Patent Application
20160055983
The present invention relates to all-solid-state supercapacitor (ASSP) with enhanced electrode-electrolyte interface which gives very high specific capacitance, areal capacitance and very low internal resistance (ESR). The invention is particularly directed to the fabrication of all-solid-state supercapacitor by intercalation of solid electrolyte inside the conducting porous substrate coated with a charge storage electrode material to achieve the desired effect.
Developing methods for efficient energy storage systems, which is also environmentally benign, has been an emerging field in the research programmes due to intermittent nature of energy from the renewable energy sources. Among the various energy storage devices, energy storage systems such as batteries and supercapacitors, which store energy electrochemically are highly preferred due to their efficient storage capacity and also since the processes are environmentally friendly.
Electrochemical supercapacitors, as potential candidates for energy storage, are very promising over batteries such as lithium ion batteries in terms of their high power density, fast charge-discharge rate, high columbic efficiency and long cycle life.
However, liquid electrolytes in the conventional electrochemical energy storage devices raise safety issues and thus require high-standard safety encapsulation materials and technology. Replacement of liquid electrolyte in the energy storage devices using a solid counterpart is very promising for the thin, light, cheap and flexible future devices.
Polymer electrolytes have been extensively studied as electrolytes in supercapacitors and lithium batteries. Among the various polymer electrolytes, gel/plasticised electrolytes6 show ambient conductivity and desirable mechanical properties and are promising as electrolyte materials to replace conventional liquid electrolyte in supercapacitor. Many of the earlier studies utilized gel/plasticised electrolyte to replace conventional liquid electrolyte in supercapacitor. However, the use of gel as a film between the electrodes resulted in low electrode-electrolyte interfacial area which in turn resulted in poor charge storage properties.
Apart from the low charge storage property, the above strategy increases the total device resistance due to high contact resistance9 arising from the low integrity of electrode electrolyte material. Very low internal resistance (or ESR) for storage device is highly desirable as the power rate of the device is determined by the relation Pmax=v2/4R.
In order to replace liquid electrolyte from the supercapacitor (or lithium battery and fuel cell) with solid counterpart, there is a need for an electrode-electrolyte interface that can mimic the liquid-solid interface and yet provide enhanced electrode-electrolyte interface which can help the device to attain a very low ESR, which leads to high specific capacitance, areal capacitance and show excellent cycle stability.
All solid state supercapacitors are known in the art and are disclosed in patents/Patent applications such as US2012014038, US2013083452, WO201401194, CN102509637, and CN103337376 among others. However, the all-state solid supercapacitors known in the art have the following limitations/disadvantages:
The present inventors have therefore focussed in providing all solid state supercapacitor with enhanced electrode-electrolyte interface which gives very high specific capacitance, areal capacitance and shows very low internal resistance (ESR).
The main objective of the present invention is to provide all-solid-state supercapacitor (ASSP) with enhanced electrode-electrolyte interface which gives very high specific capacitance, areal capacitance and very low internal resistance (ESR).
Another objective of the present invention is to fabrication of all-solid-state supercapacitor by intercalation of solid electrolyte inside the conducting porous substrate coated with a charge storage electrode material to achieve the desired effect.
In accordance to the above challenges, the present invention provides a simple and highly scalable fabrication of all-solid-state supercapacitor with enhanced electrode-electrolyte interface which gives very high specific capacitance and areal capacitance and show very low internal resistance (ESR).
In an aspect, the present invention provides an efficient strategy for the fabrication of all-solid-state supercapacitor comprising intercalation of solid-state polymer electrolyte (component C) inside a conducting porous substrate (component A) coated with a polymer electrode material (component B) to achieve the desired effect.
In another aspect, the present invention provides an all solid-state supercapacitor with improved performance comprising of components A, B and C where the said component A comprises of conducting porous part/substrate selected from Carbon paper, Carbon cloth, Nickel foam, 3D-graphene; said B component comprises of electrode material selected from conducting polymer selected from polyaniline (PANI), polythiophene, polypyrrole, Polyethylene Dioxythiophene (PEOT) and such like, metal oxide selected from manganese oxide, cobalt oxide, nickel oxide, ruthenium oxide, iron oxide, tin oxide, indium oxide, bismuth oxide, vanadium oxide, graphene and component C comprising of a conducting solid electrolyte material, selected from polymer electrolyte such as gel/plasticized electrolyte, PVA (poly vinyl alcohol)/Acid or Base or Salts, PEO (polyethyleneoxide)/Acid or Base wherein the acid is selected from acid such as H2SO4, H3PO4, HClO4; salts such as LiCl, LiClO4, KCl; Polyethylene dioxythiophene (PEOT), Nafion™, PBI, and the like.
Accordingly, the present invention provides an all solid state super capacitor comprising:
In another embodiment of the present invention, the three dimensional collector structure is selected from carbon paper, carbon clot, nickel foam and 3D-graphene.
In still another embodiment of the present invention, the electrically conducting polymeric material is selected from polyaniline (PANI) and polyethylene dioxythiophene (PEOT).
In still another embodiment of the present invention, the electrolyte material is selected from polymer electrolyte such as gel/plasticized electrolyte, PVA (poly vinyl alcohol)/Acid or Base or Salts, PEO (polyethylene oxide)/Acid or Base, wherein the acid is selected from acid is selected from H2SO4, H3PO4, HClO4; salts selected from LiCl, LiClO4, KCl.
In still another embodiment of the present invention, the electrically conducting polymeric material is selected from polyaniline in the range of 0.3-5 mg/cm2.
In still another embodiment of the present invention, the electrically conducting polymeric material is selected from Polyethylene dioxythiophene (PEOT), in the range of 0.6-16 mg/cm2.
In yet another embodiment of the present invention, the weight of the three dimensional collector structure is in the range of 12.5-13.5 mg.
In yet another embodiment of the present invention, the H2SO4-PVA solid electrolyte comprises 48% H2SO4, 48% PVA and remaining is water.
In yet another embodiment of the present invention, said super capacitor is stable up to about 10000-12000 cycles with columbic efficiency of 100%.
In still another embodiment of the present invention, said super capacitor is having specific conductance of 850-400 F/g, areal capacitance of 255-2000 mF/cm2 and internal resistance of 1 Ω/cm2.
In yet another embodiment of the present invention, a method of fabricating all solid state super capacitor comprising the steps of:
In the present invention, the deposition of electrically conducting polymeric material (component B) on three dimensional collector structure (component A) can be carried out by Hydrothermal, Electrochemical deposition, vapour deposition or roll coating technique. The solid polymer electrolyte is prepared by a process selected from ex-situ process, wet chemistry and such like known in the art.
In yet another aspect, the invention provides fabrication of all solid state supercapacitor with enhanced electrode-electrolyte interface having high specific conductance of 850-400 F/g, areal capacitance of 255-2000 mF/cm2 with internal resistance of 1 Ω/cm2 comprising roll coating or electrodepositing PANI or PEOT on to the surface of 3D porous carbon paper followed by loading solid polymer electrolyte selected from PVA-H2SO4 and compressing two carbon paper loaded with electrode and solid electrolyte together to form all-solid-state-supercapacitors with very high interfacial area and very low resistance.
FIG. 6(II): Cross-sectional SEM images of a) solid-state-device made from CP-300; yellow arrow indicates the PVA-H2SO4 film formed between the electrodes while pressing them together which serves as a separator between the two sandwiched electrodes; b) enlarged image of PVA-H2SO4 covered PEDOT-carbon fiber corresponding to the red box in the image a), highlighting the high integrity of the electrode components; c) enlarged image corresponding to the area marked within the blue box in the SEM image a), which indicates the upper surface of the device showing highly penetrated PVA-H2SO4 gel through the PEDOT coated carbon matrix; d) S-elemental mapping along the cross-section of the device as shown in image ‘a’.
b): Comparison of the performances of the solid- and liquid-state devices made from CP-300: a) comparison of the cyclic voltammograms of the devices taken at 50 mV/s; b) specific capacitance of PEDOT in the devices measured at different scan rates; c) charge-discharge profile of the devices taken at 0.5 A/g; d) specific capacitance of PEDOT in the devices measured at different current densities.
The present invention relates to a novel fabrication of all-solid-state supercapacitors (ASSP) with enhanced electrode-electrolyte interface which gives very high specific capacitance and areal capacitance and show very low internal resistance (ESR).
The present invention relates to fabrication of all-solid-states supercapacitor with enhanced electrode-electrolyte interface which gives very high specific capacitance and areal capacitance and show very low internal resistance (ESR) comprising intercalation of solid-state polymer electrolyte (component C) inside a conducting porous substrate (component A) coated with a conducting electrode material (component B) to achieve the desired effect.
The component A comprises of three dimensional collector structure selected from carbon paper, carbon cloth, nickel foam, 3D-graphene. To achieve the high electrode-electrolyte interface architecture, the present invention preferably uses 3D porous carbon paper as (component A) having very low sheet resistance (0.26 Ω/squire), low density (0.4 g/cc) and high porosity (97%) The highly 3-D porous carbon paper act as current collector and can accommodate both the electrode material and polymer electrolyte.
The electrically conducting polymeric material (component B) is selected from group of conducting polymers such as polyaniline, polythiophene, polypyrrole, polyethylene dioxythiophene, and the like; from metal oxide such as manganese oxide, cobalt oxide, nickel oxide, ruthenium oxide, iron oxide, tin oxide, indium oxide, bismuth oxide, vanadium oxide etc. The conducting polymer is preferably selected from polyaniline (PANI) or Polyethylene dioxythiophene (PEOT). PANI is known for its very high theoretical capacitance (>1000 F/g) even though bulk PANI shows less than 300 F/g due to its poor conductivity and low surface area. However, the porous carbon fibre paper helps for improving the specific capacitance of PANI due to its increased electrode-electrolyte interfacial area and conductivity in liquid as well as solid electrolyte.
The conducting solid electrolyte (component C) is selected from gel/plasticized electrolyte, polymer electrolyte such as PVA (poly vinyl alcohol)/Acid or base or salts PEO (polyethyleneoxide)/acid or base or salt/plasticizer, Nafion, doped PBI, poly ionic liquid etc. The acid is selected from H2SO4, H3PO4, HClO4 and the salts are selected from LiCl, LiClO4, KCl etc. Particularly, conducting solid electrolyte used in the instant invention is selected from PVA-H2SO4.
It was observed by the present inventor that due to the enhanced electrode-electrolyte interface, the ion transport between polymer matrix and electrolyte during charge-discharge becomes more facile in case of PANI or PEOT coated carbon paper. Further, the conventional approach of usage of film or dipping does not result in the expected interface. The present invention provides PVA-H2SO4 gel polymer electrolyte by in-situ solidifying inside the porous current collector which is coated with PANI or PEOT.
The component (B) selected from PANI or PEOT is coated/deposited on to the porous carbon paper (A) by roll coating or electro deposition method. The weight of the highly 3-D porous carbon papers is in the range of 12.5-13.5 mg/cm2. The carbon paper used in the instant supercapacitor possesses very low sheet resistance (0.26 Ω/square), low density (0.4 g/cc) and high porosity (97%).
PANI is loaded/coated on to the porous carbon paper by roll coating using K-coater, wherein PANI is loaded in the range of 0.3-5 mg/cm2.
Poly aniline is prepared by a method known in the art and comprises addition of ice cold solution of aniline in 1M HCl to pre-cooled (NH4)2S2O8 in 1M HCl drop wise, stirring to obtain green PANI solution which is further washed, filtered and dried.
PEOT (component B) is loaded on to the porous carbon paper by electro-deposition method. PEOT is loaded in the range of 0.3-8 mg/cm2.
The device has an excellent stability of 10000-12000 cycles with columbic efficiency of 100%, a very low leakage current of 15 μA and energy density of about 14.3 Wh/kg. The whole device is very light with total weight of the device in the range of 40-60 mg and the supercapacitor of the instant invention shows a capacitance of 0.6 to 12 F/g in terms of the whole device weight. Further, the device is observed to be consistent even under wide range of humidity (30 to 80%) and temperature (−10 to 80° C.) conditions.
The invention provides a method of fabricating all solid state supercapacitor with enhanced electrode-electrolyte interface characterized by high specific conductance of 850-400 F/g, areal capacitance of 255-2000 mF/cm2 with internal resistance of 1 Ω/cm2 comprising;
In the fabrication process, polyaniline (PANI) is made into a paste with NMP and coated onto 1 cm2 area of 3D porous carbon paper (non teflonated) having a dimension of 1×2 cm2 using K-control coater. PANI to NMP ratio ((2-20 mg/0.5 ml)) is fine tuned to get uniform deposition of PANI inside the carbon matrix. Different loading of PANI is obtained by varying concentration PANI in NMP and the electrodes are dried overnight. For making solid state supercapacitors, PVA-H2SO4 aqueous solution is used as electrolyte and is coated on to PANI coated carbon paper electrode using K-control coater on both side and dried using air gun. Two electrodes are taken after formation of fine layer on one side and are compressed together using an ambient pressure. The required electrical contacts from the electrodes were made by using metal crocodile clips.
Similarly, polyethylenedioxythiophene (PEDOT) was deposited onto the porous carbon paper by electro-deposition technique followed by intercalating the matrix with polyvinyl alcohol-sulphuric acid (PVA-H2SO4) gel electrolyte. The electrodeposited layer of PEDOT maintained a flower-like growth pattern along the treads of each carbon fibre. This morphology and the alignment of PEDOT led to enhanced surface area and electrical conductivity whereas, the pores in the system enabled effective intercalation of the polymer-gel electrolyte.
Devices were made by using polypropylene as a separator in between the two electrodes and tested in 0.5 M H2SO4. For making the solid-state supercapacitors, PVA-H2SO4 aqueous solution was used as electrolyte. They were coated on to PANI coated carbon paper electrode using K-control coater on both side and dried using air gun. Two electrodes are taken after formation of fine layer on one side and compressed using an ambient pressure. The film formed in between the electrode prevents the short circuit by acting as a separator. The required electrical contacts from the electrodes are made by using metal crocodile clips.
It was observed that porosity was still sufficient inside the PANI/carbon paper or PEOT/carbon paper for making intercalated electrode-gel electrolyte interface thus mimicking the liquid nature inside the carbon matrix.
The enhanced interface helped the solid device (ASSP) to perform like a liquid counterpart showing a capacitance of 850-400 F/g at a current density of 0.5 A/g shown in
The comparative study clearly illustrates the PANI coated carbon paper show a very high capacitance of 695 F/g at 10 mV/s (
The comparative study clearly indicates the utilisation of 3D porous carbon paper in the instant invention which helps the PANI to attain high surface area by distribution of electrode material inside the 3-D network of porous carbon paper electrode. The comparative study is further detailed in examples hereinbelow.
The present invention provides a novel approach in the design of all-solid-state supercapacitor by intercalated polymer electrolyte inside the PANI/PEOT coated carbon paper with enhanced electrode-electrolyte interface. The enhanced electrode-electrolyte integrity helps the solid device to perform like a liquid counterpart and shows a high specific capacitance of 800-400 F/g with an areal capacitance of 255-2000 mF/cm2 and able to retain 62% of capacitance at 20 A/g. The high integrity of the electrode-electrolyte helps the device to attain a very low ESR of 1Ω. Apart from this the device show excellent cycle stability of 10000-20000 with a columbic efficiency of 100%. Energy density of the device is 14.3 Wh/kg which is the highest reported value for solid-state-supercapacitor and show a very low leakage current of 16 μA.
Following examples are given by way of illustration therefore should not be construed to limit the scope of the invention.
To 1 ml of aniline in 50 ml of 1M HCl in ice cold solution, pre-cooled (NH4)2S2O8 (1:2 M ratio with aniline) in 50 ml 1M HCl is added drop wise and stirred for 6 hr. The green PANI solution is filtered and washed with DI water and dried at 60° C.
Approximately 2 gms of PVA is weighed and transferred on to 100 ml RB flask containing 20 ml of de-ionized water (DI) to prepare 10 wt % PVA solutions. The mixture is heated at 850° C. with constant stirring until clear solution of PVA is obtained after which it is cooled to room temperature (27° C.). Approximately 2 gms of concentrated H2SO4 is added to the solution and stirred gently for 30 minutes to obtain 1:1 PVA-H2SO4 solution. Example 3: Preparation of electrode by coating of PVA polymer on to the porous carbon paper:
Polyaniline was made into a paste with NMP and coated onto 1 cm2 area of Torey carbon paper (non teflonated) having a dimension of 1×2 cm2 using K-control coater. PANI to NMP ratio was fine tuned to get uniform deposition of PANI inside the carbon matrix. Different loading of PANI was obtained by varying concentration of PANI in NMP. (2-20 mg/0.5 ml) (This varied concentration will result in varied electrode-electrolyte interface (
Electrochemical Polymerization of EDOT:
Polymerization was carried out in a BioLogic SP-300 Potentio-Galvanostat using 3-electrode systems in which carbon paper was used as the working electrode, Pt was used as the counter electrode and Ag/AgCl was used as the reference electrode. Electrolyte used was acetonitrile containing 0.1 M LiClO4 as supporting electrolyte and 0.1 M EDOT. Before the experiments, nitrogen was passed through the electrolyte to remove any dissolved oxygen. 1 cm2 area of carbon paper was kept exposed to electrolyte and remaining part was masked using a Kapton adhesive tape. The experiments were carried out in constant current mode, by maintaining 10 mA/cm2 current density. The experiments were repeated for different time durations of 50, 100, 300, 600, 1200 s and the corresponding electrodes are named as CP-50, CP-100, CP-300, CP-600, and CP-1200 respectively. After completion of the electrochemical deposition, the electrodes were washed with acetonitrile solution and dried under IR lamp and the results of the characterization studies are tabulated in Table 4. For making solid state supercapacitors, PVA-H2SO4 aqueous solution is used as electrolyte and is coated on to PVOA coated carbon paper electrode using K-control coater on both side and dried using air gun. Two electrodes are taken after formation of fine layer on one side and are compressed together using an ambient pressure.
All the electrochemical studies were carried in a BioLogic SP-300 Potentio-Galvanostat. The CV measurements were taken at different scan rates from 10 to 150 mVs−1 by maintaining a potential window of 0.8 V. Charge-discharge measurement is done at different current densities (0.5 to 20 A/g) in the potential range of 0-0.8 V. Cycling stability was done by chrono charge-discharge method at 5 A/g current density. Electrochemical impedance (EIS) analysis was carried out from 106 Hz to 0.01 Hz frequency against the open circuit potential with a sinus amplitude of 10 mV Nrms=7.07 mV). All the EIS data were analysed using an EC-Lab Software V10.19. For comparison, experiments were conducted in a plain current collector using Grafoil® paper as current collector using liquid and solid electrolyte. Leakage current was measured from the plot of current Vs time obtained by charging the cell using a low current density up to 0.8 V and keeping the cell at 0.8V by chrono-amperometric technique. A voltage drop of the cell was measured for 24 hr by charging the cell at 0.8V for 20 minutes followed by measuring the open circuit potential. For all-solid-state supercapacitors having 1.5 mg/cm2 loading on each electrode were connected in series to get a working potential of 3V for glowing a LED.
SEM and EDAX elemental mapping of the surface of carbon paper showed clear picture of the surface morphology of the device. The bare carbon paper SEM images in
Cross sectional SEM images and elemental mapping of the devices depict the expected high integrity and enhanced electrode-electrolyte interface (
Sulphur mapping at the same spot in the
Electrochemical charge storage properties of polyaniline coated electrodes using cyclic voltammetry (CV) and chrono charge-discharge methods were analysed initially in acidic medium containing 0.5M H2SO4. Two PANI coated electrodes were separated by polycarbonate film dipped in electrolyte used for analysis. CV scan rate was varied from 10 mV/s to 150 mV/s and current densities from 0.5 A/g to 20 A/g. Since the present invention uses 2 electrodes for testing, capacitance values calculated from cyclic voltammogram and charge-discharge curve are multiplied by a factor of 2 to obtain capacitance of single electrode.
To establish the role of porous current collector towards the improvement of capacitance by enhancing the electrode-electrolyte interfacial area, Grafoil® was used for comparing with carbon paper. Grafoil® is a plane current collector with high conductivity (
The above result clearly indicated the superiority of use of porous substrate as current collector to design all-solid-supercapacitor (ASSP). Porosity of the carbon paper helped the polymer to go inside the carbon matrix very easily and to establish good contact with the carbon fibres rather than filtering at the surface. This in turn resulted in enhanced electrode-electrolyte interfacial area compared to PANI coated on to Grafoil. This strategy was succeeded and reflected in the capacitance of ASSP, they showed a capacitance of 647 F/g at a current density of 0.5 A/g as shown in
The specific capacitance and areal capacitance obtained for the polyaniline using porous current collector for the solid state supercapacitor is given below in Table 1. Even at a very high areal capacitance of 2 F/cm2, the device showed a specific capacitance of 400 F/g. The specific capacitance can be reached to 850 F/g with a low loading of 0.3 mg/cm2, where the areal capacitance was 0.28 F/cm2 (
Impedance analysis of ASSP confirms the high charge storage properties obtained in CV and chrono charge-discharge method. The equivalent resistant series (ESR) of the device is only 1Ω as taken from the x intercept of the Nyquist plot (
Energy density and power density were calculated from the charge-discharge method and corresponding Ragone plot as show in the
Extended cycling stability is an essential criterion for any charge storage devices. It was found that the instant design of the supercapacitor not only improves the capacitance but it also improves the stability. 10000 continuous cycling were carried at a current density of 5 A/g of ASSP which showed the capacitance of 638 F/g. % capacitance retention and columbic efficiency during the 10000 cycles are plotted in
The device of the invention is light weight due to the low density of the carbon paper. The whole device shows only 110 mg (
The leakage current was measured by charging at 0.8V and monitoring the current required to keep that potential. Normally, leakage current of the supercapacitorsis higher than the Li-ion batteries. The leakage current of the invention was observed only 50 μA at 200 s and reached 16 μA at 2000 s (
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| Number | Date | Country | Kind |
|---|---|---|---|
| 1111/DEL/2013 | Apr 2013 | IN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/IN2014/000233 | 4/15/2014 | WO | 00 |
