CN113620278A - Method for controllably preparing nano porous graphene flexible electrode based on ion adsorption - Google Patents
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Abstract
The invention discloses a controllable preparation method of a nano porous graphene flexible electrode based on ion adsorption. Ultrasonically dispersing a graphene oxide aqueous solution, placing the graphene oxide aqueous solution in an ice water bath for magnetic stirring, and simultaneously dropwise adding FeCl3The solution is centrifuged to obtain GO/Fe3+A precursor; freeze drying, calcining under inert gas, washing with dilute HCl, and washing with deionized water to neutrality to obtain nano porous graphene; dispersing in ethanol/water, performing ultrasonic treatment to uniformly disperse, performing suction filtration to obtain a filter cake, drying the filter cake, and rolling to obtain the flexible nano porous grapheneAnd an electrode sheet as a negative electrode for assembling the potassium ion battery. The method is simple and suitable for large-scale preparation of the nano-porous graphene, and the prepared graphene has uniform and controllable pore diameter, excellent charge-discharge specific capacity and good cycling stability.
Description
Technical Field
The invention relates to a preparation method of a flexible electrode, in particular to a controllable preparation method of a nano porous graphene flexible electrode.
Background
Lithium Ion Batteries (LIBs) are highly efficient and energy-denseLarge size and long cycle life, and has been successfully applied to commercial rechargeable batteries. However, LIBs face serious cost issues in future large-scale energy storage applications due to limited and unevenly distributed lithium resources on earth. Therefore, Sodium Ion Batteries (SIBs) and Potassium Ion Batteries (PIBs) have attracted considerable attention due to their low cost and abundance of resources. With Na+K/Na (-2.71V vs standard hydrogen electrode)+The redox potential of/K is lower and is closer to Li+Li (-2.93V and-3.04V vs standard hydrogen electrode). Thus, PIBs have higher open circuit potentials and energy densities than SIBs. In addition, the weaker lewis acidity of K + results in smaller stokes radii of solvated ions in the liquid electrolyte with faster kinetic characteristics. Thus, PIBs are potential candidates for large-scale energy storage devices.
However, suitable electrode materials are sought to accommodate the larger K+(radius:
) It remains a significant challenge. Among the various materials reported so far, graphene has attracted particular attention in the application of PIBs due to its inherent characteristics, such as high energy density, good conductive plane conductivity, excellent tensile modulus and mechanical durability, and the like. However, practical applications of graphene-based materials suggest that pristine graphene is prone to stacking due to strong van der waals forces and pi-pi interactions between its high specific surface area graphite planes. Stacking will result in a substantial reduction of the active surface of the graphene and a hindrance of ion transport, greatly reducing the charge/discharge capacity of graphene-based electrodes, especially at high charge/discharge rates. Introducing the pores into the basal plane of the graphene will reduce the diffusion distance of ion migration in the charging/discharging process, and can effectively improve the problems of electrode dynamics and mass transfer. In addition, the introduction of the pores can generate more defects on the basal plane of the graphene, so that the graphene can provide more active sites, and the electrochemical performance is greatly improved. Various methods have been developed, such as photocatalytic oxidation, chemical etching (e.g., KOH, H)2O2、HNO3And NaI), a metal or metal oxideEtching (e.g., Ni, Fe, Cu, and Co) and air oxidation to prepare nanoporous graphene. Among other things, metal oxide etching methods do not involve corrosive/hazardous chemicals (e.g., H)2O2And KOH) and thus is widely used to prepare nanoporous graphene. However, the reported metal oxide etching process is very prone to form a macroporous structure, which impairs the conductivity, electrochemistry and structural stability of graphene, thereby reducing power density and coulombic efficiency and shortening cycle life. Therefore, the nano-porous graphene with simple development process and controllable pore diameter has important significance for large-scale application of PIBs.
Disclosure of Invention
In order to solve the problems in the background art, an object of the present invention is to provide a low-cost, controllable and efficient strategy for preparing porous graphene with nano-pores, so as to reduce the diffusion distance of ion migration during the charging/discharging process of a rechargeable battery, and improve the electrode kinetics and mass transport problems. Meanwhile, the porous graphene is prepared into a flexible electrode which is directly used for a rechargeable battery to improve the conductivity of the electrode.
In order to solve the above technical problem, as shown in fig. 8, the present invention adopts the following technical solutions:
s1, ultrasonically dispersing a Graphene Oxide (GO) aqueous solution, placing the solution in an ice water bath for magnetic stirring, and simultaneously dropwise adding FeCl according to a certain molar ratio3Solution is added dropwise, the obtained solution is subjected to centrifugal separation, the obtained precipitate is washed by deionized water and is subjected to vacuum freeze drying, and GO/Fe is obtained3+A precursor;
s2, freeze-drying the GO/Fe3+Calcining the precursor under the protection of inert gas, washing with a dilute HCl solution, washing with deionized water to neutrality, performing centrifugal separation, and performing vacuum freeze drying to obtain nano porous graphene;
and S3, dispersing the nano porous graphene in a mixed solution of ethanol and water, performing suction filtration after ultrasonic dispersion to obtain a filter cake, drying the filter cake, and rolling to obtain the flexible porous graphene electrode plate.
The S1 specifically includes: adding 0.5mg/mL of oxidized stoneUltrasonically dispersing graphene aqueous solution, placing the graphene aqueous solution in an ice water bath for magnetic stirring, and simultaneously, adding graphene oxide and FeCl3FeCl is added dropwise at a molar ratio of 1: 0.1-23Solutions, FeCl3The concentration of the solution is 0.05-0.1 mol/L, the solution obtained after dropwise adding is subjected to centrifugal separation, the precipitate obtained by centrifugation is washed with deionized water, vacuum freeze drying is carried out, the freeze drying time is 24-72 hours, and GO/Fe is obtained3+And (3) precursor.
The S2 specifically includes: freeze drying GO/Fe3+Calcining the precursor under the protection of an inert gas atmosphere, keeping the temperature rise rate at 5-20 ℃/min until the calcining temperature reaches 500-800 ℃, then keeping the calcining temperature for 0-120 min, finally washing the calcined product by using 1-3 mol/L diluted HCl solution, repeatedly washing the calcined product by using deionized water until the product is neutral, performing centrifugal separation, and performing vacuum freeze drying on the obtained precipitate to obtain the nano porous graphene.
The method regulates and controls the pore size of the flexible porous graphene electrode plate by controlling the calcination temperature and the calcination time, and the pore size distribution range is 0.5-20 nm.
The controllable preparation of the nano porous graphene flexible electrode based on ion adsorption is directly used as a negative pole piece of a rechargeable battery.
The product of the invention can be used as a negative electrode material for rechargeable batteries.
The method is simple, is suitable for large-scale preparation of the nano-porous graphene, and the prepared graphene has uniform and controllable pore diameter and wide use value and popularization significance. Meanwhile, when the flexible electrode is directly applied to a rechargeable battery, the flexible electrode has excellent charge-discharge specific capacity and good cycling stability, and when the flexible electrode is applied to a negative electrode material of PIBs, the charge-discharge specific capacity and cycling stability of the PIBs can be effectively improved.
The invention has the beneficial effects that:
according to the method, metal oxide nanoparticles generated in situ based on single ion adsorption are used as a mild etchant to prepare the porous graphene with the nano holes, and the prepared nano porous graphene is subjected to suction filtration and rolling to obtain the flexible nano porous graphene sheet.
The prepared nano-pores on the flexible nano-porous graphene can form an interpenetrating network, so that the diffusion and permeation of electrolyte can be effectively promoted, the transmission path of ions and electrons can be shortened, and the electrode dynamics and the mass transmission of the rechargeable battery can be greatly improved. Meanwhile, the edges of the introduced holes can provide more ion insertion/emigration sites, and the charge-discharge specific capacity of the rechargeable battery is effectively improved.
When the nano porous graphene flexible electrode is used as a negative electrode material and applied to PIBs (particle image sensing devices), the nano porous graphene flexible electrode shows excellent charge-discharge specific capacity, good rate performance and lasting cycle stability.
Drawings
FIG. 1 is GO/Fe prepared in example3+Scanning electron micrographs of the precursor (a) electron energy spectrograms (b-d are C, O, Fe spectra, respectively);
FIG. 2 is GO/Fe prepared in example3+Spherical aberration electron microscope picture of the precursor;
FIG. 3 is a transmission electron microscope image (a-d) of the nanoporous graphene prepared in examples 1, 2, 3, 4;
fig. 4 shows the flexible nano-porous graphene electrode prepared in example 2 (a) and after bending (b);
fig. 5 shows short cycle performance of the nano-porous graphene flexible electrodes prepared in examples 1, 2, 3 and 4 applied to PIBs;
fig. 6 is a rate capability of the nano-porous graphene flexible electrodes prepared in examples 1, 2, 3, and 4 applied to PIBs;
fig. 7 shows the long-cycle performance of the nano-porous graphene flexible electrode prepared in example 1 applied to PIBs.
FIG. 8 is a schematic view of the process of the method of the present invention.
Detailed Description
Specific embodiments of the present invention will be further described with reference to the accompanying drawings.
The examples of the invention are as follows:
example 1
(1)GO/Fe3+Preparing a precursor: graphene oxide (0.5 mg/mL)GO) aqueous solution for 60min to form a uniform and stable solution. Placing in ice water bath, magnetically stirring for 30min, and adding FeCl dropwise at a molar ratio of 1:13Solutions, FeCl3The concentration of the solution is 0.05mol/L, the obtained solution is centrifugally separated after the dropwise addition is finished, the rotating speed of a centrifugal machine is 10000r/min, and the obtained precipitate is washed by deionized water to obtain GO/Fe3+The precursor is subjected to vacuum freeze-drying at-60 ℃, the freeze-drying time is 48h, and Fe can be seen from an electronic energy spectrogram and a spherical aberration electron microscope image3+The GO is uniformly distributed on the surface of the GO and shows a monodisperse state;
(2) preparing nano porous graphene: freeze drying GO/Fe3+And placing the precursor in a tubular furnace, calcining under the protection of inert gas atmosphere, wherein the heating rate is 10 ℃/min, the calcining time is 0min, the calcining temperature is 600 ℃, finally, washing the calcined product by using 1mol/L HCl, repeatedly washing the product to be neutral by using deionized water, centrifugally separating, and carrying out vacuum freeze drying on the obtained precipitate at the temperature of-60 ℃ to obtain the nano porous graphene, wherein the aperture of the nano porous graphene is about 0.5-1 nm.
(3) Preparing a nano porous graphene flexible electrode: and (3) redispersing the nano-porous graphene in ethanol/water, performing ultrasonic treatment to fully disperse the nano-porous graphene, and performing suction filtration to obtain a nano-porous graphene filter cake. And drying the filter cake, and then rolling, wherein the temperature of an oven is 40 ℃, and the rolling thickness is 0.2mm, so as to obtain the flexible nano porous graphene electrode plate.
Dissolving a flexible nano-porous graphene electrode plate serving as a negative electrode, metal potassium serving as a positive electrode and Whatman GF/D glass fiber serving as a diaphragm in 0.8M KPF6Ethylene carbonate/diethyl carbonate (1: 1 by volume) in solution as electrolyte in a glove box (H)2O<0.1ppm and O2<0.1ppm) of assembled PIBs having a specific discharge capacity of about 390mAh/g at a current density of 0.1A/g. Under the high current density of 1A/g, after 1500 cycles, the discharge specific capacity of the material is still kept at about 250mAh/g, and the material has excellent rate capability and cycling stability.
Example 2
(1)GO/Fe3+Preparing a precursor: and (3) carrying out ultrasonic treatment on the Graphene Oxide (GO) aqueous solution with the concentration of 0.5mg/mL for 60min to form a uniform and stable solution. Placing in ice water bath, magnetically stirring for 30min, and adding FeCl dropwise at a molar ratio of 1:13Solutions, FeCl3The concentration of the solution is 0.05mol/L, the obtained solution is centrifugally separated after the dropwise addition is finished, the rotating speed of a centrifugal machine is 10000r/min, and the obtained precipitate is washed by deionized water to obtain GO/Fe3+Performing vacuum freeze drying on the precursor at-60 ℃, wherein the freeze drying time is 48 h;
(2) preparing nano porous graphene: freeze drying GO/Fe3+And placing the precursor in a tubular furnace, calcining under the protection of inert gas atmosphere, wherein the heating rate is 10 ℃/min, the calcining time is 0min, the calcining temperature is 700 ℃, finally washing the calcined product by using 1mol/L HCl, repeatedly washing the product to be neutral by using deionized water, centrifugally separating, and carrying out vacuum freeze drying on the obtained precipitate at the temperature of-60 ℃ to obtain the nano porous graphene, wherein the aperture of the nano porous graphene is about 1-2 nm.
(3) Preparing a nano porous graphene flexible electrode: and (3) redispersing the nano-porous graphene in ethanol/water, performing ultrasonic treatment to fully disperse the nano-porous graphene, and performing suction filtration to obtain a nano-porous graphene filter cake. And drying the filter cake, and then rolling, wherein the temperature of an oven is 40 ℃, and the rolling thickness is 0.2mm, so as to obtain the flexible nano porous graphene electrode plate.
Dissolving a flexible nano-porous graphene electrode plate serving as a negative electrode, metal potassium serving as a positive electrode and Whatman GF/D glass fiber serving as a diaphragm in 0.8M KPF6Ethylene carbonate/diethyl carbonate (1: 1 by volume) in solution as electrolyte in a glove box (H)2O<0.1ppm and O2<0.1ppm) of assembled PIBs, having a specific discharge capacity of about 350mAh/g at a current density of 0.1A/g and a specific discharge capacity of about 190mAh/g at a current density of 2A/g.
Example 3
(1)GO/Fe3+Preparing a precursor: and (3) carrying out ultrasonic treatment on the Graphene Oxide (GO) aqueous solution with the concentration of 0.5mg/mL for 60min to form a uniform and stable solution. It is placed inMagnetically stirring in ice-water bath for 30min, and adding FeCl dropwise at a molar ratio of 1:13Solutions, FeCl3The concentration of the solution is 0.05mol/L, the obtained solution is centrifugally separated after the dropwise addition is finished, the rotating speed of a centrifugal machine is 10000r/min, and the obtained precipitate is washed by deionized water to obtain GO/Fe3+Performing vacuum freeze drying on the precursor at-60 ℃, wherein the freeze drying time is 48 h;
(2) preparing nano porous graphene: freeze drying GO/Fe3+And placing the precursor in a tubular furnace, calcining under the protection of inert gas atmosphere, wherein the heating rate is 10 ℃/min, the calcining time is 0min, the calcining temperature is 800 ℃, finally washing the calcined product by using 1mol/L HCl, repeatedly washing the product to be neutral by using deionized water, centrifugally separating, and carrying out vacuum freeze drying on the obtained precipitate at the temperature of-60 ℃ to obtain the nano porous graphene, wherein the aperture of the nano porous graphene is 3-5 nm.
(3) Preparing a nano porous graphene flexible electrode: and (3) redispersing the nano-porous graphene in ethanol/water, performing ultrasonic treatment to fully disperse the nano-porous graphene, and performing suction filtration to obtain a nano-porous graphene filter cake. And drying the filter cake, and then rolling, wherein the temperature of an oven is 40 ℃, and the rolling thickness is 0.2mm, so as to obtain the flexible nano porous graphene electrode plate.
Dissolving a flexible nano-porous graphene electrode plate serving as a negative electrode, metal potassium serving as a positive electrode and Whatman GF/D glass fiber serving as a diaphragm in 0.8M KPF6Ethylene carbonate/diethyl carbonate (1: 1 by volume) in solution as electrolyte in a glove box (H)2O<0.1ppm and O2<0.1ppm) of assembled PIBs, the specific discharge capacity of the assembled PIBs is about 380mAh/g at a current density of 0.1A/g, the specific discharge capacity of the assembled PIBs is about 380mAh/g at a current density of 2A/g, and the specific discharge capacity of the assembled PIBs is about 120mAh/g at a current density of 2A/g.
Example 4
(1)GO/Fe3+Preparing a precursor: and (3) carrying out ultrasonic treatment on the Graphene Oxide (GO) aqueous solution with the concentration of 0.5mg/mL for 60min to form a uniform and stable solution. Placing in ice water bath, magnetically stirring for 30min, and dripping F at a molar ratio of 1:1eCl3Solutions, FeCl3The concentration of the solution is 0.05mol/L, the obtained solution is centrifugally separated after the dropwise addition is finished, the rotating speed of a centrifugal machine is 10000r/min, and the obtained precipitate is washed by deionized water to obtain GO/Fe3+Performing vacuum freeze drying on the precursor at-60 ℃, wherein the freeze drying time is 48 h;
(2) preparing nano porous graphene: freeze drying GO/Fe3+And placing the precursor in a tubular furnace, calcining under the protection of inert gas atmosphere, wherein the heating rate is 10 ℃/min, the calcining time is 1h, the calcining temperature is 800 ℃, finally washing the calcined product by using 1mol/L HCl, repeatedly washing the product to be neutral by using deionized water, centrifugally separating, and carrying out vacuum freeze drying on the obtained precipitate at-60 ℃ to obtain the nano porous graphene, wherein the aperture of the nano porous graphene is about 20 nm.
(3) Preparing a nano porous graphene flexible electrode: and (3) redispersing the nano-porous graphene in ethanol/water, performing ultrasonic treatment to fully disperse the nano-porous graphene, and performing suction filtration to obtain a nano-porous graphene filter cake. And drying the filter cake, and then rolling, wherein the temperature of an oven is 40 ℃, and the rolling thickness is 0.2mm, so as to obtain the flexible nano porous graphene electrode plate. Dissolving a flexible nano-porous graphene electrode plate serving as a negative electrode, metal potassium serving as a positive electrode and Whatman GF/D glass fiber serving as a diaphragm in 0.8M KPF6Ethylene carbonate/diethyl carbonate (1: 1 by volume) in solution as electrolyte in a glove box (H)2O<0.1ppm and O2<0.1ppm) of assembled PIBs having a specific discharge capacity of about 300mAh/g at a current density of 0.1A/g and a specific discharge capacity of about 50mAh/g at a current density of 2A/g.
Example 5
(1)GO/Fe3+Preparing a precursor: and (3) carrying out ultrasonic treatment on the Graphene Oxide (GO) aqueous solution with the concentration of 0.5mg/mL for 80min to form a uniform and stable solution. Placing in ice water bath, magnetically stirring for 45min, and adding FeCl dropwise at a molar ratio of 1:13Solutions, FeCl3The concentration of the solution is 0.08mol/L, the obtained solution is centrifugally separated after the dropwise adding is finished, the rotating speed of a centrifugal machine is 8000r/min, and the obtained precipitate is deionizedWashing with water to obtain GO/Fe3+Performing vacuum freeze drying on the precursor at-60 ℃, wherein the freeze drying time is 48 h;
(2) preparing nano porous graphene: freeze drying GO/Fe3+And placing the precursor in a tubular furnace, calcining under the protection of inert gas atmosphere, wherein the heating rate is 5 ℃/min, the calcining time is 30min, the calcining temperature is 600 ℃, finally washing the calcined product by using 2mol/L HCl, repeatedly washing the product to be neutral by using deionized water, centrifugally separating, and carrying out vacuum freeze drying on the obtained precipitate at-60 ℃ to obtain the nano porous graphene.
(3) Preparing a nano porous graphene flexible electrode: and (3) redispersing the nano-porous graphene in ethanol/water, wherein the ratio of ethanol to water is 2:1, and performing suction filtration after fully dispersing the nano-porous graphene by ultrasonic waves to obtain a nano-porous graphene filter cake. And drying the filter cake and then rolling to obtain the flexible nano porous graphene electrode plate. And (3) redispersing the nano-porous graphene in ethanol/water, performing ultrasonic treatment to fully disperse the nano-porous graphene, and performing suction filtration to obtain a nano-porous graphene filter cake. And drying the filter cake, and then rolling, wherein the temperature of the oven is 60 ℃, and the rolling thickness is 0.3mm, so as to obtain the flexible nano porous graphene electrode plate.
Example 6
(1)GO/Fe3+Preparing a precursor: and (3) carrying out ultrasonic treatment on a Graphene Oxide (GO) aqueous solution with the concentration of 0.5mg/mL for 120min to form a uniform and stable solution. Placing in ice water bath, magnetically stirring for 60min, and adding FeCl dropwise at a molar ratio of 1:13Solutions, FeCl3The concentration of the solution is 0.1mol/L, the obtained solution is centrifugally separated after the dropwise addition is finished, the rotating speed of a centrifugal machine is 9000r/min, and the obtained precipitate is washed by deionized water to obtain GO/Fe3+Performing vacuum freeze drying on the precursor at-60 ℃, wherein the freeze drying time is 48 h;
(2) preparing nano porous graphene: freeze drying GO/Fe3+Placing the precursor in a tube furnace, calcining under the protection of inert gas atmosphere, wherein the heating rate is 5 ℃/min, the calcining time is 120min, the calcining temperature is 800 ℃, and finally calciningAnd washing the post product by using 3mol/L HCl, repeatedly washing the post product to be neutral by using deionized water, centrifugally separating, and carrying out vacuum freeze drying on the obtained precipitate at the temperature of-60 ℃ to obtain the nano porous graphene.
(3) Preparing a nano porous graphene flexible electrode: and (3) redispersing the nano-porous graphene in ethanol/water, wherein the ratio of ethanol to water is 3:1, and performing suction filtration after fully dispersing the nano-porous graphene by ultrasonic waves to obtain a nano-porous graphene filter cake. And drying the filter cake and then rolling to obtain the flexible nano porous graphene electrode plate. And (3) redispersing the nano-porous graphene in ethanol/water, performing ultrasonic treatment to fully disperse the nano-porous graphene, and performing suction filtration to obtain a nano-porous graphene filter cake. And drying the filter cake, and then rolling, wherein the temperature of the oven is 80 ℃, and the rolling thickness is 0.3mm, so as to obtain the flexible nano porous graphene electrode plate.
The protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (5)
1. A method for preparing a nano-porous graphene flexible electrode based on ion adsorption control is characterized by comprising the following steps:
s1, ultrasonically dispersing a Graphene Oxide (GO) aqueous solution, placing the solution in an ice water bath for magnetic stirring, and simultaneously dropwise adding FeCl according to a certain molar ratio3Solution is added dropwise, the obtained solution is subjected to centrifugal separation, the obtained precipitate is washed by deionized water and is subjected to vacuum freeze drying, and GO/Fe is obtained3+A precursor;
s2, freeze-drying the GO/Fe3+Calcining the precursor under the protection of inert gas, washing with a dilute HCl solution, washing with deionized water to neutrality, performing centrifugal separation, and performing vacuum freeze drying to obtain nano porous graphene;
and S3, dispersing the nano porous graphene in a mixed solution of ethanol and water, performing suction filtration after ultrasonic dispersion to obtain a filter cake, drying the filter cake, and rolling to obtain the flexible porous graphene electrode plate.
2. The method for controllably preparing the nano-porous graphene flexible electrode based on ion adsorption according to claim 1, wherein: the S1 specifically includes:
ultrasonically dispersing a graphene oxide aqueous solution with the concentration of 0.5mg/mL, placing the graphene oxide aqueous solution in an ice-water bath for magnetic stirring, and simultaneously carrying out magnetic stirring according to graphene oxide and FeCl3FeCl is added dropwise at a molar ratio of 1: 0.1-23And (3) after the solution is dropwise added, carrying out centrifugal separation treatment on the obtained solution, washing precipitates obtained by centrifugation with deionized water, and carrying out vacuum freeze drying for 24-72 h to obtain GO/Fe3+And (3) precursor.
3. The method for controllably preparing the nano-porous graphene flexible electrode based on ion adsorption according to claim 1, wherein: the S2 specifically includes:
freeze drying GO/Fe3+Calcining the precursor under the protection of an inert gas atmosphere, keeping the temperature rise rate at 5-20 ℃/min until the calcining temperature reaches 500-800 ℃, then keeping the calcining temperature for 0-120 min, finally washing the calcined product by using 1-3 mol/L diluted HCl solution, repeatedly washing the calcined product by using deionized water until the product is neutral, performing centrifugal separation, and performing vacuum freeze drying on the obtained precipitate to obtain the nano porous graphene.
4. The utility model provides a controllable preparation nanometer porous graphite alkene flexible electrode based on ion absorption which characterized in that: prepared by the method of any one of claims 1 to 3.
5. The application of the ion adsorption-based controllable preparation of the nano-porous graphene flexible electrode according to claim 4 is characterized in that: the controllable preparation of the nano porous graphene flexible electrode based on ion adsorption is directly used as a negative pole piece of a rechargeable battery.
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