CN113422005B - Porous electrode, preparation method thereof and lithium battery - Google Patents
Porous electrode, preparation method thereof and lithium battery Download PDFInfo
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Abstract
The invention relates to a porous electrode, a preparation method thereof and a lithium battery. The preparation method comprises the steps of adding a pore-forming agent into electrode material slurry for preparing an electrode to prepare an electrode slice; soaking the electrode slice in a solution containing a boron-based anion receptor compound BBARS, and enabling the pore-forming agent to generate anion and cation dissociation through the combination of BBARS and anions of the pore-forming agent, so that the pore-forming agent is dissolved in the solution, and micropores are left at the original position; taking the electrode out of the solution, and drying in vacuum to obtain a porous electrode; or adding pore-forming agent into electrode material slurry for preparing the electrode to prepare an electrode slice; assembling the electrode plate into a battery, injecting a solution containing a boron-based anion receptor compound BBARS into the battery, and combining BBARS and anions of a pore-forming agent to enable the pore-forming agent to be dissociated by anions and cations so as to dissolve the pore-forming agent in the solution and leave micropores at the original position; and (4) drying the battery in vacuum to obtain the porous electrode.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a porous electrode, a preparation method thereof and a lithium battery.
Background
Lithium Ion Batteries (LIBs), which have high energy density and rechargeable characteristics, have become the most attractive power source in current electric vehicles. The charging speed is slow, the endurance mileage is short, and the charging method is one of the main factors restricting the development of the electric automobile.
The continuous improvement of the energy density of the power battery enables the continuous improvement of the endurance mileage of the electric automobile, the endurance mileage of the current mainstream automobile generally exceeds 400km, the high-end automobile reaches 500km, even part of the automobile reaches over 600km, and the mileage anxiety of the electric automobile can be basically solved. However, the rate capability and charging facilities of the battery are not perfect enough at present, so the demand of the electric automobile on the rate is generally high.
At present, the multiplying power problem of the battery is generally solved by the following methods: 1) the thickness of the pole piece is reduced, the transmission path of lithium ions is reduced, and the multiplying power performance is improved; 2) a rate material system is used, for example, expanded graphite, lithium titanate and amorphous carbon are used for a negative electrode, a polycrystalline material is used for a positive electrode, the particle size of the material is reduced, and the like; 3) battery design optimization, such as width, location, number of tabs, etc.; 4) optimizing electrolyte, namely, reducing the interface impedance between the electrolyte and a material by optimizing the viscosity and the conductivity of the electrolyte, and the like; 5) and (4) battery replacement technology.
However, the above methods have disadvantages. For example: the reduction of the thickness of the pole piece can lead to the reduction of energy density and the shortening of endurance mileage; the energy density of the battery adopting the lithium titanate cathode is low; the expanded graphite has high cost and is not easy to scale; the problem of non-uniformity of various vehicle types exists in battery replacement, and the like.
Therefore, a solution that can improve the rate performance of the battery, meet other performance requirements, and is easy to scale is urgently needed to be proposed in the industry.
Disclosure of Invention
The embodiment of the invention provides a porous electrode, a preparation method thereof and a lithium battery. The internal resistance of the battery can be reduced, the migration rate of ions can be improved, the rate capability of the battery can be improved while the energy density of the battery is not influenced, and the preparation method is simple, convenient and feasible and is easy for large-scale production.
In a first aspect, an embodiment of the present invention provides a method for preparing a porous electrode, including:
adding a pore-forming agent into electrode material slurry for preparing an electrode to prepare an electrode slice;
soaking the electrode slice in a solution containing a boron-based anion receptor compound BBARS, and enabling the pore-forming agent to generate anion and cation dissociation through the combination of BBARS and anions of the pore-forming agent, so that the pore-forming agent is dissolved in the solution, and micropores are left at the original position; and taking the electrode out of the solution, and drying in vacuum to obtain the porous electrode.
Preferably, the BBARS specifically comprises: any one of perfluoro-substituted Triphenylboron (TPFPB), pentafluorophenylboronate oxalate (PFPBO), 4,5,6, 7-tetrafluoro-2- (2,3,4,5, 6-pentafluorophenyl) -1,3, 2-benzodioxoborane (PFPTFBB), or tris hexafluoroisopropyl borate (THFPB);
the concentration of the solution is 0.01mol/L-1 mol/L.
Preferably, the pore-forming agent comprises: one or more of lithium chloride, lithium carbonate, lithium bromide, lithium fluoride, lithium iodide, lithium carbide, lithium oxide, lithium peroxide and lithium hydride are mixed;
the particle size of the pore-forming agent is 0.1nm-100 mu m;
the pore-forming agent accounts for 0.01-20 wt% of the electrode.
Preferably, the vacuum degree of the vacuum drying is 1-1000Pa, the temperature is 30-280 ℃, and the time is 1-48 hours.
In a second aspect, an embodiment of the present invention provides a method for preparing a porous electrode, including:
adding a pore-forming agent into electrode material slurry for preparing an electrode to prepare an electrode slice;
assembling the electrode plate into a battery, injecting a solution containing a boron-based anion receptor compound BBARS into the battery, and enabling the pore-forming agent to generate anion and cation dissociation through the combination of the BBARS and anions of the pore-forming agent so as to dissolve the pore-forming agent in the solution and leave micropores at the original position;
and carrying out vacuum drying on the battery to obtain the porous electrode.
Preferably, the BBARS specifically comprises: any one of perfluoro-substituted Triphenylboron (TPFPB), pentafluorophenylboronate oxalate (PFPBO), 4,5,6, 7-tetrafluoro-2- (2,3,4,5, 6-pentafluorophenyl) -1,3, 2-benzodioxoborane (PFPTFBB), or tris hexafluoroisopropyl borate (THFPB);
the concentration of the solution is 0.01mol/L-1 mol/L.
Preferably, the pore-forming agent comprises: one or more of lithium chloride, lithium carbonate, lithium bromide, lithium fluoride, lithium iodide, lithium carbide, lithium oxide, lithium peroxide and lithium hydride are mixed;
the particle size of the pore-forming agent is 0.1nm-100 mu m;
the pore-forming agent accounts for 0.01-20 wt% of the electrode.
Preferably, the vacuum degree of the vacuum drying is 1-1000Pa, the temperature is 30-280 ℃, and the time is 1-48 hours.
In a third aspect, the embodiments of the present invention provide a porous electrode prepared by the preparation method of the first or second aspect.
In a fourth aspect, embodiments of the present invention provide a lithium battery, including the porous electrode of the third aspect.
According to the preparation method of the porous electrode, the pore-forming agent is added in the preparation process of the electrode, and then the boron-based anion receptor solvent is combined with anions of the pore-forming agent, so that the pore-forming agent is subjected to anion and cation dissociation, the pore-forming agent is dissolved in the solution, and micropores are left at the original position, so that the porous electrode is formed, the internal resistance of the battery is effectively reduced, the migration rate of ions is improved, the rate capability of the battery is improved, and the energy density of the battery is not influenced. The preparation method is simple, convenient and feasible, and is easy for scale production.
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 method for preparing a porous electrode according to an embodiment of the present invention;
fig. 2 is a flow chart of another method for preparing a porous electrode according to an embodiment 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 invention provides a preparation method of a porous electrode, which can be realized in two specific modes as follows. FIG. 1 is a flow chart of a method for preparing a porous electrode according to an embodiment of the present invention; FIG. 2 is a flow chart of another method for preparing a porous electrode according to an embodiment of the present invention. The following description will be made with reference to these two flowcharts, respectively.
As shown in fig. 1, the preparation method of a porous electrode of the present invention mainly comprises the steps of:
and step 130, taking the electrode out of the solution, and drying in vacuum to obtain the porous electrode.
As shown in fig. 2, another method for preparing a porous electrode according to the present invention comprises the following main steps:
and step 230, carrying out vacuum drying on the battery to obtain the porous electrode.
In any of the above methods, the essence is that the pore-forming agent is added into the electrode material slurry for preparing the electrode, so that the pore-forming agent is dispersed in the electrode, and then the boron-based anion receptor solvent is combined with anions of the pore-forming agent, so that the pore-forming agent is dissociated by anions and cations, the pore-forming agent is dissolved in the solution, and micropores are left at the original position, thereby forming the porous structure of the electrode. Preferably, the pore former forms pores with a size of 0.1nm to 100 μm.
In the above two methods, the solution is specifically organic solution of BBARS.
Wherein the boron-based anion receptor compound (BBARS) has the general formula:
wherein, R1, R2 and R3 are selected from one of alkyl, aryl or heteroaryl.
The method specifically comprises the following steps: perfluoro-substituted Triphenylboron (TPFPB), pentafluorophenylboronate oxalate (PFPBO), 4,5,6, 7-tetrafluoro-2- (2,3,4,5, 6-pentafluorophenyl) -1,3, 2-benzodioxoborane (PFPTFBB), or tris hexafluoroisopropyl borate (THFPB).
The organic solvent includes: ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, 1, 4-butyrolactone, methyl formate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate, and mixtures of one or more of their halogenated derivatives.
The concentration of the solution is 0.01mol/L-1 mol/L.
The pore-forming agent comprises: one or more of lithium chloride, lithium carbonate, lithium bromide, lithium fluoride, lithium iodide, lithium carbide, lithium oxide, lithium peroxide and lithium hydride are mixed; the particle size of the pore-forming agent is 0.1nm-100 mu m; the pore-forming agent accounts for 0.01-20 wt% of the electrode.
The vacuum degree of vacuum drying is 1-1000Pa, the temperature is 30-280 ℃, and the time is 1-48 hours.
The porous electrode formed by the method can effectively reduce the internal resistance of the battery, improve the migration rate of ions, improve the rate capability of the battery and does not influence the energy density of the battery. The preparation method is simple, convenient and feasible, and is easy for scale production. The method can be used for preparing the anode and the cathode and is applied to the lithium ion battery.
In order to better understand the technical solutions provided by the present invention, the following description will respectively illustrate specific processes for preparing lithium battery electrodes by using the methods provided by the above embodiments of the present invention with a plurality of specific examples.
Example 1
In this embodiment, the boron-based anion receptor compound is pentafluorophenylboronate (PFPBO) having the following structural formula:
selecting LiNi0.5Co0.2Mn0.3O2As a positive electrode material, LiNi is used as a positive electrode material0.5Co0.2Mn0.3O2Mixing with CNTs, LiF and polyvinylidene fluoride (PVDF) according to a mass ratio of 97.2: 1.3: 0.2: 1.3, coating the mixture on an aluminum foil current collector, drying the aluminum foil current collector by an oven, and rolling the aluminum foil current collector by a roller press to obtain a required positive plate;
selecting artificial graphite as a negative electrode material, and mixing graphite, sodium carboxymethyl cellulose (CMC), CNTs, LiF and Styrene Butadiene Rubber (SBR) serving as a binder according to a mass ratio of 95.7: 1.4: 0.8: 0.1: 2.0, coating the mixture on a copper foil current collector, drying the copper foil current collector by an oven, and rolling the copper foil current collector by a roller press to obtain a required negative plate;
selecting a Polyethylene (PE) film coated with ceramic as a diaphragm (12+4) um, and manufacturing a pole piece into a small soft package battery of 2Ah by a lamination method;
in a glove box with water content less than 0.1ppm and oxygen content less than 0.1ppm and filled with argon, dimethyl carbonate (DMC) and Ethylene Carbonate (EC) are mixed according to a mass ratio of 1: 1, then adding the pentafluobenzene boron oxalate (PFPBO) into the mixed solution of DMC and EC according to 0.1mol/L to prepare the solution containing the boron-based anion receptor compound.
And (2) injecting the solution containing the boron-based anion receptor compound into a small soft package battery with the volume of 2g/Ah, standing for 24 hours at 45 ℃, and removing the solution by adopting a vacuumizing and heating method to obtain the rate battery containing the porous electrode, wherein the vacuum degree is 150Pa, the heating operation temperature for drying is 80 ℃, and the time is 36 hours.
Example 2
The boron-based anion acceptor compound in this example is tris (pentafluorophenyl) borane (TPFPB), having the following structural formula:
selecting LiNi0.5Co0.2Mn0.3O2As a positive electrode material, LiNi is used as a positive electrode material0.5Co0.2Mn0.3O2With CNTs, Li2O2PVDF as 97.1: 1.3: 0.3: 1.3, coating the mixture on an aluminum foil current collector, drying the aluminum foil current collector by an oven, and rolling the aluminum foil current collector by a roller press to obtain a required positive plate;
selecting nano silicon as a negative electrode material, and mixing the nano silicon, CMC, CNTs, LiF and SBR according to a proportion of 94.3: 1.5: 2.0: 0.2: 2.0, coating the mixture on a copper foil current collector, drying the copper foil current collector by an oven, and rolling the copper foil current collector by a roller press to obtain a required negative plate;
in a glove box with moisture less than 0.1ppm and oxygen less than 0.1ppm and filled with argon, DEC and EC are mixed according to the mass ratio of 1: 1, and then adding tris (pentafluorophenyl) borane (TPFPB) into the mixed solution of DEC and EC according to 0.1mol/L to prepare a solution containing the boron-based anion acceptor compound.
And soaking the prepared positive plate and the prepared negative plate in the solution containing the boron-based anion receptor compound for 24 hours, and then drying the soaked plates in vacuum to obtain the porous electrode, wherein the vacuum degree is 200Pa, the heating operation temperature for drying is 100 ℃, and the time is 6 hours.
Selecting a Polyethylene (PE) film coated with ceramic as a diaphragm (12+4) um, and manufacturing the pole piece into a 2Ah rate battery containing the porous electrode by a pole piece through a lamination method.
Example 3
The boron-based anion receptor compound in this example is 4,5,6, 7-tetrafluoro-2- (2,3,4,5, 6-pentafluorophenyl) -1,3, 2-benzodioxoborane (PFPTFBB), having the following structural formula:
selecting LiNi0.5Co0.2Mn0.3O2As a positive electrode material, LiNi is used as a positive electrode material0.5Co0.2Mn0.3O2With CNT, Li2O, PVDF was measured according to 97.2: 1.3: 0.2: 1.3, coating the mixture on an aluminum foil current collector, drying the aluminum foil current collector by an oven, and rolling the aluminum foil current collector by a roller press to obtain a required positive plate;
selecting artificial graphite as a negative electrode material, and mixing graphite, CMC, CNTs, LiF and SBR according to the weight ratio of 95.6: 1.4: 0.8: 0.2: 2.0, coating the mixture on a copper foil current collector, drying the copper foil current collector by an oven, and rolling the copper foil current collector by a roller press to obtain a required negative plate;
selecting a Polyethylene (PE) film coated with ceramic as a diaphragm (12+4) um, and manufacturing a pole piece into a small soft package battery of 2Ah by a lamination method;
in a glove box which is filled with argon and has the moisture content of less than 0.1ppm and the oxygen content of less than 0.1ppm, DMC and EC are mixed according to the mass ratio of 1: 1, and then adding 4,5,6, 7-tetrafluoro-2- (2,3,4,5, 6-pentafluorophenyl) -1,3, 2-benzodioxoborane (PFPTFBB) into a mixed solution of DMC and EC by 0.2mol/L to prepare a solution containing the boron-based anion receptor compound.
And (2) injecting the solution containing the boron-based anion receptor compound into a small soft package battery with the volume of 2g/Ah, standing for 24 hours at 45 ℃, and removing the solution by adopting a vacuumizing and heating method to obtain the rate battery containing the porous electrode, wherein the vacuum degree is 150Pa, the heating operation temperature for drying is 80 ℃, and the time is 24 hours.
Example 4
In this example, the boron-based anion acceptor is selected from tris hexafluoroisopropyl borate (THFPB), and has the following structural formula:
selecting LiNi0.5Co0.2Mn0.3O2As a positive electrode material, LiNi is used as a positive electrode material0.5Co0.2Mn0.3O2With CNTs, Li2O2PVDF as 97.2: 1.3: 0.2: 1.3, coating the mixture on an aluminum foil current collector, drying the aluminum foil current collector by an oven, and rolling the aluminum foil current collector by a roller press to obtain a required positive plate;
selecting artificial graphite as a negative electrode material, and mixing graphite, CMC, CNTs, LiF and SBR according to the weight ratio of 95.6: 1.4: 0.8: 0.2: 2.0, coating the mixture on a copper foil current collector, drying the copper foil current collector by an oven, and rolling the copper foil current collector by a roller press to obtain a required negative plate;
selecting a Polyethylene (PE) film coated with ceramic as a diaphragm (12+4) um, and manufacturing a pole piece into a small soft package battery of 2Ah by a lamination method;
in a glove box which is filled with argon and has the moisture content of less than 0.1ppm and the oxygen content of less than 0.1ppm, DMC and EC are mixed according to the mass ratio of 1: 1, and then adding 0.1mol/L of tris (hexafluoroisopropyl) borate (THFPB) into the mixed solution of DMC and EC to prepare a solution containing the boron-based anion receptor compound.
And (2) injecting the solution containing the boron-based anion receptor compound into a small soft package battery with the volume of 2g/Ah, standing for 24 hours at 45 ℃, and removing the solution by adopting a vacuumizing and heating method to obtain the rate battery containing the porous electrode, wherein the vacuum degree is 300Pa, the heating operation temperature for drying is 90 ℃, and the time is 24 hours.
For convenience of explanation of the effects of the present invention, the following two comparative examples are compared.
Comparative example 1
Selecting LiNi0.5Co0.2Mn0.3O2As a positive electrode material, LiNi is used as a positive electrode material0.5Co0.2Mn0.3O2With CNTs, PVDF according to 97.4: 1.3: 1.3, coating the mixture on an aluminum foil current collector, drying the aluminum foil current collector by an oven, and rolling the aluminum foil current collector by a roller press to obtain a required positive plate;
selecting artificial graphite as a negative electrode material, and mixing graphite, CMC, CNTs and SBR according to a ratio of 95.8: 1.4: 0.8: 2.0, coating the mixture on a copper foil current collector, drying the copper foil current collector by an oven, and rolling the copper foil current collector by a roller press to obtain a required negative plate;
selecting a PE film coated with ceramic as an isolation film (12+4) um, and manufacturing the pole piece into a small soft package battery of 2Ah by a lamination method.
Comparative example 2
Selecting LiNi0.5Co0.2Mn0.3O2As a positive electrode material, LiNi is used as a positive electrode material0.5Co0.2Mn0.3O2CNT, PVDF as per 97.4: 1.3: 1.3, coating the mixture on an aluminum foil current collector, drying the aluminum foil current collector by an oven, and rolling by a roller press to obtain a required positive plate;
selecting nano silicon as a negative electrode material, and mixing the nano silicon, CMC, CNT and SBR according to a mixing ratio of 94.5: 1.5: 2.0: 2.0, coating the mixture on a copper foil current collector, drying the copper foil current collector by an oven, and rolling the copper foil current collector on a roller press to obtain the required negative plate;
selecting a PE film coated with ceramic as an isolation film (12+4) um, and manufacturing the pole piece into a small soft package battery of 2Ah by a lamination method.
The batteries of the above respective examples and comparative examples were injected with an electrolyte.
In a glove box which is filled with argon and has the moisture content of less than 0.1ppm and the oxygen content of less than 0.1ppm, Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) are mixed according to the mass ratio of 3: 2: 5, and adding lithium hexafluorophosphate (LiPF)6) And adding auxiliary additives, namely fluoroethylene carbonate (FEC), LiFSI and ethylene sulfate (DTD) into the lithium salt with the concentration of 1mol/L and the mass fractions of 1%, 1% and 1% respectively to prepare the electrolyte.
Injecting the electrolyte into a small soft package battery of 2Ah according to the amount of 2g/Ah, and testing the cycle performance and the rate performance through formation, capacity grading and test, wherein the charge-discharge voltage window of the lithium battery is 2.75-4.2V; the cycle test of the battery is at room temperature of 25 ℃, the cyclic charge-discharge current is 1C, and the multiplying power charge-discharge is 0.5C-1C-2C-5C-10C, so that the following test results are obtained.
TABLE 1
The comparison shows that when the porous electrode prepared by the embodiment of the invention is applied to the lithium ion battery, the capacity retention rate and the discharge capacity of the porous electrode are superior to those of the battery with the electrode prepared by the traditional method, the direct current impedance is greatly reduced, and the internal resistance of the battery is lower.
Therefore, the porous electrode prepared by the method is beneficial to improving the migration rate of ions and the rate performance of the battery, does not influence the energy density of the battery, and has good application prospect.
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 method of making a porous electrode, comprising:
adding a pore-forming agent into electrode material slurry for preparing an electrode to prepare an electrode slice;
soaking the electrode slice in a solution containing a boron-based anion receptor compound BBARS, enabling the pore-forming agent to generate anion and cation dissociation through the combination of BBARS and anions of the pore-forming agent, enabling the pore-forming agent to be dissolved in the solution, leaving micropores at the original position, taking the electrode out of the solution, and performing vacuum drying to obtain the porous electrode;
wherein the BBARS specifically comprises: perfluoro-substituted Triphenylboron (TPFPB), pentafluorophenylboronate oxalate (PFPBO), 4,5,6, 7-tetrafluoro-2- (2,3,4,5, 6-pentafluorophenyl) -1,3, 2-benzodioxoborane (PFPTFBB), or tris hexafluoroisopropyl borate (THFPB).
2. The method according to claim 1, wherein the concentration of the solution is 0.01mol/L to 1 mol/L.
3. The method of claim 1, wherein the pore-forming agent comprises: one or more of lithium chloride, lithium carbonate, lithium bromide, lithium fluoride, lithium iodide, lithium carbide, lithium oxide, lithium peroxide and lithium hydride are mixed;
the particle size of the pore-forming agent is 0.1nm-100 mu m;
the pore-forming agent accounts for 0.01-20 wt% of the electrode
The size of the micropores is 0.1nm-100 μm.
4. The method according to claim 1, wherein the vacuum drying is performed at a vacuum degree of 1 to 1000Pa, a temperature of 30 to 280 ℃ and a time of 1 to 48 hours.
5. A method of making a porous electrode, comprising:
adding a pore-forming agent into electrode material slurry for preparing an electrode to prepare an electrode slice;
assembling the electrode plate into a battery, injecting a solution containing a boron-based anion receptor compound BBARS into the battery, and enabling the pore-forming agent to generate anion and cation dissociation through the combination of the BBARS and anions of the pore-forming agent so as to dissolve the pore-forming agent in the solution and leave micropores at the original position;
vacuum drying the battery to obtain the porous electrode;
wherein the BBARS specifically comprises: perfluoro-substituted Triphenylboron (TPFPB), pentafluorophenylboronate oxalate (PFPBO), 4,5,6, 7-tetrafluoro-2- (2,3,4,5, 6-pentafluorophenyl) -1,3, 2-benzodioxoborane (PFPTFBB), or tris hexafluoroisopropyl borate (THFPB).
6. The method according to claim 5, wherein the concentration of the solution is 0.01mol/L to 1 mol/L.
7. The method of claim 5, wherein the pore-forming agent comprises: one or more of lithium chloride, lithium carbonate, lithium bromide, lithium fluoride, lithium iodide, lithium carbide, lithium oxide, lithium peroxide and lithium hydride are mixed;
the particle size of the pore-forming agent is 0.1nm-100 mu m;
the pore-forming agent accounts for 0.01-20 wt% of the electrode;
the size of the micropores is 0.1nm-100 μm.
8. The method according to claim 5, wherein the vacuum drying is performed at a vacuum degree of 1 to 1000Pa, a temperature of 30 to 280 ℃ and a time of 1 to 48 hours.
9. A porous electrode prepared by the method of any one of claims 1 to 4 or 5 to 8.
10. A lithium battery comprising the porous electrode of claim 9.
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