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.
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, a comparison graph of 100-week cycle performance at 0.1 ℃ is shown in fig. 2, a comparison graph of rate performance is shown in fig. 3, the 100-week cycle performance of the electrode prepared by the dry method at 0.1 ℃ is improved by 69% compared with that prepared by the traditional wet method, and the rate charge and discharge performance is also improved.
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.
The embodiment of the invention introduces the processing aid in the preparation method, can provide high-efficiency dispersibility, and enables the obtained mixture to be mixed through adding and mixing the processing aidThe composition is a paste-like substance, and is easy to process and mold. 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.