CN102034959A - Composite electrode material and secondary battery made of same - Google Patents
Composite electrode material and secondary battery made of same Download PDFInfo
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- CN102034959A CN102034959A CN2009101780885A CN200910178088A CN102034959A CN 102034959 A CN102034959 A CN 102034959A CN 2009101780885 A CN2009101780885 A CN 2009101780885A CN 200910178088 A CN200910178088 A CN 200910178088A CN 102034959 A CN102034959 A CN 102034959A
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Abstract
The invention discloses a composite electrode material. Nitrogen-containing electroconductive polymer is blended with an electroconductive carbon material, wherein the electroconductive carbon material accounts for 1 to 40 percent of the total weight of the blended material; and the blended material is activated with 0.2 to 5M hydrogen ion-containing acid electrolyte. The invention further comprises a secondary battery taking the composite electrode material as an anode material. The electroconductive carbon material and the hydrogen ion-containing acid electrolyte with high concentration are added into the electrode material of the battery, so the electrical conductivity performance of the composite electrode can be improved to further improve the charge-discharge efficiency and the service life of the secondary battery.
Description
Technical field
The present invention refers to a kind of electroconductive polymer combination electrode material especially relevant for a kind of electrode material, and it can make electrode have the feature of fast charging and discharging and high storage capacitors amount.The present invention comprises the proton secondary cell of the above-mentioned combination electrode material of use as electrode in addition.
Background technology
Hydrogen ion (proton type) conducting polymer secondary cell is the middle-size and small-size storage battery of a new generation behind lithium rechargeable battery, because hydrogen ion has littler ionic radius and ionic mobility faster than lithium ion, has the operating voltage height so plant novel chemical power source, the discharge potential curve is steady, self discharge is little, have extended cycle life, the advantage that pollution-free grade is outstanding, in addition, but it is the battery of an overall height molecularization design, has the function (the electric current scope of application that monocell can discharge and recharge can reach 10 amperes) that high electric current charges and discharge, except being applied in Portable battery (2Ah) use, also can utilize at hull cell (200 μ Ah), on compact battery (200mAh) and the large-sized battery (50Ah).
The performance of conducting polymer secondary cell and positive pole, negative pole, electrolytical characteristic are closely bound up, with positive electrode decisive influence are arranged more especially.Detailed opinion, if positive electrode relative negative material on electrical conductivity has high potential, the change of its composition is little to the influence of cell voltage, the good electron conductive performance is arranged again, and flatness, the IR impedance that then can obtain high working voltage, voltage is little, voltage descends changes the battery of characteristic such as little; If positive electrode itself has cation embeds, embedding goes out invertibity and high diffusibility, high storage characteristics, difficultly influence volume of battery because of discharging and recharging to react, then can obtain the battery of characteristics such as high cycle life, high-capacitance, high electric current; The thermostability when if the chemical property of positive electrode has electrolytical stability with charging, then can obtain the battery of characteristics such as high cycle life and stability.
In other words, the good battery of processability, make it to have high working voltage, the flatness of voltage, IR impedance are little, voltage descends changes the characteristic of little, high-capacitance, high cycle life and stability, the only positive electrode of searching earlier.Use the electroconductive polymer active material to be positive and negative pole material as poly-indoles (indole), secondary cell or the application on the capacitor with the proton fast charging and discharging under sour environment provide than other batteries (as lithium cobalt battery) better advantage of system, comprise: the assembling of (1) proton-electron can be integrally formed, as directly form battery on metal forming yarn or porous metal substrate or conductive carbon base material; (2) battery charge and discharge circulation can be near perfect invertibity (not having Memorability), the number of times that can charge and discharge circulation is more than 100,000 times; (3) process technique can be used the process technique manufacturing of existing traditional electrical pond; (4) its main carrier that discharges and recharges is a proton.
At present the main synthetic method of poly-indoles is to adopt electrochemical process and utilize oxidant to carry out chemical polymerization, and the latter's oxidant comprises frerrous chloride, sodium thiosulfate etc.Constitute because this polymer is the combination of hydrocarbon nitrogen, so be friendly to environment, along with the maturation of synthetic technology, its price has met business-like demand.Synthesis of cyclic indoles three monomer prepolymers are arranged in early days, in acidic electrolyte solution, utilize the cation adsorption/desorption to discharge and recharge mechanism and have, reach more than 100,000 times in stable circulation under 90% charge and discharge circulation life up to 50 to 60mAh/g quality capacitance.And the known technology that United States Patent (USP) U.S.6300015B1 discloses is further introduced a diaphragm between the both positive and negative polarity conducting polymer, but compares still too lowly with lithium battery at the capacitance of battery and operation electromotive force, and it is required to be not suitable for practical application.
In sum, how to make the positive electrode of poly-nitroindoline have powerful anion adsorption capacity and the conductivity that promotes battery combination, to promote the discharging efficiency of proton in the electrode for secondary battery, the still target of making great efforts for the secondary cell industrial circle.
Summary of the invention
Because but the discharging efficiency of existing electrode material still has improvements, the object of the present invention is to provide a kind of combination electrode material and use the secondary cell of this electrode material, it has the feature of fast charging and discharging and high storage capacitors amount.
For reaching the above object, combination electrode material of the present invention is with nitrogenous electroconductive polymer and conductive carbon material blending, this nitrogenous electroconductive polymer is poly quinoline (polyquinoline), polyphenylene quinoxaline (polyphenylquinoxaline), polycarbazole (polycarbazole), polypyridine (polypyridine), polypyrrole (polypyrrole), polyaniline (polyaniline) or poly-indoles (polyindole), this conductive carbon material accounts for 1% to 40% of material total weight after this blending, and the material after the blending is activated with the acidic electrolysis bath that 0.2M～5M contains hydrogen ion again.
Secondary cell of the present invention uses above-mentioned combination electrode material as positive electrode.
Secondary cell of the present invention comprises:
One positive electrode, it is with nitrogenous electroconductive polymer and conductive carbon material blending, this nitrogenous electroconductive polymer is poly quinoline (polyquinoline), polyphenylene quinoxaline (polyphenylquinoxaline), polycarbazole (polycarbazole), polypyridine (polypyridine), polypyrrole (polypyrrole), polyaniline (polyaniline) or poly-indoles (polyindole), this conductive carbon material accounts for 1% to 40% of material total weight after this blending, and the material after the blending is activated with the acidic electrolysis bath that 0.2M～5M contains hydrogen ion again;
One negative material, it is with electroconductive polymer and conductive carbon material blending, this electroconductive polymer is the poly-phenyl ethene (polyphenyl vinylene) of stretching, poly-furans (polyfuran), polysulfide (polysulfide), polythiophene (polythiophene), poly quinoline (polyquinoline), polyphenylene quinoxaline (polyphenylquinoxaline), polycarbazole (polycarbazole), polypyridine (polypyridine), polypyrrole (polypyrrole), polyaniline (polyaniline) or poly-indoles (polyindole), this conductive carbon material accounts for 1% to 40% of material total weight after this blending, and the material after the blending is activated with the acidic electrolysis bath that 0.2M～5M contains hydrogen ion again;
One barrier film, it separates the positive and negative electrode material;
One electrolyte, it is arranged at this positive and negative electrode storeroom, and this electrolyte includes aqueous sulfuric acid or acid organic electrolyte;
One cathode collector, it contacts with this positive electrode;
One anode collector, it contacts with this negative material; And
The attainable concrete effect of the present invention comprises:
1. the present invention adds the material with carbon element of high conductivity and with the hydrogeneous ion electrolyte of high concentration, therefore can improve conductive performance, and then make secondary cell have high charge-discharge efficient and high cycle life in battery electrode material.
Description of drawings
Fig. 1 is the system schematic of the secondary cell of preferred embodiment of the present invention;
Fig. 2 is the sulfur acid battery cyclic voltammetry curve figure of preferred embodiment of the present invention;
Fig. 3 is the manufacturing flow chart of preferred embodiment of the present invention;
Fig. 4 contains the energy curve figure of organic electrolyte cell under different constant-current discharges for preferred embodiment of the present invention.
Description of reference numerals:
The 1-housing; The 2-positive electrode; The 3-negative material; The 4-barrier film; 5-electrolyte; The 6-cathode collector; The 7-anode collector.
Embodiment
Please refer to shown in Figure 1ly, the preferred embodiment of secondary cell of the present invention comprises a housing 1, a positive electrode 2, a negative material 3, a barrier film 4, an electrolyte 5, a cathode collector 6 and an anode collector 7, wherein;
This housing 1 is in order to hold and to seal above-mentioned each material and element, and its material can be the mixture of metal, plastics or metal and plastics;
This positive electrode 2 is with nitrogenous electroconductive polymer material and conductive carbon material blending, to promote the conductivity of positive electrode, this conductive carbon material accounts for 1% to 40% of material total weight after this blending, material after the blending is activated with the acidic electrolysis bath that 0.2M～5M contains hydrogen ion again, forms the positive electrode with macroion conducting power; In this preferred embodiment, this nitrogenous electroconductive polymer material example can be poly quinoline (polyquinoline), polyphenylene quinoxaline (polyphenylquinoxaline), polycarbazole (polycarbazole), polypyridine (polypyridine), polypyrrole (polypyrrole), polyaniline (polyaniline) or poly-indoles (polyindole), wherein based on poly-indoles, as contain the poly-indoles of nitro, cyano-containing gathers indoles, halogen-containing base gathers indoles, the boracic acidic group gathers indoles, phosphorous acidic group gathers indoles, contain the poly-indoles of sulfonic group, contain the poly-indoles material that poly-indoles of cyanic acid base or the poly-indoles of isocyanato group containing etc. contain drawing electron group, wherein again to contain the poly-indoles the best of nitro, the preparation of this positive electrode 2 is based on chemical synthesis process, but do not limit this synthetic method, this conductive carbon material can be micron order even nano-level conducting carbon black, graphite whisker, amorphous carbon, activated carbon, mesoporous carbon, porous carbon fiber, carbon nano-fiber, CNT (carbon nano-tube) or carbon fiber etc., its particle diameter is less than 10 microns, and this acidic electrolysis bath can include sulfuric acid;
This negative material 3 is with electroconductive polymer material and conductive carbon material blending, to promote the electron conduction of negative material, this conductive carbon material accounts for 1% to 40% of material total weight after this blending, material after the blending is activated with the acidic electrolysis bath that 0.2M～5M contains hydrogen ion again, forms the negative material 3 with macroion conducting power; In this preferred embodiment, this electroconductive polymer material is as the poly-phenyl ethene (polyphenyl vinylene) of stretching, poly-furans (polyfuran), polysulfide (polysulfide), polythiophene (polythiophene), poly quinoline (polyquinoline), polyphenylene quinoxaline (polyphenylquinoxaline), polycarbazole (polycarbazole), polypyridine (polypyridine), polypyrrole (polypyrrole), polyaniline (polyaniline), poly-indoles (polyindole) etc., wherein more excellent with nitrogenous electroconductive polymer, especially polyaniline the best, the preparation of this negative material 3 is based on chemical synthesis process, but do not limit this synthetic method, this conductive carbon material can be micron order even nano-level conducting carbon black, graphite whisker, amorphous carbon, activated carbon, mesoporous carbon, porous carbon fiber, carbon nano-fiber, CNT (carbon nano-tube) or carbon fiber etc., its particle diameter is less than 10 microns, and this acidic electrolysis bath can include sulfuric acid or acid organic electrolyte;
This barrier film 4 is separated positive and negative electrode material 2,3, and it can be the micropore separation membrane of polypropylene, polyethylene and polypropylene co-polymer or fluorine resin, and its hole is less than 50 microns;
This electrolyte 5 just is being arranged at this, negative material 2,3, this electrolyte 5 includes sulfuric acid or acid organic electrolyte, and its can with in order to the activation just, the acidic electrolysis bath of negative pole is a same solution, in this preferred embodiment, this organic electrolyte can include propyl carbonate (propyl carbonate), ethyl carbonate (ethyl carbonate), ammonium dihydrogen phosphate (mono-ammonium phosphate), lithium perchlorate (lithium perchlorate), dimethyl formamide (DMF) and tetrachloro tetraethylammonium borate salt (TEATFB), can further include a nano inoganic particle in this electrolyte, as nano titanium oxide, nano silicon or nano fullerene, make electrolyte 5 thus than not adding the inorganic nanoparticles period of the day from 11 p.m. to 1 a.m, conductivity has promoted more than 10 times;
This cathode collector 6 contacts with this positive electrode 2, it can wire netting, metal forming or conductive carbon material are main, wherein wire netting, metal forming can include gold-plated copper mesh, gold-plated Copper Foil, gold-plated aluminium net, gold-plated aluminium foil, copper mesh, Copper Foil, aluminium net or aluminium foil, and conductive carbon material can be used carbon fiber adhesive-bonded fabric, carbon nano-fiber adhesive-bonded fabric or graphite whisker fiber adhesive-bonded fabric;
This anode collector 7 contacts with this negative material 3, it can wire netting, metal forming or conductive carbon material are main, wherein wire netting, metal forming can include gold-plated copper mesh, gold-plated Copper Foil, gold-plated aluminium net, gold-plated aluminium foil, copper mesh, Copper Foil, aluminium net or aluminium foil, and conductive carbon material can be used carbon fiber adhesive-bonded fabric, carbon nano-fiber adhesive-bonded fabric or graphite whisker fiber adhesive-bonded fabric;
Because conducting polymer is formed for singly-bound itself that have conjugation and two keys replace bond (conjugated bond), make that pi-electron can be mobile on the strand, and have essence (intrinsic) conductivity.The electrical conductivity of the conducting polymer of tool essence (intrinsic) conductivity, still being not enough to be applied in the present invention organises entirely and uses on the active positive and negative electrode of secondary cell, so conducting polymer of the present invention needs by the percentage of controlled doping (doping) as sulfuric acid, introduce specific active material such as hydrogen ion and change its conductivity, provide the redox state of high-energy-density to improve the electrodes conduct degree, can be by not mixing preceding 10
-6～10
-4The S/cm electrical conductivity increases to 10 after the doping
1S/cm or higher electrical conductivity differ and can reach more than several orders of magnitude.
The doping preparation procedure of active positive and negative electrode mainly is chemically conducting polymer directly to be contacted with alloy in being present in gas phase or liquid phase, or is finished by electrochemical oxidation or method of reducing.The result who mixes can make that belonging to semi-conductive conducting polymer originally produces a new energy state, forms a more low-energy energy gap median (midgap) between band gap (bandgap), it is generally acknowledged that this energy gap median can help electrical conductivity.From vitochemical angle, alloy (dopant) is being played the part of the role who removes or increase electronics on the conducting polymer just, be example just with poly-indoles, when sulfuric acid is entrained on the poly-indoles, sulfuric acid can attract electronics of indole ring, and makes the indole ring structure that loses electronics on the poly-indoles and can form a radical cation (radical cation); (be called polar biased again, polaron) positive charge on is owing to the relation of enclosed pasture electrostatic force, and its translational speed is very low for this cation; On the other hand, its hydrogen ion that is adsorbed on above the poly-indoles then can move fast.Therefore hydrogen ion will be on the conductive polymer subchain fast moving, the sulfuric acid alloy that just must give high concentration improves the poly-cationic indole ring structure of indoles internal freedom base, this has explained that also the present invention is why when positive and negative electrode doped sulfuric acid or acid organic electrolyte degree are high more, its conductivity is good more, but still has an optimization doping level.
Each pH-value of secondary battery system provided by the present invention will be lower than 3, and the positive and negative electrode material after the acidic electrolysis bath activation has higher electron conduction and electron storage amount.Secondary battery system of the present invention is one to have the battery of following condition: (1) high operation voltage; (2) high-energy-density; (3) quiet run voltage; (4) broad operating temperature range; (5) excellent cycle; (6) long term storage does not contain heavy metal element poisonous, that pollute with (7), so be a high-performance conductive macromolecule secondary battery system.Therefore in this battery material, positive electrode is the main key of decision battery performance, adds the material with carbon element of high conductivity and be core technology of the present invention with the acidic electrolysis bath activated electrode in battery electrode.
Positive electrode provided by the present invention is a core material to contain poly-indoles such as drawing electron group such as nitro, sulfonic group, cyanic acid base again based on nitrogenous electroconductive polymer material, utilizes easy oxidation polymerization method reaction to form poly-indoles main body macromolecule.Poly-indole structure is as shown in following:
X＝NO
2orSO
3H
Import drawing electron group again in poly-indole structure X position, structurally to increase its thermal stability and push-and-pull electronic capability thereof, improving its charging and discharging capabilities is example with the battery of the present invention of 40% (5.3 moles) sulfuric acid that mixes, inquire into the basic principle of the present invention's conduction: the poly-cyclic voltammetry curve of indoles material in sulfuric acid has two characteristics, the one, at 0～0.9 volt of place, two unsettled irreversible peaks are arranged, but above-mentioned instability will disappear after the circulation for several times.The 2nd, at 1.05 volts of places, a highly stable reversible peak is arranged.
Poly-nitroindoline material cyclic voltammetry curve in sulfuric acid then has following characteristic, only sees the reversible peak that is present in 1.15 volts of places, and there are not two irreversible peaks in 0～0.9 volt of place.And the current potential at reversible peak has improved 0.1 volt, and its reason is that the poly-indoles of nitration has improved that nitrogen-atoms draws electronic capability in the indoles.Therefore the charge and discharge cycles of poly-nitroindoline material is finished by following two steps, and the one, because the interionic of poly-nitroindoline and doping is that completely reversibility reacts corresponding to 0～0.9 volt range in cyclic voltammetry curve.The 2nd, because poly-nitroindoline is accompanied by the reversible process of adsorption/desorption proton when finishing redox reaction, in its cyclic voltammetry curve, react the scope at peak corresponding to a high position of 0.9～1.2 volt.
Because this process is accompanied by the state of adsorption/desorption proton all the time, and proton is the volume minimum, can determine that this precursor reactant process is very stable, and therefore being used for anode can obtain very long useful life.Therefore with the positive pole of poly-nitroindoline conductive polymer applications at secondary cell, it also is mixed with conductive carbon material and when being activated by the organic or inorganic acid electrolyte that contains proton, and its formed conductive reaction mechanism is as follows:
(1) be the discharging and recharging of the doping anion adsorption/desorption of poly-nitroindoline 0～0.9 volt of (silver/silver chloride electrode relatively) cyclic voltammetric voltage tester scope, the reversible reaction process is following mechanism:
(2) 0.9～1.2 volt (silver/silver chloride electrode relatively), cyclic voltammetric voltage tester scope is discharging and recharging of proton adsorption/desorption for the redox of poly-nitroindoline, and the reversible reaction process is following mechanism:
Can demonstrate the proton battery when 0.9～1.2 voltaism kinetic potential is operated by above-mentioned reaction mechanism, charge and discharge process mainly is with the behavior of proton adsorption desorption, so the proton battery is that a fast charging and discharging reaches the good battery (discharging and recharging under the condition of the quality capacitance that keeps 60% battery) up to battery cycle life more than 10,000 times.
Produce in the process of redox reaction at Polyaniline Doped 40% (5.3 moles) sulfuric acid, also produced the reversible process of adsorption/desorption proton simultaneously, the current potential of its reaction is-0.2～0.4 volt, and its characteristic is highly stable, is suitable as battery cathode and uses.The reversible reaction process of polyaniline in Bronsted acid solution is following mechanism:
Comprehensive above-mentioned two electrode material combinations become secondary cell, and it can reversiblely finish redox reaction, resulting cyclic voltammetry curve as shown in Figure 2, lithium battery relatively, the present invention is safety but also reliable not only, can satisfy the demand in future.
Battery material content of the present invention is to the influence of battery capacity, because positive limiting quantity mode is adopted in design, excessive 10～15% of the positive pole that is about of negative pole, for obtaining the highest quality than capacitance and volumetric capacitance amount, determine that the poly-optimum content of nitroindoline in positive pole is 75～80%, reached the technical indicator of 100mAh/g.When the positive and negative electrode raw material adopted sulfuric acid to mix, the concentration that must control sulfuric acid was with the demand that satisfies diffusion of protons and guarantee not the activity and the stability of conductive polymer polymer are impacted.
The following example is used for exemplary illustration the present invention.These embodiment are intended to limit the scope of the invention never in any form, how to implement material of the present invention and method but be used for indication.
Embodiment one: nitrated poly-indoles synthetic
Processing procedure (one): gather the synthetic of indoles
Experimental procedure: (the starting material indoles adds solvent and is made into about 1.5～2 liters 1M solution based on 200 grams)
1. earlier reaction temperature is reduced to-5～15 ℃ (ice bath), again the iron chloride (1.5.eq) that weighs up is inserted in the reaction bulb, add about 0.1～0.2 liter chloroform dissolving iron chloride earlier, stir about 5～25 minutes;
2. again with the starting material indoles (1eq that weighs up, 200 grams), add in iron chloride/chloroformic solution in batches, added required time about one hour in batches, need the limit to add indoles limit solubilizer (chloroform) in the process, not so indoles can stick to reaction bulb wall (because the reaction of indoles and iron chloride is very violent, so at the beginning will necessary control reaction temperature);
3. reaction (process) device needs logical nitrogen, adds once ice in about 1～3 hour, and the reaction time is to keep-5～15 ℃ in 2～10 hours, allows its room temperature of getting back to naturally overnight;
4. when collecting product, need earlier solvent (chloroform) to be filtered to collect filter cake, again filter cake is carried out about 1～3 liter washing, because meeting heat release this moment, must carry out ice bath so wash certainly when initial, avoid the product can heat release and splash everywhere, treat that the reaction of product and water relaxes after, product is filtered again and with clear water washing several in batches;
5. at last product is inserted vacuum drying oven oven dry (60～100 ℃ of temperature).
Processing procedure (two): poly-indoles nitration reaction
Experimental procedure: (the poly-indoles of starting material adds solvent and is made into about 1.5～2 liters based on 200 grams)
1. earlier reaction temperature is reduced to-5～15 ℃ (ice bath), insert in the reaction bulb with the acetic anhydride (1～6eq:522 gram) that weighs up again, again the nitric acid (1.5eq) that weighs up is slowly added in the reaction bulb after (1 of 1～10 second) drip off stir about 15～20 minutes with addition funnel;
2. the more poly-indoles of ready starting material is added in acetic anhydride/salpeter solution in batches, slowly add about 0.5～5 hour time of adding in the reaction bulb.(poly-indoles and acetic anhydride/salpeter solution reaction acutely, so at the beginning will control reaction temperature);
3. added ice cube one time in per approximately 10～30 minutes in the course of reaction, make temperature be controlled at-5～15 ℃ always, up to poly-indoles add add in the reactor till, stir about is 15～20 minutes again;
4. when collecting product, need earlier solvent filter to collect filter cake, again filter cake is added about 1 liter washing earlier, because meeting heat release this moment, must carry out ice bath so wash certainly when initial, avoid the product can heat release and the place of flashing spray, treat that the reaction of product and water is than mitigation after, product is filtered and washes with water in batches again, it is become till the clear, colorless.
5. at last product is placed and at room temperature dried in the shade 2 days, insert vacuum drying oven oven dry (temperature: 60～100 ℃) again, need baking 1～5 day.
Embodiment two: gather the synthetic of 5-nitroindoline
Experimental procedure: (starting material 5-nitroindoline is based on 250 grams, and solvent is made into about 1.5～2 liters 1M solution)
1. earlier reaction temperature is reduced to-5～15 ℃ (ice bath), (1～6.eq) inserts in the reaction bulb, adds about 0.5 liter chloroform dissolving iron chloride earlier, stir about 10～15 minutes with the iron chloride that weighs up again;
2. again with the starting material 5-nitroindoline (1eq that weighs up, 200 grams), add in iron chloride/chloroformic solution in batches, added required time about 0.5～5 hour in batches, need the limit to add 5-nitroindoline limit solubilizer (chloroform) in the process, not so the 5-nitroindoline can stick to reaction bulb wall (because the reaction of indoles and iron chloride is very violent, so at the beginning will necessary control reaction temperature);
3. reaction (process) device needs logical nitrogen, adds once ice in about 2 hours, and the reaction time is to keep-5～15 ℃ in 6 hours, allows its room temperature of getting back to naturally overnight;
4. when collecting product, need earlier solvent (chloroform) to be filtered to collect filter cake, again filter cake is added about 1～4 liter washing earlier, because meeting heat release this moment, must carry out ice bath so wash certainly when initial, avoid the product can heat release and splash everywhere, treat that the reaction of product and water relaxes after, product is filtered again and with clear water washing several in batches;
5. at last product is inserted vacuum drying oven oven dry (60～100 ℃ of temperature).
Embodiment three: polyaniline synthetic
Experimental procedure:
1. two ammonium sulfate of peroxide (11.5 gram) and hydrochloric acid (HCl) (1M, 200 milliliters) wiring solution-forming, process needs to be kept being about 1 ℃ by ice bath;
2. aniline (aniline) (20 milliliters) and hydrochloric acid (HCl) (1M, 300 milliliters) wiring solution-forming, process needs to be kept being about 1 ℃ by ice bath;
3. prepare about 750 milliliters reaction bulb, the aniline (aniline) and the mixed solution of hydrochloric acid (HCl) are inserted in the reaction bulb, mixed solution with two ammonium sulfate of peroxide and hydrochloric acid (HCl) slowly is added dropwise in the aniline solution again, about 1 minute of process, and whole mixed liquor stirred 1.5 hours again;
4. when collecting product, filter out blackish green sediment, (1M) wash product with hydrochloric acid (HCl) again, till filtrate is colourless with funnel;
5. the product that washes is again with NH
4The OH aqueous solution (0.1M, 500 milliliters) clean with obtain polyaniline (Polyaniline, PAN).
Embodiment four: prescription and the manufacturing technology (adopting sulfuric acid activation positive and negative electrode material) that contains the proton secondary cell of poly-indoles/polyaniline of the present invention
Positive electrode adopts poly-5-nitroindoline or active conducting polymer of nitrated poly-indoles and conductive carbon material blending, wherein conductive carbon material accounts for 1～40% of material total weight after this blending, add solvent subsequently and stir back drying under vacuum condition, last the sieving of pulverizing then, the electrolyte sulfuric acid that adds 0.2～0.5 mole again stirs into cream, and it is online to be uniformly coated on current collection, removes unnecessary electrolyte sulfuric acid, promptly obtains positive electrode;
Negative material adopts polyaniline and the conductive carbon material blending that can be conductive carbon black, graphite whisker, carbon nano-fiber or CNT (carbon nano-tube), wherein conductive carbon material accounts for 1～40% of material total weight after this blending, add solvent subsequently also, it is dry under vacuum condition to stir the back, last the sieving of pulverizing then, the sulfuric acid that adds 0.2～0.5 mole again stirs into cream, and it is online to be uniformly coated on current collection, remove unnecessary electrolyte sulfuric acid, promptly obtain negative material;
Barrier film adopts adhesive-bonded fabric (as PP, PP/PE/PP), and both positive and negative polarity and electrolyte all adopt the electrolyte sulfuric acid of same concentrations, adopt positive limiting quantity during assembling, the mode that negative pole is excessive, and controlling each unit has suitable electrolyte content.Each the unit production procedure of combination secondary cell as shown in Figure 3.
In present embodiment, when battery volume of the present invention is 1.5cm * 5cm * 1cm, about 13.5 grams of its weight, capacitance is 500mAh, this moment, cell voltage was 1.25 volts.
Embodiment five: prescription and the manufacturing technology (employing contains the acid organic electrolyte activation positive and negative electrode material of organic bath) that contains the proton secondary cell of poly-indoles/polyaniline of the present invention
Positive electrode is with gathering 5-nitroindoline or active conducting polymer of nitrated poly-indoles and conductive carbon material blending, wherein conductive carbon material accounts for 1～40% of material total weight after this blending, add solvent subsequently and stir back drying under vacuum condition, last the sieving of pulverizing then, the organic acid electrolyte that adds 3～5 moles again stirs into cream, and it is online to be uniformly coated on current collection, removes unnecessary organic acid electrolyte under 1370KPa pressure, promptly obtains positive electrode;
Negative material with polyaniline with can be the conductive carbon material blending of conductive carbon black, graphite whisker, carbon nano-fiber or CNT (carbon nano-tube), wherein conductive carbon material accounts for 1～40% of material total weight after this blending, add solvent subsequently and stir back drying under vacuum condition, last the sieving of pulverizing then, the organic acid electrolyte that adds 0.2～5 mole again stirs into cream, and it is online to be uniformly coated on current collection, removes unnecessary organic acid electrolyte, promptly obtains negative material;
Barrier film adopts the micropore separation membrane of polypropylene, polyethylene and polypropylene co-polymer, nylon, polyether sulfone or fluorine resin, and both positive and negative polarity and electrolyte all adopt the organic bath (including propyl carbonate (propyl carbonate), ethyl carbonate (ethyl carbonate), ammonium dihydrogen phosphate (mono-ammonium phosphate), lithium perchlorate (lithium perchlorate), DMF and TEATFB etc.) of same concentrations.
In present embodiment, when battery volume of the present invention is 3.5cm * 5.5cm * 0.8cm, about 100 grams of its weight, capacitance is 4000mAh, this moment, cell voltage was 4 volts.
Embodiment five～six macromolecule secondary cell discharge performances of the present invention, please refer to shown in Figure 4, when advance copy is invented 1.2 grammes per square metre batteries under the different constant-current discharges of 100mA～1A, when 3.5～4.2 volts of voltages, the specific discharge capacity that can discharge is about 200～250mAh/g.Characteristic and lithium storage battery, lead acid accumulator performance that the battery of the present invention of embodiment four～five is relevant are compared as follows:
Remarks: * organic electrolysis formula of liquid-1. contain 1.0M tetrem alkane quaternary amine (TEATFB) in the PC organic bath 2. contains 1.0M tetrem alkane quaternary amine (TEATFB) in the AN organic bath.
Design focal point of the present invention is how to make anodal poly-nitroindoline to have powerful anion adsorption capacity and the electric conductivity that promotes battery combination, and then promotes the discharging efficiency of proton in the electrode for secondary battery.In addition, the present invention also designs preferable organic bath solvent, and the operating voltage that not only can increase the proton secondary cell reaches more than 3 volts, promotes its quality and volumetric capacitance amount simultaneously.Poly-nitroindoline/the polyaniline of preferred embodiment utilization of the present invention is active positive and negative electrode, the composition of positive and negative electrode is with micron order even the common composition of nano-level conducting carbon black or CNT (carbon nano-tube) institute, electrolyte adopts Bronsted acid electrolyte aqueous solution composition or organic electrolyte solution composition etc. in addition, its electromotive force of the organic secondary cell of the resulting proton of the latter can reach and be beset with more than the spy, its charge and discharge circulation life can reach more than 100,000 times, the charge and discharge process electromotive force changes about 3.5 volts between 4 volts the time, the capacity that discharges and recharges can reach more than 90%, and the quality of battery can reach 240mAh/g than capacitance.
The above description of this invention is illustrative, and nonrestrictive, and those skilled in the art is understood, and can carry out many modifications, variation or equivalence to it within spirit that claim limits and scope, but they will fall within the scope of protection of the present invention all.
Claims (30)
1. combination electrode material, it is characterized in that, with nitrogenous electroconductive polymer and conductive carbon material blending, this electroconductive polymer is poly quinoline, polyphenylene quinoxaline, polycarbazole, polypyridine, polypyrrole, polyaniline or poly-indoles, this conductive carbon material accounts for 1%～40% of material total weight after this blending, and the material after the blending is activated with the acidic electrolysis bath that 0.2M～5M contains hydrogen ion again.
2. combination electrode material as claimed in claim 1, it is characterized in that this nitrogenous electroconductive polymer is for containing the poly-indoles of nitro, the poly-indoles of cyano-containing, the poly-indoles of halogen-containing base, the poly-indoles of boracic acidic group, the poly-indoles of phosphorous acidic group, contain the poly-indoles of sulfonic group, containing poly-indoles of cyanic acid base or the poly-indoles of isocyanato group containing.
3. combination electrode material as claimed in claim 2 is characterized in that, this nitrogenous electroconductive polymer is for containing the poly-indoles of nitro.
4. as claim 1 or 2 or 3 described combination electrode materials, it is characterized in that, this conductive carbon material is conductive carbon black, graphite whisker, amorphous carbon, activated carbon, mesoporous carbon, porous carbon fiber, carbon nano-fiber, CNT (carbon nano-tube) or carbon fiber, and its particle diameter is less than 10 microns.
5. combination electrode material as claimed in claim 4 is characterized in that this acidic electrolysis bath contains sulfuric acid.
6. combination electrode material as claimed in claim 4 is characterized in that this acidic electrolysis bath contains acid organic electrolyte.
7. secondary cell, it is characterized in that, use a positive electrode, this positive electrode is with nitrogenous electroconductive polymer and conductive carbon material blending, this electroconductive polymer is poly quinoline, polyphenylene quinoxaline, polycarbazole, polypyridine, polypyrrole, polyaniline or poly-indoles, this conductive carbon material accounts for 1%～40% of material total weight after this blending, and the material after the blending is activated with the acidic electrolysis bath that 0.2M～5M contains hydrogen ion again.
8. secondary cell as claimed in claim 7, it is characterized in that this poly-indoles electroconductive polymer is for containing the poly-indoles of nitro, the poly-indoles of cyano-containing, the poly-indoles of halogen-containing base, the poly-indoles of boracic acidic group, the poly-indoles of phosphorous acidic group, contain the poly-indoles of sulfonic group, containing poly-indoles of cyanic acid base or the poly-indoles of isocyanato group containing.
9. secondary cell as claimed in claim 8 is characterized in that, this electroconductive polymer is best for containing the poly-indoles of nitro.
10. as claim 7 or 8 or 9 described secondary cells, it is characterized in that, this conductive carbon material is conductive carbon black, graphite whisker, amorphous carbon, activated carbon, mesoporous carbon, porous carbon fiber, carbon nano-fiber, CNT (carbon nano-tube) or carbon fiber, and its particle diameter is less than 10 microns.
11. secondary cell as claimed in claim 10 is characterized in that, this acidic electrolysis bath contains sulfuric acid.
12. secondary cell as claimed in claim 10 is characterized in that, this acidic electrolysis bath contains acid organic electrolyte.
13. secondary cell as claimed in claim 12 is characterized in that, this organic electrolyte includes propyl carbonate, ethyl carbonate, ammonium dihydrogen phosphate, lithium perchlorate, dimethyl formamide and tetrachloro tetraethylammonium borate salt.
14. a secondary cell is characterized in that, comprises:
One positive electrode, it is with electroconductive polymer and conductive carbon material blending, this electroconductive polymer is poly quinoline, polyphenylene quinoxaline, polycarbazole, polypyridine, polypyrrole, polyaniline or poly-indoles, this conductive carbon material accounts for 1%～40% of material total weight after this blending, and the material after the blending is activated with the acidic electrolysis bath that 0.2M～5M contains hydrogen ion again;
One negative material, it is with electroconductive polymer and conductive carbon material blending, this electroconductive polymer is poly-phenyl ethene, poly-furans, polysulfide, polythiophene, poly quinoline, polyphenylene quinoxaline, polycarbazole, polypyridine, polypyrrole, polyaniline or the poly-indoles stretched, this conductive carbon material accounts for 1%～40% of material total weight after this blending, and the material after the blending is activated with the acidic electrolysis bath that 0.2M～5M contains hydrogen ion again;
One barrier film, it separates the positive and negative electrode material;
One electrolyte, it is arranged at this positive and negative electrode storeroom, and this electrolyte includes aqueous sulfuric acid or acid organic electrolyte;
One cathode collector, it contacts with this positive electrode;
One anode collector, it contacts with this negative material.
15. secondary cell as claimed in claim 14, it is characterized in that the poly-indoles electroconductive polymer of this positive electrode is for containing the poly-indoles of nitro, the poly-indoles of cyano-containing, the poly-indoles of halogen-containing base, the poly-indoles of boracic acidic group, the poly-indoles of phosphorous acidic group, contain the poly-indoles of sulfonic group, containing poly-indoles of cyanic acid base or the poly-indoles of isocyanato group containing.
16. secondary cell as claimed in claim 14 is characterized in that, the electroconductive polymer of this negative material is nitrogenous electroconductive polymer, includes poly quinoline, polyphenylene quinoxaline, polycarbazole, polypyridine, polypyrrole, polyaniline or poly-indoles.
17. secondary cell as claimed in claim 15 is characterized in that, the electroconductive polymer of this positive electrode is for containing the poly-indoles of nitro.
18. secondary cell as claimed in claim 17 is characterized in that, the electroconductive polymer of this negative material is a polyaniline.
19. as claim 14 to 18 each described secondary cell wherein, it is characterized in that, this conductive carbon material is conductive carbon black, graphite whisker, amorphous carbon, activated carbon, mesoporous carbon, porous carbon fiber, carbon nano-fiber, CNT (carbon nano-tube) or carbon fiber, and its particle diameter is less than 10 microns.
20. secondary cell as claimed in claim 19 is characterized in that, this barrier film is the micropore separation membrane of polypropylene, polyethylene and polypropylene co-polymer, nylon, polyether sulfone or fluorine resin, and its hole is less than 50 microns.
21. secondary cell as claimed in claim 20 is characterized in that, this organic electrolyte includes propyl carbonate, ethyl carbonate, ammonium dihydrogen phosphate, lithium perchlorate, dimethyl formamide and tetrachloro tetraethylammonium borate salt.
22. secondary cell as claimed in claim 21 is characterized in that, the electrolyte of this secondary cell further includes a nano inoganic particle.
23. secondary cell as claimed in claim 22 is characterized in that, this nano inoganic particle is nano titanium oxide, nano silicon or nano fullerene.
24. secondary cell as claimed in claim 23 is characterized in that, this positive and negative electrode current-collector is wire netting, metal forming or conductive carbon material.
25. secondary cell as claimed in claim 24 is characterized in that, this wire netting is gold-plated copper mesh, gold-plated aluminium net, copper mesh or aluminium net, and this metal forming is gold-plated Copper Foil, gold-plated aluminium foil, Copper Foil or aluminium foil.
26. secondary cell as claimed in claim 24 is characterized in that, the conductive carbon material of this positive and negative electrode current-collector is carbon fiber adhesive-bonded fabric, carbon nano-fiber adhesive-bonded fabric or graphite whisker fiber adhesive-bonded fabric.
27. secondary cell as claimed in claim 14 is characterized in that, this barrier film is the micropore separation membrane of polypropylene, polyethylene and polypropylene co-polymer, nylon, polyether sulfone or fluorine resin, and its hole is less than 50 microns.
28. secondary cell as claimed in claim 14 is characterized in that, this organic electrolyte includes propyl carbonate, ethyl carbonate, ammonium dihydrogen phosphate, lithium perchlorate, dimethyl formamide and tetrachloro tetraethylammonium borate salt.
29. secondary cell as claimed in claim 14 is characterized in that, the electrolyte of this secondary cell further includes a nano inoganic particle.
30. secondary cell as claimed in claim 14 is characterized in that, this positive and negative electrode current-collector is wire netting, metal forming or conductive carbon material.
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| CN103311512A (en) * | 2013-05-27 | 2013-09-18 | 浙江大学 | Preparation method of indole-modified carbon sulfur-coated and compound lithium sulfur battery anode material |
| CN103958742A (en) * | 2011-10-27 | 2014-07-30 | 日立金属株式会社 | Method for manufacturing porous aluminum foil, porous aluminum foil, positive electrode collector for electricity storage device, electrode for electricity storage device, and electricity storage device |
| CN109742343A (en) * | 2018-12-20 | 2019-05-10 | 中南民族大学 | High-valued electrode active material of nylon engineering plastic and preparation method thereof |
| CN113264517A (en) * | 2021-04-30 | 2021-08-17 | 暨南大学 | Mesoporous carbon sphere and preparation method and application thereof |
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| JP2001035494A (en) * | 1999-07-22 | 2001-02-09 | Nec Corp | Secondary battery using indole polymer and capacitor |
| US20050042522A1 (en) * | 2003-08-08 | 2005-02-24 | Max-Planck-Gesellschaft Zur Forderung Der Wissenschaften E.V., A German Corporation | Non-aqueous electrolyte for use in a battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001035494A (en) * | 1999-07-22 | 2001-02-09 | Nec Corp | Secondary battery using indole polymer and capacitor |
| US20050042522A1 (en) * | 2003-08-08 | 2005-02-24 | Max-Planck-Gesellschaft Zur Forderung Der Wissenschaften E.V., A German Corporation | Non-aqueous electrolyte for use in a battery |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103958742A (en) * | 2011-10-27 | 2014-07-30 | 日立金属株式会社 | Method for manufacturing porous aluminum foil, porous aluminum foil, positive electrode collector for electricity storage device, electrode for electricity storage device, and electricity storage device |
| CN103958742B (en) * | 2011-10-27 | 2016-07-13 | 日立金属株式会社 | The manufacture method of porous aluminium foil, porous aluminium foil, electrical storage device positive electrode collector, electrode for power storage device, and electrical storage device |
| US9812700B2 (en) | 2011-10-27 | 2017-11-07 | Hitachi Metals, Ltd. | Method for producing porous aluminum foil, porous aluminum foil, positive electrode current collector for electrical storage devices, electrode for electrical storage devices, and electrical storage device |
| CN103311512A (en) * | 2013-05-27 | 2013-09-18 | 浙江大学 | Preparation method of indole-modified carbon sulfur-coated and compound lithium sulfur battery anode material |
| CN103311512B (en) * | 2013-05-27 | 2015-04-15 | 浙江大学 | Preparation method of indole-modified carbon sulfur-coated and compound lithium sulfur battery anode material |
| CN109742343A (en) * | 2018-12-20 | 2019-05-10 | 中南民族大学 | High-valued electrode active material of nylon engineering plastic and preparation method thereof |
| CN113264517A (en) * | 2021-04-30 | 2021-08-17 | 暨南大学 | Mesoporous carbon sphere and preparation method and application thereof |
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