TW200421655A - Energy storage device with asymmetric electrodes - Google Patents

Abstract

An energy storage device with asymmetric electrodes is provided. The energy storage device contains a first electrode, a second electrode and an electrolyte solution of metal salts. The first electrode has conductive polymers to show p-doping behavior, and the second electrode possesses characteristics of reversible oxidation-reduction reactions with the metal ions in the electrolyte to form new structures by carrying a metal oxide with nanostructure. The electrolyte provides ionic metal salts to react with the two electrodes. In addition, the nanocomposite of the second electrode metal oxide and an active additive having high conductivity shows further enhancement in performance.

Description

200421655 V. Description of the invention (1) [Technical field to which the invention belongs] The present invention relates to a type of conductive polymer electrode · conductive polymer electrode and oxidation ^ φ several pieces' especially refers to a kind of combination [prior technology] Electrode asymmetric electrode energy storage element. With the introduction of portable information, the main goals of rapid charge and discharge, long use time, and concurrent development of the capacity and system are as follows. The energy storage elements of, and f become the power supply system. The energy storage element is eight. The battery itself uses two types of batteries: battery and capacitor. Electric energy 'is designed to be normal: use: the principle of generated chemical energy to store the redox rate is slow, and the waiting time of several hours is spent on the chemical. Therefore, people need to pay attention to improving their charge and discharge when charging. Speed. Then—there are more research directions for secondary batteries. ”With a short period of time ::: ;; electricity: J Ju physical storage of energy, fully discharged, the current ultra high power = the stored power is quickly charged and discharged in an instant The special feature is to focus on the short-term current, so it can provide a considerable amount of secondary batteries when discharging in a power supply system, so that J-capacitors are often used with various types of secondary batteries to avoid over-discharge. Manufacturing = power distribution is regulated, which can increase the number of times by 7 times. However, looking at the current super name, it can make the activated carbon stored in the cycle as an energy storage system as the H device system. _Storing i's ^ The main point is the use of high power and high power. Page 7 V. Description of the invention (2) The energy of the helmet is too low, and all types of helmets can borrow power; Limited to the source system. SI1 is enough to store two or two batteries to form a hybrid electric power :: 作: made of components, the container makes it a common electrode material in the pen pen device ^ 枓 system choice. Yu Chaozhe Limited by its low-operating electric satellite = Tong or Ru02, but before Raw material price is very expensive, increase the law, and the latter by a battery of "high energy", as well as the field capacitance G competitive. Capable of combining the characteristics of only forward-looking conductive polymers with more forward-looking characteristics, the capacitors have the principle of dedoPing) energy storage. Due to their high electrical conductivity, they should be fairly fast and highly reversible. Material system with 8 ^ t doped anti-discharge potential. This type of electric two = two T becomes the electrode composition with fast charge. One of the electrodes is better connected with p-type, and the other electrode is doped with n-type (n: d: 2 The combination of storage not only has a high working voltage, meaning: this degree. In terms of conductive polymers with a fine doping ability, V; Λ volume density f (polyanlllne), polypyrrole ^ PQlyphenylvlnylene ), As well as conductive polymers such as polytMophene and their related derivatives, have considerable stability and performance; but in the case of doped = conductive polymers, the only ones commonly used are Thiophene (thiophene) class 2, 200421655 V. Description of the invention (3), there is still a lot of room for improvement in its stability and performance. It is still impossible to overcome the type 11 doping reaction of conductive polymers. This miscellaneous material ^ = self,%: Each research has tried to replace the η-type dopant with other materials; sacred materials must be highly reversible and stable for a long time. Existing research is based on activated carbon anodes with conductive polymers. Energy storage-systems, such as Polymer PMeT (Poly 3-methylthiophene, this =) 7 3 Te, ylthlophene) positive electrode, or PFPT (Poly 3- (4-fluorophenylthiodicarbons / (i-fUlOrOPhenylth10Phene)) The positive electrode and the living ancient = early w, 'and all the pieces are trying to replace the problem of poor conductivity with the activated carbon negative electrode. However, in these systems, the electric capacity of the Thunderbolt (activated carbon) of PFPT is about 30mAh / g, ^ the number of components in the helmet, you must use a considerable amount of active materials 7 seasons 5¾ ^ right also ^ plus the weight of the overall components. In addition, this type of electrochemical system has considerable power 虽It is low and can not be used for long-ratio = the energy provided can still be too much. Activated carbon electric double-layer capacitors designed symmetrically with two identical electrodes ι · [Γ 二: C? 〇Uble—Uyer Capacitor (EDLC)), although it has : Quick charge and discharge, ability and excellent cycle life, & its energy density is really too high. = Pieces in Bu 5Wh / kg), can not be put under high power for a long time: domain. U competes with various types of batteries, and also limits its practical application. [Summary of the Invention] The technical problem to be solved by the present invention is to find

Page 9 200421655 V. Description of the invention (4) ~ Suitable materials for polymer operation to replace n-type doped conductive electrode storage; Ming; Asymmetric electrical composition provided. Among them, the first electrode contains: a metal oxide of the mine electrode and an electrolyte, which makes the electrolysis reversible redox anti-itch, and J kinds of new structures' and carry out = sub-salts. The metal oxide of the second electrode can be further combined with a thunder-active additive to form a composite nano-anode conductivity and performance. Ingots are better guided by ΞΓ, which can greatly improve the energy-tight characteristics of the overall energy storage element. ΓΓ; (that is, a fast and reversible doping-de-doping material, which can be used as a sibling electrode. (Positive electrode) active material heterogeneous characteristics ^ anion (A-) action to form a stable P-type metal exchange element: is a metal oxide with a structure of 12 = nano-structure (M (metal ion (c /), Place any number of times), C, 0y in the electrolyte, and the active metalization reduction reaction of a new structure of the metal oxide M0y of V can be formed as a second electricity (negative connection) formation: No, it is called the energy storage element of the electrode. However, when the element is charged, the anion (A-) in the electrolyte moves to the positive electrode 200421655, the description of the invention (5) makes the conductive polymer (CP) into a p-type doped state. And the metal ion (c +) forms a new structure CxM〇y with the metal oxide M0y (M: metal element, y is between 0.5 to 3) of the nanometer structure of the negative electrode; , The gold ion (C +) and anion (A-) are separated from the two electrodes and returned to the hit respectively. The reaction during charging and discharging is as equations (1) ~ (3). Positive electrode: (CP) + xA ~ charge and discharge + xe ~ ⑴ negative electrode + xC + + xe ~ charge and discharge

CxM〇y (2) Lu Quan reaction: (CP) + MOv + x (C + A ~) ㈣y (CP) (3) Next, the basic theory and explanation of the present invention will be further explained. element. First, according to the existing literature, the conventional storage uses electrochemical methods to polymerize, but the applicable molecules are mostly electrode materials, and the synthesis of conductive polymers requires a large growth of 2. In the process, the use of monomers A simple and easy-to-use conductive polymer that can be directly weathered with an appropriate oxidizing agent. Therefore, according to the present invention, the polymer can be obtained through depolymerization. The polymer is a conductive material that is used in the expansion of thiophene monomers.

Page 丨 2004200421655 V. Description of the invention (6) phen (3-methylthiophene, MeT), 3- (4-fluorophenthiophene) (3- (4- {111〇1: 〇 口 11611711: 111〇0} 16116), 1 ′), 3,4-ethylenedioxythiophene (ED0T), etc., directly with oxidants containing ferric iron such as FeCl3, Fe2 (S04) 3, Fe (N03) 3. Fe (C104) 3 and Fe (CH3-C6H4-S〇3) 3 are polymerized. After washing and drying, conductive polymers such as poly (3-methylthiophene) are obtained. , PMeT), poly (3- (4- (fluorofluorothiothiophene), PFPTT), poly (3,4-ethylenedioxythiophene), PEDOT) 〇 For example, in the present invention, MeT and FPT monomers are added, 2 to 4 times the equivalent ratio of F e C I3 as an oxidant, and the reaction is carried out in trichloromethane solvent at 〇. Methanol is known-the product of depletion of soil ^, and further drying under a vacuum of 70 C, to obtain powdery conductive polymers PMeT and PFPT. In addition to the foregoing thiophene derivatives, the other conductive with p-type doping characteristics Polymer materials such as polyaniline ine, PANI), polypyrrole (PPY), polyphenylvinylene (PPV), etc. 'may also be used.

Active material. The distribution of electricity to I to the second electrode, in the subsequent embodiments will be based on the sol_gel nanometer structure requirements, because the electrode material ^ /, structure directly affects the ion diffusion behavior; if you want; : The surface shape and the rate of de-scattering increase. Only by increasing the material's carrying holes in the material (the surface area is greater than

200421655 V. Description of the invention (7) --------- ^ 00m2 / g is preferred), and the size of these holes must be large enough to allow ions to enter and exit freely. In general, the average pore diameter of the material must be greater than 5 rim ′ to reduce its resistance to diffusion and reduce the time required for diffusion to achieve rapid charge and discharge performance. As for the sol-gel method, it can be used to prepare metal oxide materials with molecular uniformity and smaller particles, and can be prepared at lower temperatures than traditional solid-state reactions, and can pass through different process conditions. The microstructure of the obtained metal oxide is suitable for the manufacture of the nano-structure material of the present invention. In the present invention, the preparation of difluorene pentoxide v205 (M0y, where M = ν, ρ2 · 5) is taken as an example. First, the sodium vanadate aqueous solution is passed through the cationic resin branch,

A vanadic acid aqueous solution precursor is obtained, and the vanadic acid aqueous solution is then left to stand. ’Interstitial growth- 丄 condensation? —Finally, it becomes A—V2 05 wet gel (hydrogel); the water in% 〇5 wet gel is replaced with solvents such as acetone, acetone, and n-hexane, and finally the solvent is volatilized to form an amorphous porous directly. VJ5 nanostructure with high specific ratio; surface area (136 m2 / g), average pore diameter is 30nm. The nanometer structure of the present invention has a %% structure, and acts with an electrolyte containing a bell metal ion to form an L1zV205 junction ^ (CxMOy, OLi 'x = z / 2, M = V, y 2.5, where ζ can be Any number) Xia has the characteristics of high capacity (> 300mAh / g). In addition, in the selection of the electrolyte, it must be a metal ion (C +) that can interact with the negative electrode material M0y of the present invention, and a p-type doping material for the positive electrode ^ I sub-material (CP). The concentration range of the anion (a-) metal salt solution knife can be between 0.1M ~ 3M, and more preferably between 0.5M ~ 2M. In terms of metal ions (C +), they can be alkali metals such as lithium, sodium, potassium (l +, Na +, K +), etc. 200421655 V. Description of the invention (8) Alkaline earth metal ions such as ions, magnesium, calcium (Mg2 +, Ca2 +), or Transition metal ions such as aluminum, yttrium, zinc (Al3 +, Y3 +, Zn2 +). The matching anions (A_) include hexafluorophosphate (PF6_), tetrafluoroborate (BF4-), hexafluoroarsenate (AsF6-), hexafluoroantimonate (SbF6-) perchlorate (C104-), Trifluoromethanesulfonate (CF3S03-), bis (trifluoromethanesulfonium) amine (N (CF3S02) 2-), bis (pentafluoroethanesulfonium) amine (N (C2F5S02) 2-) or tri ( Trifluoromethanesulfonyl) methane (c (CF3S02) 3-) is available. Dissolve such metal salts (C + A-) in carbonate (c a r b ο n a t e) solvents such as ethylene carbonate (e t h y 1 e n e carbonate, EC), propyl carbonate (pr0pyiene carbonate,

PC), dimethyl carbonate (DMC) 'diethyl carbonate (DEC), ethyl methyl carbonate ... (e ΐ hy—1 _me thy] —carbonate 5 EMC) _ f (lactone) Solvents such as Gamma-butyrolactone (GBL), etc., others such as dimethoxyxy (DME), diethoxyethane (DEE), or other solvents The group mixture of solvents is configured to be suitable for the electrolytic solution of the present invention.

The charge-discharge mechanism of the asymmetric electrode energy storage element composed of the first electrode, the second electrode, and the electrolyte is shown in Fig. 1. During the charging, the conductive polymer chain of the first electrode 100 (positive electrode) is partially oxidized, which attracts the anion 310 in the electrolysis / night to form a p-type doping (p_doping), and the second electrode (negative electrode) is in contact with the metal in the electrolyte. The ion 3 2 0 reacts to form a new structure; upon discharge, the anion 31 0 and the metal ion 32 0 are separated from the first electrode 100 and the second electrode 2 00 and returned to the electrolyte. Take the first

Page 14 V. Description of the invention (9) The electrode 100 has doping-dedoping, which belongs to the type of metal fence = type in the electrolyte, with 200 new structures of the second electrode for reversible η energy and this metal. The formation of a combination of oxides not only overcomes the problem of the conductive polymer η-type dopant avoidance, but also the type of energy storage. Such a problem is also due to the unstable energy density I of the second table (n-dOPlng). The gasification reduction reaction can be improved, and the following examples have been verified. Example 1: The production method of the pole is to mix the chemically polymerized p black and polytetramethylene (PTFE) with a weight ratio of 80: 15: 5. No.2, f 丄-again ... ^ ^ ^-° ^ ^ t. The method is to mix v, 〇5 with the nano structure of the first rule, and the fast black and PTFE at a weight ratio of 80: 15 · 5, The mixed slurry is coated on a stainless steel net, and the pressure is then applied to a temperature of 100 ° C for drying. The electrode was cut into a 12mm diameter disc and weighed. The weight of the first electrode material was 7.6mg, and the weight of the first electrode material was. Subsequently, the two electrode sheets were sequentially placed into a 2 0 32 button-type battery case, and a PP separator was placed between the two electrodes, and injected with "LiPF6, EC / PC / DEC (volume ratio 3: 2: 5 ) Electrolyte to complete the assembly of the test element. After charging this test element to 3.0 volts, discharge at a constant current of ImA / cm2, 2 mA / cm2, 5 mA / cm2, 10 mA / cm2, As shown in the attached figure, 'At a current of 1 mA / cm2, the pMeT capacitance is 35mAh / g, and the energy. Density is 38 · 5Wh / kg. If the total electrode material weight is considered, it is converted to

Page 15 200421655 V. Description of the Invention (~) The energy density is L 63Wh / kg. The manufacturing method of the first electrode of Example 2 is to mix chemically polymerized PFPT, acetylene black, and PTFE at a weight ratio of 80: 1 5: 5, and apply the mixed slurry to a stainless steel mesh, and apply pressure to the roller. It was pressed and then dried at its temperature. The method of making the second electrode is to mix the nano-structured, ethylene fast black, and PTFE at a weight ratio of 80: 15: 5, and apply the mixed slurry to a stainless steel net and roll it under pressure. It was then dried at a temperature of 100 t. The electrode was cut into a disc with a diameter of 12 mm and weighed. The first electrode material was reset to 10 · 2 and 1 to 23 · 9rng. Subsequently, the two electrode sheets were sequentially placed into a 2032 button-type battery case, and a pp insulation film was placed between the two electrodes, and injected with 1M Upf6, EC / PC / DEC (volume ratio 3: 2 ·· 5 ) Electrolyte, the assembly of the test element is completed. After charging this test element to 2.0 volts, they were discharged at a constant current of 0.1 imA / cm2 and 0.2 mA / cm2, as shown in FIG. 2, when the current density was 0.1 ImA / cm2, the PFPT electricity The capacity is 47mAh / g and the energy density is 39Wh / kg. If the total electrode material weight is considered, the converted energy density is 9 · 40Wh / kg. Example 3 The first electrode is prepared by chemically polymerizing pMeT, acetylene black, and polytetrafluoroethylene (PTFE). Ratio 7 5: 1 5: 1 0 mix and mix

Page 16 200421655 V. Description of the invention (11) The combined slurry is coated on a stainless steel net, rolled under pressure, and then dried at a temperature of 100 ° C. The manufacturing method of the second electrode is to mix the first propylene diene monomer) at a weight ratio of 77:13:10, and apply the mixed slurry to a stainless steel net, roll it under pressure, and then place it at 100 C> Dry at the profitability. Cut the electrode to lcni * lcni size. Take the first electrode and the second electrode, and separate them with a PP isolation film, with 2M LiPF6, EC / GBL (volume ratio 1: 3) as the electrolyte, composition 2〇 16-button battery for performance testing. After charging to 1 · 6 V with constant current, charge at 1 · 6 v constant voltage, and then discharge to ov at different constant current rates. The discharge curve is shown in Figure 3 of the attachment. At a current rate of 14 mA / g of PMeT, the pMeT capacitance is 51.2 mAh / g. If the total electrode material weight is considered, the converted 爿 b i bifurcation is 7 · 25Wh / kg. With the increase of the discharge current, its electric denier appears to decline. Here, the Moy metal oxide mentioned in the present invention is V2 05 (M0y, M = V, y = 2.5) in the previous embodiment, but it is not limited to v2o (y = l ~ Any number of 2.5), and have lower oxygen 222, 'milk. Emulsifying potentials such as niobium Ub), manganese (Mn), tungsten (W), titanium (Ti), chromium (Cr), < (Fe), Shao (Mo), Shu (Ru), Ming (Co), steel (Cu), tin-iron octaoxide MOy (M, b, Mn, W, T !, Cr, Fe, M〇)

Sn; y (any number from 0 to 3) structure, etc., can interact with Cu in the electrolyte, (C "to form a new structure CxMOy, and perform reversible properties, should also be included in the use of the above materials Operation, and lice reduction and reversion 200421655 V. Description of the invention (12) The living electrode of the second electrode (negative electrode) is described in the following. The following list uses sharp oxygen::;; Example 2 of the active material of the second electrode (negative electrode) of the four-element niobium oxide with a meter structure is used as an asymmetric electrode and material. // Middle-nano-grade niobium oxide Nb205 (MOy, M = Nb, y- ·) Can also be used with electricity containing lithium metal ions

LlzNb2 05 structure (CxM0 C: U χ-ζ / 9 M Nlh 0 ^ Mo cup standing batch, made lu, x — z / 2, M = Nb, y = 2.5, where ζ can be any arbitrary number ). The preparation method is as follows: a commercial grade powder (: 〇〇:? / G 'HC is directly reacted with an aqueous hydrogen peroxide solution (35%), and a muscle water drop solution is added to the mixture; after the solution is completely dissolved, the solution is converted to a drink; 'That is to get-a pale yellow clear solution. Let the solution stand for a while until the bubbles are no longer ^, the color of the solution gradually deepens spontaneously and turns into a yellow-white mixture, and finally a white-like gel precipitate is formed. A yellow-white powder can be obtained by removing most of the water from the precipitate at 100 c. The obtained powder is heat-treated at different temperatures. When it is heated to 500 ° C, non-aa shellfish particles of 20 nm are obtained. c When heat treatment is performed, a long core 205 crystal with a length of 280 nm and a width of 100 nm is obtained. The first electrode is produced by chemically polymerizing PMeT and acetylene black (. or graphite), CMC ( carboxymethy lcel lulose) mixed at a weight ratio of 20:10, and added with deionized water / methanol solution and mixed to form a slurry to coat the knife on A1 foil, and place it at room temperature until the solvent evaporates. , Set

Page 18 200421655 V. Description of the invention (13) Dry in 8 ^ f vacuum. The manufacturing method of the second electrode is to mix the ribs of nanostructure 205, acetylene black, and EPDM at a weight ratio of 50: 3: 2: 20 at room temperature. After the solvent evaporates, place them in a vacuum of 80t. Allow to dry.

The two private pole knives were cut into a diameter of 5 gu, and the first electrode and the second electrode were taken, and they were separated from each other by a PP isolation film, with 2M ^^ / ^ (volume ratio 丨: ⑴ As an electrolyte, it constitutes the Chuanxiong buckle, two = in performance. After testing, the maximum energy density of the asymmetric electrode element can be tested. ^ Introducing s species of metal oxides M0 with a structure of 1 meter, so that the metal ion C + in the thorium solution can form a new type with this metal oxide M0y. • Reversible redox 5 The reaction is used as the negative electrode material, stone 2. Element. Energy storage of activated carbon with activated carbon. In addition, the present invention further introduces an active additive and a metal emulsion of the band to form a composite active material. This active addition package is conductive. Substances such as organic semiconductors or nano-carbon tubes can increase ^ to: high conductivity, and further improve the overall performance. 1 pole to V205 as an example, its conductivity is only about 10-5 ~ lO-4S / cm, pED formed by conductive polymer monomer EDOT For T_V205 composite materials, the electricity input is about 2.95 * 10-1 s / cm, which is better than simple cymbals; and the improvement of its performance is confirmed by the following examples. , Month b

200421655

Example 5 The first electrode polymer PMeT is mixed with n-hexane and the solvent is volatilized. The second electrode conducts the reflux reaction of the conductive polymer and deionized water V2 05 composite material black, EPDM with 80 materials and a doctor blade. The preparation method in ° C vacuum is to use chemical method to convert the black block and the surface of the block into a slurry, coat the KA1 flute with a doctor blade, and then place it in the "True". In terms of materials, the pedot-v2o5 composite was first prepared. Early body EDOT and 〇5, in an aqueous solution of 1: 2 Molar ratio, after 24 hours, the resulting blue-black powder was washed with acetone and at 80. (: Drying in an oven to obtain PEDOT-> Then PEDOT-V2 05 composite powder is mixed with acetylene in a weight ratio of 1 · 5 ·· 5 and mixed with n-hexane to form a slurry on A1 foil. After the solvent evaporates at room temperature, it is left to dry. The two electrodes are cut to lcm * lcni size and weighed, the weight of the first electrode material is 3.68mg, and the weight of the second electrode material is 6mg. A PP insulation film is isolated from each other, with 1M LiPF6, EC / PC / DEC (volume ratio 3: 2: 5) as electrolyte solution. 206 button-type batteries for performance test. Charged to constant current with constant current charging method 2. After 〇ν, discharge at different constant current rates to 0V. The discharge curve is shown in Figure 4 of the annex. The capacitance of this component is 0.8mAh at 0.4mA current. With the increase of discharge current 'The capacitance shows a decline phenomenon. Charge and discharge the component with this composition at a current rate of 1.54mA. 200421655 V. Description of the invention (15)-:: 如! ^: Not shown in Figure 5. At 5 0 In 0 constant current charge and discharge tests, the capacitance of this component has just turned on. 65 I

Reduce the speed and reduce the capacity to 25mAh at the 500th time. (Ii) In the control group pm τ, in terms of an electrode material, the weight ratio of 1 acetylene black and EPDMa80: 15: 5 obtained by chemical polymerization will be combined. Add n-p alkane to mix into 5 slurry, and apply it with a doctor blade. . Dry in vacuum. Place to ...- agent. For the second electrode material, first use the powder in "〇 ....", to remove the possible crystal water. EPDM 80 : 10: 10A ^ e, ^ ^ material, coated on the A i box with a knife, placed in a chamber and dried in a vacuum of 80t. 〇mg。 Placed early in the heart The two electrodes were cut to lcm * lcm size and weighed, respectively, with a belt material weight of 2.8mg, the second electrode material weight was 6.0mm. The basins are separated from each other by a pp insulation film, and 1M LiPFe, EC / pc / DEc (volume ratio 3.2.5) is used as the electrolyte to form a 20-button battery for performance testing. Charge at a constant current to the upper voltage limit of 2 · 0V and then increase the ribbon to 0V at different constant current rates. The discharge curve is shown in Figure 6 of the appendix. The constant current at 303imA ^ The capacitance of this component is 〇68mAh. With the increase of the discharge current, the complex: the six amount appears to decline. /, Hong Fen, the components of this composition, charge and discharge test at a current rate of 23mA, as shown in Figure 7 of the annex. In 5000 constant current charge and discharge tests, I

200421655 V. Description of the invention (16) We can observe that the capacitance of this component has begun to fall from 0 · 032mAh to the 50th time, and then it appears stable, but the capacity up to the 5000th time is only 2 ^ 100 ^^^ 7 in this embodiment has a higher conductivity and conductive polymer complex eight soil mono-oxidation too much m " this X 〇 active material, it is indeed a metal earlier than the performance of the performance Oxidants are preferred. Ji Gongyuan, the above-mentioned ones are merely examples of the present invention and are not intended to limit the scope of the present invention; anyone skilled in this art will do so without departing from the spirit and scope of the present invention. Equal changes and modifications should be α 盍 within the patent scope of the present invention. ~ / Μ%

200421655 Brief description of the diagram The first diagram is a schematic diagram of a mechanism for removing electricity provided by the present invention; the discharge curve of the first example of charging and discharging of the battery is stored in the diagram, and the third diagram is a diagram provided by the present invention. The discharge curve of the second symmetrical example; the figure 4 of the besch which is broken up with this element is the fifth line of the present invention. The discharge curve of the third example is not the same as that of the fifth embodiment. The discharge curve of the fifth embodiment of the asymmetric electrode energy storage element provided by Ben Aming is shown in FIG. 6. FIG. 6 is a side view of the electrode provided by the present invention. Implementation of the energy element ^ 贝 ^ # 太 2 谷 $ —The number of cycles of the relationship curve; Example 5: the discharge curve of the second group of 7, the fifth of the known group; and Figure 8 is a comparison of the fifth example provided by the present invention Capacitance of the group_Implementation of the number of cycle energy element [Illustration of the graphical symbols] Qu, spring 10 0 First electrode 2 0 0 Second electrode 3 0 0 Electrolyte 310 Anion 3 2 0 Metal ion

Page 23

Claims (1)

200421655 VI. Application Patent Scope 1. An asymmetric electrode energy storage element, comprising: an electrolyte 'containing at least one metal ion salt and at least one soluble anion and a plurality of metal ions, the solvent is capable of dissolving the metal ions Salts; a first electrode including a conductive polymer to interact with the anions to form a p-type doping (pdoping) characteristic; and a second electrode including a metal oxide having a nanostructure to With these metal ions, a new structure is formed, and a reversible redox reaction is performed. 2. The asymmetric electrode energy storage element according to item 1 of the scope of the patent application, wherein the conductive fluorene molecule is selected from poly 3-methylthiophene (poly (3-me thy 1 thiophene)), poly 3- ( 4-fluorobenzenethiophene) (p〇iy (3- (4-〇11〇): (^) 1611 乂 1 七 111 (^) 16116)), poly 3,4-ethyldioxythiophene (p〇ly (3,4-ethylenedioxythiophene)), polypyrrole, polyaniline, and polyphenylvinylene. 3 · As described in item 1 of the scope of patent application Symmetric electrode energy storage element, wherein the metal oxide is MOy, M is a metal element, and y is any number between 0.5 and 3. 4. Asymmetric electrode energy storage as described in the first item of the scope of patent application Element, wherein the metal oxide system is selected from vanadium (V), niobium (Nb), manganese (Mn), tungsten (W), titanium (Ti), chromium (Cr), iron (Fe), molybdenum (Mo), Ruthenium (ru), cobalt (C0), copper (Cu), and a group combination of oxides of tin (Sπ). 5 · The asymmetric electrode energy storage element described in item 1 of the scope of patent application, its 200421655 VI. In the scope of the patent application, the metal oxide system is hafnium pentoxide (V205) or niobium pentoxide (Nb2 05) 〇6. Rushen symmetrical electrode energy storage element, which The agent is selected from ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl methyl carbonate (EMC), gamma-butyrolactone (GBL), di me thoxy ethane (DME), and diethoxyethane (DEE) ). 7. The asymmetric electrode energy feeding element according to item 1 of the scope of the patent application, wherein the metal ions are selected from the group consisting of lithium ions (Li +), sodium ions (Na +), potassium ions (K), and magnesium ions (Mg2 + ), | Bow ion (ca2 +), Ming ion (a! 3+), period ion (Y3 +) and zinc ion (Zn2 +), and these anions are selected from hexafluorophosphate (PFe-), Tetrafluoroborate (BIL? 4 —), hexafluoroarsenate (AsF6-), hexafluoroantimonate (SbF6 —), perchlorate (clOr), triflate (CF3S〇3-) , Bis (trifluoromethylene yellow) amine root (n (CF3S〇2) 2-), bis (pentafluoroethanesulfonyl) amine root (N (C2F5S〇2)) and samulus) burned root (c (cf3so2) 3-). Κ 8 · The asymmetric electrode energy storage element according to item 1 of the scope of the patent application, wherein the electrolyte is a solution of lithium hexafluorophosphate (L i ρρ6). "9. According to the asymmetric electrode energy storage element described in item 1 of the scope of patent application, the second electrode further contains an active additive, the active additive, 200421655 Patent application scope = organic semiconductor or nano carbon tube to improve the conductivity of the second electrode. 1 ^: Energy storage element ^ ', 忒 active additive system is poly 3,4-ethylenedioxythiophene (PEDOT, poly (3, 4-ethylenedioxythic) phene)). u. The asymmetric electrode energy storage element described in item 1 of the scope of the patent application, where the metal oxide is made through a sol-gel (solo-geo method). 1 2 The symmetrical electrode energy storage element includes: an electrolytic solution including at least one metal ion salt and at least one solvent; the metal ion salt system can provide a plurality of anions and a plurality of metal ions; the solvent system can dissolve the metal ion salt; A first electrode including a conductive polymer to interact with the anions to form a p-type doping (p-doping) characteristic; and a second electrode including a metal oxide with a nanostructure and / activity Additive, the metal oxide is used to interact with the metal ions to form a new structure and perform a reversible redox reaction, and the active additive is used to provide electrical conductivity. The asymmetric electrode energy storage device according to item 2, wherein the conductive polymer is selected from the group consisting of poly (3-methylthiophene), poly (3-fluorophenylthiophene) (poly (3 — (4-: fluorophenylthiophene)) Poly-3,4-ethylene-pyrazol dioxygen thiophene (poly (3, 4-ethylenedioxythiophene)), each of the opening ratio of poly Jie (polypyrrole), polyaniline (p〇lyaniline) and poly B Page 26 200421655 6. Scope of patent application Group combination of polyphenylvinylene. 14. The asymmetric electrode energy storage element as described in item 12 of the scope of patent application, any number between 0 · 5 and 3. 15 · The asymmetric electrode energy storage element according to item 12 of the scope of the patent application, wherein the metal oxide is selected from vanadium (V), niobium (Nb), manganese (Mn), tungsten (W), thorium (Ti), chromium (Cr), iron (Fe), hafnium (Mo), ru (Ru), cobalt (Co), copper (Cu), and group oxides of tin (Sn) oxides. 16 · The asymmetric electrode energy storage element according to item 12 of the scope of patent application, wherein the metal oxide system is V205 or Nb205. 17 · The asymmetric electrode energy storage element according to item 12 in the scope of the patent application, wherein the solvent is selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), and carbonic acid. Dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), Gamma — butyrolactone (GBL), dioxin Dimethoxyethane (DME), and diethoxye :): di ethoxye thane (DEE) of the king and shame group. 1 8. The asymmetric electrode energy storage element according to item 12 of the scope of the patent application, wherein the metal ion salt system comprises a plurality of metal ions and a plurality of anions, and the metal ion system is selected from the group consisting of lithium ions. (L i +), sodium ion Page 27 200421655 VI. Scope of patent application 'One-! One:-(Na +), potassium ion (K +), magnesium ion (Mg2 +), calcium ion (Ca2 +), aluminum ion (Al3 +), yttrium ion (γ3 +) and zinc ion ( Zn2 +) group combination, (bf4-), hexafluoroarsenate (AsF6_), hexafluoroantimonate (where ^ —), perchlorate (cior), trifluorosulfonate (CF3S〇3_), Bis (trifluoromethylamine (n (CF3S〇2) 2-), bis (pentafluoroethanesulfonyl) sulfonium) (N (C2F5S02) 2-) and tris (trifluorosulfonylsulfonium) phosphonium (CKCFsSO2 ) 3-). 1 9. The asymmetric electrode energy storage element as described in item 2 of the patent application scope, wherein the electrolyte is a solution of lithium hexafluorophosphate (Li PF6). 20. The asymmetric electrode energy storage element according to item 12 of the scope of application for a patent, wherein the metal oxide is prepared by a sol-gel method. 2 1 · The asymmetric electrode energy storage element as described in item 2 of the patent application, wherein the active additive is an organic semiconductor or a nanometer complex tube. 2 2 · The asymmetric electrode energy storage element as described in item 12 of the patent application scope, wherein the active additive is poly 3,4-ethylenedioxythiophene (pedOt, P〇1y (3,4- ethylenedioxythiophene)). Page 28