rolled thin material on copper foil at 45 ℃ and 35psi to obtain a negative plate, and finally gradually heating the negative plate to 230 ℃ under the vacuum condition to obtain the negative plate.
Example 8
The embodiment provides a solvent-free dry preparation process of a high-specific energy lithium battery electrode, which comprises the following steps of:
under the condition of 80 ℃, mixing artificial graphite, conductive carbon black, carbon nanofiber and styrene butadiene rubber according to the mass part ratio of 72.5: 15: 5: 7.5 simply mixing in a planetary ball mill at 3000rpm, adding 90 parts of polytrimethylene carbonate (PTMC) and stirring at the same rotating speed for 2 hours, then rolling and molding the obtained homogeneous mixture under 800psi, hot-pressing the rolled thin material on copper foil at 45 ℃ and 35psi to obtain a negative plate, and finally gradually heating the negative plate to 230 ℃ under the vacuum condition to obtain the negative plate.
According to the embodiment of the invention, the processing aid is introduced into the preparation method, so that high-efficiency dispersibility can be provided, and the obtained mixture becomes a paste-like substance through adding and mixing of the processing aid, so that the processing and forming are easy. The pole piece is finally heated to the decomposition temperature of the processing aid and can be completely decomposed to generate H2O、CO2And the depolymerization product can be further recovered and used for re-synthesizing the processing aid, so that the cost is reduced by recycling. The dry preparation technology has universality, can be applied to various active substances, can be used for preparing the anode and the cathode, and the obtained electrode can be used in lithium batteries including liquid lithium ion batteries, mixed solid-liquid metal lithium batteries, all-solid lithium ion batteries and all-solid metal lithium batteries. The lithium battery prepared by the method has better cycle stability, storage life, high-temperature performance, safety performance and rate capability.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A dry preparation method of a high specific energy lithium battery electrode is characterized by comprising the following steps:
under the heating condition, uniformly mixing the electrode material and the processing aid according to the mass of the processing aid which accounts for 10-80% of the total mass of the electrode material and the processing aid to form a paste mixture; wherein the electrode material comprises: electrode active material, conductive agent, adhesive; the processing aid comprises: one or more combinations of poly (ethylene carbonate) PEC, poly (propylene carbonate) Poly (propylene carbonate), poly (butylene carbonate), poly (cyclohexene polycarbonate), or poly (trimethylene carbonate) PTMC;
rolling and molding the paste mixture, and then hot-pressing the paste mixture on a current collector to obtain an electrode plate;
and carrying out heat treatment on the electrode slice under a vacuum condition to obtain the high-specific-energy lithium battery electrode.
2. The method according to claim 1, wherein the heating condition is 40 ℃ to 90 ℃;
the method for uniformly mixing specifically comprises the following steps: ball milling and mixing are carried out in a ball mill, or mechanical milling and mixing are carried out.
3. The production method according to claim 1, wherein the mass of the processing aid accounts for 25 to 50% of the total mass of the electrode material and the processing aid in terms of mass ratio.
4. The method of claim 1, wherein the pressure of the rolling is in the range of 400psi to 800 psi; the hot pressing temperature is 40-90 deg.C, and the pressure is 20-50 psi.
5. The production method according to claim 1, wherein the electrode active material includes a positive electrode active material or a negative electrode active material;
the positive electrode active material includes: one or more of nickel cobalt lithium manganate, lithium iron phosphate, lithium manganate, lithium cobaltate, lithium nickel cobalt aluminate and lithium-rich manganese-based materials;
the negative active material includes: one or more of nano silicon, silica, silicon carbon, graphite, soft carbon and hard carbon;
the conductive agent includes: one or a combination of more of conductive carbon black, carbon fiber, conductive graphite and carbon nano tube;
the adhesive includes: one or a combination of more of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, nitrile rubber, sodium carboxymethylcellulose, polyacrylic acids, polyacrylonitrile and sodium alginate.
6. The method of manufacturing of claim 1, wherein the current collector comprises an aluminum foil or a copper foil.
7. The preparation method according to claim 1, wherein the heat treatment of the electrode sheet under vacuum conditions specifically comprises:
heating the electrode sheet to at least the decomposition temperature of the processing aid under a vacuum condition so that the processing aid is decomposed; and continuously vacuumizing the environment of the heat treatment in the heat treatment process.
8. The method of claim 1, wherein the thickness of the obtained high specific energy lithium battery electrode is 1 μm to 200 μm.
9. A high specific energy lithium battery electrode prepared by the method of any one of claims 1 to 8.
10. A lithium battery comprising an electrode for a high specific energy lithium battery according to claim 9.
CN202010966968.5A 2020-09-15 2020-09-15 High specific energy lithium battery electrode, dry preparation method thereof and lithium battery Active CN111916678B (en)

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CN112542563A (en) * 2020-12-02 2021-03-23 湖北亿纬动力有限公司 Pole piece and preparation method thereof, lithium ion battery and preparation device
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CN113078296A (en) * 2021-03-26 2021-07-06 天津斯科兰德科技有限公司 Dry powder coating method of battery pole piece based on phosphate positive electrode material
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CN114864860A (en) * 2022-05-20 2022-08-05 三一技术装备有限公司 Feeding mechanism, feeding device and dry-method electrode film preparation device
CN114864860B (en) * 2022-05-20 2023-11-17 三一技术装备有限公司 Feeding mechanism, feeding device and dry electrode film preparation device

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