CN103093970B - A kind of electric energy energy storage film and preparation method thereof, electric energy storage device - Google Patents
A kind of electric energy energy storage film and preparation method thereof, electric energy storage device Download PDFInfo
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- CN103093970B CN103093970B CN201210591393.9A CN201210591393A CN103093970B CN 103093970 B CN103093970 B CN 103093970B CN 201210591393 A CN201210591393 A CN 201210591393A CN 103093970 B CN103093970 B CN 103093970B
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Abstract
Embodiments provide a kind of electric energy energy storage film, with poly-metanilic acid lithium for skeleton, count by ratio of weight and the number of copies, comprising: poly-metanilic acid lithium 110 ~ 120 parts, thickener 1 ~ 15 part, and binding agent 1 ~ 15 part.This electric energy energy storage film can deposit without electrolyte in case directly and collector form electric energy storage device and use, unit are magnitude of the stored charge is high, energy per volume density is high, environmental protection, with low cost, is suitable for large-scale production.The embodiment of the present invention additionally provides the preparation method of this electric energy energy storage film, comprises the poly-metanilic acid lithium of electrochemical polymerization method preparation, and the process of method of electrostatic spinning film forming, obtained electric energy energy storage film.The embodiment of the present invention additionally provides the electric energy storage device comprising this electric energy energy storage film, and structure is simple, improves the electric energy energy storage capacity of secondary cell when applying in the secondary battery, makes secondary cell can be applicable to high-power sparking and standby electrical domain.
Description
Technical field
The present invention relates to energy field, particularly relate to a kind of electric energy energy storage film and preparation method thereof, electric energy storage device.
Background technology
Electric energy storage device as the alternative energy of one for electric solution, it is widely used in no-break power unit (UPS) power supply, and it is also applied to communication electronics field as power-type power supply and as the transport field such as flywheel, hybrid electric vehicle.Due to climate change and energy shortage, electric power energy stores and management just becomes urgent problem.Therefore, people more and more recognize the negative effect of traditional energy to environment, promote people thus and constantly seek alternative green sustainable energy.
Current energy storage technology is mainly fixed against the secondary cells such as lead-acid battery, ickel-cadmium cell, Ni-H cell and lithium ion battery, and these secondary cells are made up of positive pole, negative pole, barrier film, housing and the electrolyte containing ion conducting medium usually.This kind of energy storage technology be based upon comprise electrolyte complicated structure basis on, therefore there is production scale and be difficult to scale up the problem high with cost, and exist electrolyte reveal hidden danger, may destroy environment.
Ultracapacitor (being double electric layer capacitor again) is a kind of new electric energy energy storage device, be made up of a pair polarizable electrode and electrolyte, its charge-discharge principle is: after apply electric field on two electrodes, anions and canons in electrolyte moves respectively to positive and negative electrode, forms electric double layer at the interface of electrode and electrolyte contacts; After cancelling electric field, the positive and negative electric charge on electrode and the counterions in electrolyte attract mutually and electric double layer are stablized, and produce metastable potential difference between positive and negative electrode; When the two poles of the earth are communicated with external circuit, the charge migration on electrode and in external circuit generation current, become electric neutrality in the Ion transfer in electrolyte to electrolyte.Although ultracapacitor in capacitance etc. relatively other secondary cells had significant progress, it still meets the application requirement of high-power spark field and standby electrical domain not.This is because, the size that the capacitance of ultracapacitor is less than greatly electric double layer region area is directly proportional (electric charges of those unordered no plans in non-electric double layer region do not participate in energy storage), and the interface size of this electric double layer region area and electrode and electrolyte contacts is limited and electric double layer region is very thin, therefore, the electricity that electric double layer region can store is subject to certain restrictions.
Given this, the simple structure of development of new, cheap, environmental protection and the efficient electric energy storage device of energy storage and dependency structure material seem very important as early as possible.
Summary of the invention
In view of this, embodiment of the present invention first aspect provides a kind of electric energy energy storage film, its can deposit without electrolyte in case directly and collector form electric energy storage device and use, unit are magnitude of the stored charge is high, environmental protection, with low cost, can large-scale production be suitable for.Embodiment of the present invention second aspect provides the preparation method of described electric energy energy storage film.The embodiment of the present invention third aspect provides the electric energy storage device comprising described electric energy energy storage film, and this electric energy storage device structure is simple, can be suitable for large-scale production.
First aspect, embodiments provides a kind of electric energy energy storage film, described electric energy energy storage film with poly-metanilic acid lithium for skeleton, count by ratio of weight and the number of copies, comprise: poly-metanilic acid lithium 110 ~ 120 parts, thickener 1 ~ 15 part, and binding agent 1 ~ 15 part.
Described electric energy energy storage film is nanometer filamentary material, with poly-metanilic acid lithium for skeleton, auxiliary appropriate thickener and binding agent are filmogen, have good toughness and flexibility, can following process be various pattern (such as curling and stretch).
(Poly-m-aminobenzenesulfonic lithium, is abbreviated as P-m-ABSA to described poly-metanilic acid lithium
-: Li
+) can by metanilic acid (m-aminobenzenesulfonic acid, is abbreviated as m-ABSA) and lithium compound (such as LiOH, LiClO
4and Li
2cO
3) formed by electrochemical polymerization polymerization.
Preferably, described thickener is polyacrylic acid (PAA) or sodium carboxymethylcellulose (CMC).
Preferably, described binding agent is polytetrafluoroethylene (PTFE), polyethylene (PE), carboxylic propyl methocel (HPMC), butadiene-styrene rubber breast (SBR), polyvinyl alcohol (PVA) or polyethylene glycol oxide (PEO).
Preferably, described solvent is 1-METHYLPYRROLIDONE (NMP).
Preferably, count by ratio of weight and the number of copies, described electric energy energy storage film comprises: poly-metanilic acid lithium 115 parts, thickener 10 parts, binding agent 10 parts.
Preferably, the thickness of described electric energy energy storage film is 0.10 ~ 0.15mm.
The preparation method that described a kind of electric energy energy storage film provides according to embodiment of the present invention second aspect obtains.
The electric energy energy storage film that embodiment of the present invention first aspect provides can deposit without electrolyte in case directly and collector form electric energy storage device and use.Under room temperature condition, polymer poly metanilic acid lithium cationic Li
+be in electronegative poly-metanilic acid root P-m-ABSA
-around; When starting to charge, movable cation Li
+to Electrode Negative be shifted to, occur the polarization phenomena departing from former poised state, meanwhile, as the poly-metanilic acid root P-m-ABSA of high molecular polymer skeleton
-fixing not movement, therefore at Li
+and P-m-ABSA
-between will there is certain electrical potential difference, whole electric energy energy storage film forms a polarization body, and electric energy is stored in electric energy energy storage film in this form; When electric energy energy storage film is in discharge condition, cation Li
+electronegative poly-metanilic acid root P-m-ABSA can be come back to again
-around, whole electric energy energy storage film is made to be in electric neutrality state.As can be seen here, described electric energy energy storage film, based on bulk polairzed area mechanism storage power, overcomes the limitation that ultracapacitor only leans on the electric double layer region energy storage at electrode and electrolyte contacts interface, and does not need the outer electrolyte that adds to transmit cation Li
+.The electric energy energy storage film unit are magnitude of the stored charge that embodiment of the present invention first aspect provides is high, energy per volume density is high, environmental protection, with low cost, can be suitable for large-scale production.
Second aspect, embodiments provides a kind of preparation method of electric energy energy storage film, comprises the following steps:
In molar ratio for the ratio of 10:12 ~ 15 gets metanilic acid and lithium compound LiOH, LiClO
4or Li
2cO
3be mixed with mixed solution, the pH value of described mixed solution is regulated to be 2 ~ 5, under nitrogen protection, by electrochemical polymerization work station, three-electrode system polymerization is carried out to mixed solution, applying voltage is-0.5 ~ 1.0V, and polymerization time is 1.5 ~ 2h, at the obtained poly-metanilic acid lithium of working electrode surface;
Count by ratio of weight and the number of copies, get poly-metanilic acid lithium 110 ~ 120 parts respectively, thickener 1 ~ 15 part, binding agent 1 ~ 15 part, and solvent 80 ~ 150 parts, be mixed with the miscible body of stream-like after mixing, by method of electrostatic spinning, miscible for described stream-like body is carried out film forming process, obtained electric energy energy storage film.
Described three-electrode system comprises work electrode, to electrode and reference electrode.Preferably, work electrode is natural electrode sheet, artificial graphite electrode sheet or Ti electrode sheet, is platinum plate electrode to electrode, and reference electrode is saturated calomel electrode.
In the process of the poly-metanilic acid lithium of described electrochemical polymerization method preparation, electrochemical oxidation reactions is there is in monomer metanilic acid and lithium compound within the scope of voltage range, class polyaniline type conducting high polymers thing is formed by the mode of chain polymerization at working electrode surface, π in an acidic solution on high molecular polymer main chain-pi-conjugated electron region and proton form electron conduction passage, and on phenyl ring skeleton side chain, negative electrical charge sulfonic acid group forms ionic conducting path.On the main chain under non-acidic conditions, proton is replaced, forms sub-quinoid structure, loses π-pi-conjugated system and loses this conductive channel.But Ionized sulfonic acid group belongs to Ionic conductivity body on side chain, the electric conductivity of leading poly-metanilic acid lithium under neutral or basic conditions.
Whole electrochemical polymerization process carries out under nitrogen protection, can be logical constant flow rate high pure nitrogen in electrochemical reaction cell.The oxygen in electrolyte can be removed on the one hand, prevent the structural destruction of product; To ventilate on the other hand the stirring action that can play electrolyte, be beneficial to the carrying out of electrochemical polymerization reaction, form the material of compact texture.
Preferably, lithium compound is Li
2cO
3.Li
2cO
3abundance on the one hand, low price, easily obtains, on the other hand it has relatively friendly water-soluble, can in neutral aqueous solution system and monomer metanilic acid dissolve each other, strengthen whole system conductivity, accelerate the growth of electric energy energy storage film, improve the homogeneity of electric energy energy storage film.
Preferably, the pH value of described mixed solution is by adding hydrochloric acid or nitric acid adjustment.
Preferably, described thickener is polyacrylic acid (PAA) or sodium carboxymethylcellulose (CMC).More preferably, described thickener is polyacrylic acid (PAA), and molecular weight is between 2000-3500.
Preferably, described binding agent is polytetrafluoroethylene (PTFE), polyethylene (PE), carboxylic propyl methocel (HPMC), butadiene-styrene rubber breast (SBR), polyvinyl alcohol (PVA) or polyethylene glycol oxide (PEO).More preferably, described binding agent is polyethylene (PE), and molecular weight is between 5000-6000.
Preferably, described solvent is 1-METHYLPYRROLIDONE (NMP).
Preferably, get poly-metanilic acid lithium 115 parts respectively, thickener 10 parts, binding agent 10 parts, and solvent 100 parts.
Preferably, be mixed with the miscible body of stream-like after mixing and comprise: thickener is dissolved in solvent and prepares sizing material, in sizing material, add poly-metanilic acid lithium and binding agent, the obtained miscible body of stream-like after stirring.
Preferably, by method of electrostatic spinning, miscible for described stream-like body is carried out film forming process to comprise: with aluminium foil for accepting electrode, by the mode of electrostatic spinning miscible for described stream-like body is sprayed on and describedly accepts electrode surface film forming, from accepting electrode surface, film is taken off subsequently, dry, 10ml ~ 25ml syringe and supporting syringe needle is selected in described electrostatic spinning process, high-voltage DC power supply regulation voltage is 13kv ~ 14.5kv, syringe needle is 20 ~ 25cm with the distance accepting electrode, and spinning flow is 0.15 ~ 0.2 ml/hour.
More preferably, from accepting electrode surface, film being taken off by standard scraper blade coating, to be placed in baking oven in 60 ~ 80 DEG C of dry out solvent, subsequently the film of drying to be placed in absolute ethyl alcohol and to soak, then put into vacuum drying oven and dry.
Described method of electrostatic spinning becomes membrane treatment process simple, film forming is even, easy to operate, masking time short and environmental friendliness, obtained electric energy energy storage film is nanometer filamentary material, and with poly-metanilic acid lithium for skeleton, auxiliary appropriate thickener and binding agent are filmogen, having good toughness and flexibility, can following process be various pattern (such as curling and stretch etc.).
Preferably, count by ratio of weight and the number of copies, described electric energy energy storage film comprises: poly-metanilic acid lithium 115 parts, thickener 10 parts, binding agent 10 parts, and solvent 100 parts.
Preferably, the thickness of described electric energy energy storage film is 0.10 ~ 0.15mm.
The preparation method of the electric energy energy storage film that embodiment of the present invention second aspect provides has obtained a kind of novel electric energy energy storage film, this preparation method's environmental protection, with low cost, can be suitable for large-scale production.
The third aspect, embodiments provide a kind of electric energy storage device, described electric energy storage device is made up of the plus plate current-collecting body set gradually, electric energy energy storage film and negative current collector, described electric energy energy storage film with poly-metanilic acid lithium for skeleton, count by ratio of weight and the number of copies, comprising: poly-metanilic acid lithium 110 ~ 120 parts, thickener 1 ~ 15 part, and binding agent 1 ~ 15 part, plus plate current-collecting body and negative current collector are compressing tablet native graphite, Delanium or Graphene.
Described electric energy storage device applies constant pressure by tablet press machine and obtains.Preferably, described constant pressure is 7.5 ~ 8Mpa.Preferably, the compacted depth of described electric energy storage device is 1mm.
Preferably, the particle diameter of native graphite is 10 ~ 30 μm, and include the low-crystallinity turbostratic carbon shell of coated natural graphite, crystal layer spacing is 0.335nm ~ 0.346nm, and tap density is 0.95 ~ 1.05g/ml, and specific area is 4.0 ~ 7.5m
2/ g; The particle diameter of Delanium is 10 ~ 20 μm, and crystal layer spacing is 0.336nm ~ 0.362nm, and tap density is 0.90 ~ 1.21g/ml, and specific area is 5.0 ~ 9.5m
2/ g; Graphene is of a size of 20nm ~ 2 μm, is multi-layer graphene, and the number of plies is 3 ~ 5 layers.
The preparation method that described electric energy energy storage film provides according to embodiment of the present invention second aspect obtains.
The electric energy storage device that the embodiment of the present invention third aspect provides directly is combined to form for depositing electric energy energy storage film and collector in case without electrolyte, and structure is simple, and environmental protection is with low cost, can be suitable for large-scale production.Wherein, electric energy energy storage film unit are magnitude of the stored charge is high, energy per volume density is high, plus plate current-collecting body and negative current collector conductance high, positive and negative collector and electric energy energy storage film affinity high, higher high rate performance and power-performance can be reached.
The advantage of the embodiment of the present invention will partly be illustrated in the following description, and a part is apparent according to specification, or can be known by the enforcement of the embodiment of the present invention.
Accompanying drawing explanation
The schematic diagram of the electric energy energy storage film energy storage principle that Fig. 1 provides for embodiment of the present invention first aspect.
The schematic diagram (constant-resistance judgement) of the electric energy energy storage film discharge principle that Fig. 2 provides for embodiment of the present invention first aspect.
Electrostatic spinning apparatus figure in the preparation method of the electric energy energy storage film that Fig. 3 provides for embodiment of the present invention second aspect.
Embodiment
The following stated is the preferred implementation of the embodiment of the present invention; should be understood that; for those skilled in the art; under the prerequisite not departing from embodiment of the present invention principle; can also make some improvements and modifications, these improvements and modifications are also considered as the protection range of the embodiment of the present invention.
Multiple embodiment is divided to be further detailed the embodiment of the present invention below.The embodiment of the present invention is not limited to following specific embodiment.In the scope of constant principal right, carrying out that can be suitable is changed and implements.
Embodiment of the present invention first aspect provides a kind of electric energy energy storage film, its can deposit without electrolyte in case directly and collector form electric energy storage device and use, unit are magnitude of the stored charge is high, environmental protection, with low cost, can be suitable for large-scale production.Embodiment of the present invention second aspect provides the preparation method of described electric energy energy storage film.The embodiment of the present invention third aspect provides the electric energy storage device comprising described electric energy energy storage film, and this electric energy storage device structure is simple, can be suitable for large-scale production.Embodiment of the present invention fourth aspect provides the application in the secondary battery of this electric energy storage device.
First aspect, embodiments provides a kind of electric energy energy storage film, described electric energy energy storage film with poly-metanilic acid lithium for skeleton, count by ratio of weight and the number of copies, comprise: poly-metanilic acid lithium 110 ~ 120 parts, thickener 1 ~ 15 part, and binding agent 1 ~ 15 part.
Described electric energy energy storage film is nanometer filamentary material, with poly-metanilic acid lithium for skeleton, auxiliary appropriate thickener and binding agent are filmogen, have good toughness and flexibility, can following process be various pattern (such as curling and stretch).
(Poly-m-aminobenzenesulfonic lithium, is abbreviated as P-m-ABSA to described poly-metanilic acid lithium
-: Li
+) can by metanilic acid (m-aminobenzenesulfonic acid, is abbreviated as m-ABSA) and lithium compound (such as LiOH, LiClO
4and Li
2cO
3) formed by electrochemical polymerization polymerization.
Described thickener is polyacrylic acid (PAA, molecular weight is 2000 ~ 3500) or sodium carboxymethylcellulose (CMC, molecular weight is 80000 ~ 150000).
Described binding agent is polytetrafluoroethylene (PTFE, molecular weight is 100000 ~ 150000), polyethylene (PE, molecular weight is 5000 ~ 6000), carboxylic propyl methocel (HPMC, molecular weight is 324), butadiene-styrene rubber breast (SBR, molecular weight is 150000 ~ 200000), polyvinyl alcohol (PVA, molecular weight is 16000 ~ 20000) or polyethylene glycol oxide (PEO, molecular weight is molecular weight is 100000 ~ 120000).
Described solvent is 1-METHYLPYRROLIDONE (NMP).
Count by ratio of weight and the number of copies, described electric energy energy storage film comprises: poly-metanilic acid lithium 115 parts, thickener 10 parts, binding agent 10 parts.
The thickness of described electric energy energy storage film is 0.10 ~ 0.15mm.
The preparation method that described a kind of electric energy energy storage film provides according to embodiment of the present invention second aspect obtains.
The electric energy energy storage film that embodiment of the present invention first aspect provides can deposit without electrolyte in case directly and collector form electric energy storage device and use.The schematic diagram of the electric energy energy storage film energy storage principle that Fig. 1 provides for embodiment of the present invention first aspect, 1 is Li
+, 2 is poly-metanilic acid root P-m-ABSA
-skeleton, 3 is-SO
3 -, 4 is negative current collector, and 5 is plus plate current-collecting body.The schematic diagram (constant-resistance judgement) of the electric energy energy storage film discharge principle that Fig. 2 provides for embodiment of the present invention first aspect.Under room temperature condition, polymer poly metanilic acid lithium cationic Li
+be in electronegative poly-metanilic acid root P-m-ABSA
-around; When starting to charge, movable cation Li
+to Electrode Negative be shifted to, occur the polarization phenomena departing from former poised state, meanwhile, as the poly-metanilic acid root P-m-ABSA of high molecular polymer skeleton
-fixing not movement, therefore at Li
+and P-m-ABSA
-between will there is certain electrical potential difference, whole electric energy energy storage film forms a polarization body, and electric energy is stored in electric energy energy storage film in this form; When electric energy energy storage film is in discharge condition, cation Li
+electronegative poly-metanilic acid root P-m-ABSA can be come back to again
-around, whole electric energy energy storage film is made to be in electric neutrality state.As can be seen here, described electric energy energy storage film, based on bulk polairzed area mechanism storage power, overcomes the limitation that ultracapacitor only leans on the electric double layer region energy storage at electrode and electrolyte contacts interface, and does not need the outer electrolyte that adds to transmit cation Li
+.The electric energy energy storage film unit are magnitude of the stored charge that embodiment of the present invention first aspect provides is high, energy per volume density is high, environmental protection, with low cost, can be suitable for large-scale production.
Second aspect, embodiments provides a kind of preparation method of electric energy energy storage film, comprises the following steps:
In molar ratio for the ratio of 10:12 ~ 15 gets metanilic acid and lithium compound LiOH, LiClO
4or Li
2cO
3be mixed with mixed solution, the pH value of described mixed solution is regulated to be 2 ~ 5, under nitrogen protection, by electrochemical polymerization work station, three-electrode system polymerization is carried out to mixed solution, applying voltage is-0.5 ~ 1.0V, and polymerization time is 1.5 ~ 2h, at the obtained poly-metanilic acid lithium of working electrode surface;
Count by ratio of weight and the number of copies, get poly-metanilic acid lithium 110 ~ 120 parts respectively, thickener 1 ~ 15 part, binding agent 1 ~ 15 part, and solvent 80 ~ 150 parts, be mixed with the miscible body of stream-like after mixing, by method of electrostatic spinning, miscible for described stream-like body is carried out film forming process, obtained electric energy energy storage film.
Described three-electrode system comprises work electrode, to electrode and reference electrode.Work electrode is natural electrode sheet, artificial graphite electrode sheet or Ti electrode sheet, is platinum plate electrode to electrode, and reference electrode is saturated calomel electrode.
In the process of the poly-metanilic acid lithium of described electrochemical polymerization method preparation, electrochemical oxidation reactions is there is in monomer metanilic acid and lithium compound within the scope of voltage range, class polyaniline type conducting high polymers thing is formed by the mode of chain polymerization at working electrode surface, π in an acidic solution on high molecular polymer main chain-pi-conjugated electron region and proton form electron conduction passage, and on phenyl ring skeleton side chain, negative electrical charge sulfonic acid group forms ionic conducting path.On the main chain under non-acidic conditions, proton is replaced, forms sub-quinoid structure, loses π-pi-conjugated system and loses this conductive channel.But Ionized sulfonic acid group belongs to Ionic conductivity body on side chain, the electric conductivity of leading poly-metanilic acid lithium under neutral or basic conditions.
Whole electrochemical polymerization process carries out under nitrogen protection, can be logical constant flow rate high pure nitrogen in electrochemical reaction cell.The oxygen in electrolyte can be removed on the one hand, prevent the structural destruction of product; To ventilate on the other hand the stirring action that can play electrolyte, be beneficial to the carrying out of electrochemical polymerization reaction, form the material of compact texture.
Lithium compound is Li
2cO
3.Li
2cO
3abundance on the one hand, low price, easily obtains, on the other hand it has relatively friendly water-soluble, can in neutral aqueous solution system and monomer metanilic acid dissolve each other, strengthen whole system conductivity, accelerate the growth of electric energy energy storage film, improve the homogeneity of electric energy energy storage film.
The pH value of described mixed solution is by adding hydrochloric acid or nitric acid adjustment.
Described thickener is polyacrylic acid (PAA) or sodium carboxymethylcellulose (CMC).More preferably, described thickener is polyacrylic acid (PAA), and molecular weight is between 2000-3500.
Described binding agent is polytetrafluoroethylene (PTFE), polyethylene (PE), carboxylic propyl methocel (HPMC), butadiene-styrene rubber breast (SBR), polyvinyl alcohol (PVA) or polyethylene glycol oxide (PEO).More preferably, described binding agent is polyethylene (PE), and molecular weight is between 5000-6000.
Described solvent is 1-METHYLPYRROLIDONE (NMP).
Get poly-metanilic acid lithium 115 parts respectively, thickener 10 parts, binding agent 10 parts, and solvent 100 parts.
Electrostatic spinning apparatus figure in the preparation method of the electric energy energy storage film that Fig. 3 provides for embodiment of the present invention second aspect, 1 is flow injection pump housing system, and 11 is syringe pump, and 12 is syringe, and 13 is syringe needle, and 2 is high-voltage dc voltage, and 3 for accepting electrode.
Be mixed with the miscible body of stream-like after mixing to comprise: thickener is dissolved in solvent and prepares sizing material, in sizing material, add poly-metanilic acid lithium and binding agent, the obtained miscible body of stream-like after stirring.
By method of electrostatic spinning, miscible for described stream-like body is carried out film forming process to comprise: with aluminium foil for accepting electrode, by the mode of electrostatic spinning miscible for described stream-like body is sprayed on and describedly accepts electrode surface film forming, from accepting electrode surface, film is taken off subsequently, dry, 10ml ~ 25ml syringe and supporting syringe needle is selected in described electrostatic spinning process, high-voltage DC power supply regulation voltage is 13kv ~ 14.5kv, syringe needle is 20 ~ 25cm with the distance accepting electrode, and spinning flow is 0.15 ~ 0.2 ml/hour.
From accepting electrode surface, film being taken off by standard scraper blade coating, to be placed in baking oven in 60 ~ 80 DEG C of dry out solvent, subsequently the film of drying to be placed in absolute ethyl alcohol and to soak, then put into vacuum drying oven and dry.
Described method of electrostatic spinning becomes membrane treatment process simple, film forming is even, easy to operate, masking time short and environmental friendliness, obtained electric energy energy storage film is nanometer filamentary material, and with poly-metanilic acid lithium for skeleton, auxiliary appropriate thickener and binding agent are filmogen, having good toughness and flexibility, can following process be various pattern (such as curling and stretch etc.).
Count by ratio of weight and the number of copies, described electric energy energy storage film comprises: poly-metanilic acid lithium 115 parts, thickener 10 parts, binding agent 10 parts, and solvent 100 parts.
The thickness of described electric energy energy storage film is 0.10 ~ 0.15mm.
The preparation method of the electric energy energy storage film that embodiment of the present invention second aspect provides has obtained a kind of novel electric energy energy storage film, this preparation method's environmental protection, with low cost, can be suitable for large-scale production.
The third aspect, embodiments provide a kind of electric energy storage device, described electric energy storage device is made up of the plus plate current-collecting body set gradually, electric energy energy storage film and negative current collector, described electric energy energy storage film with poly-metanilic acid lithium for skeleton, count by ratio of weight and the number of copies, comprising: poly-metanilic acid lithium 110 ~ 120 parts, thickener 1 ~ 15 part, and binding agent 1 ~ 15 part, plus plate current-collecting body and negative current collector are compressing tablet native graphite, Delanium or Graphene.
Described electric energy storage device applies constant pressure by tablet press machine and obtains.Described constant pressure is 7.5 ~ 8Mpa.The compacted depth of described electric energy storage device is 1mm.
The particle diameter of native graphite is 10 ~ 30 μm, and include the low-crystallinity turbostratic carbon shell of coated natural graphite, crystal layer spacing is 0.335nm ~ 0.346nm, and tap density is 0.95 ~ 1.05g/ml, and specific area is 4.0 ~ 7.5m
2/ g; The particle diameter of Delanium is 10 ~ 20 μm, and crystal layer spacing is 0.336nm ~ 0.362nm, and tap density is 0.90 ~ 1.21g/ml, and specific area is 5.0 ~ 9.5m
2/ g; Graphene is of a size of 20nm ~ 2 μm, is multi-layer graphene, and the number of plies is 3 ~ 5 layers.
The preparation method that described electric energy energy storage film provides according to embodiment of the present invention second aspect obtains.
The electric energy storage device that the embodiment of the present invention third aspect provides directly is combined to form for depositing electric energy energy storage film and collector in case without electrolyte, and structure is simple, and environmental protection is with low cost, can be suitable for large-scale production.Wherein, electric energy energy storage film unit are magnitude of the stored charge is high, energy per volume density is high, plus plate current-collecting body and negative current collector conductance high, positive and negative collector and electric energy energy storage film affinity high, higher high rate performance and power-performance can be reached.
Embodiment one
A preparation method for electric energy energy storage film, comprises the following steps:
In molar ratio for the ratio of 10:13 gets metanilic acid and lithium compound Li
2cO
3be mixed with mixed solution, be that the hydrochloric acid of 1mol/L regulates the pH value of described mixed solution to be 3 by adding concentration, be under the protection of the nitrogen flow of 99.99% in 20ml/min purity, by electrochemical polymerization work station, three-electrode system polymerization is carried out to mixed solution, applying voltage is 0.5V, and polymerization time is 2h, at the obtained poly-metanilic acid lithium of working electrode surface;
The work electrode of described three-electrode system is natural electrode sheet, is platinum plate electrode to electrode, and reference electrode is saturated calomel electrode;
Count by ratio of weight and the number of copies, get poly-metanilic acid lithium 115 parts respectively, thickener polyacrylic acid 10 parts of (PAA, molecular weight is 2000 ~ 3500), binding agent polyethylene 10 parts of (PE, molecular weight is 5000 ~ 6000), and solvent N-methyl pyrilidone (NMP) 100 parts;
Thickener 10 parts is dissolved in 40 parts of solvents, in mixer, stirs 30min, then add 25 parts of stirring solvent 15min, then add 35 parts of stirring solvent 45min, obtained sizing material;
115 parts of poly-metanilic acid lithiums are stirred 1h with 10HZ revolution in de-airing mixer, add 20% of above-mentioned obtained sizing material, 30min is stirred with 10HZ revolution, add 60% of above-mentioned obtained sizing material again, stir 30min with 50HZ revolution and rotation stirring 10min, then add remaining above-mentioned obtained sizing material, each 100min is stirred with 55HZ revolution and rotation, finally add 10 parts of binding agents, stir 60min with 50HZ rotation, the obtained miscible body of stream-like;
With aluminium foil for accepting electrode, by the mode of electrostatic spinning miscible for described stream-like body is sprayed on and describedly accepts electrode surface film forming, 25ml syringe and supporting syringe needle is selected in electrostatic spinning process, high-voltage DC power supply regulation voltage is 14.5kv, syringe needle is 25cm with the distance accepting electrode, spinning flow is 0.2 ml/hour, both positive and negative polarity terminals to be connected on syringe needle and at a distance of 5cm simultaneously, the even ground connection of whole process system, be placed in the glass box of electric field shielding, the inside is placed solid silicone particle and is kept environmental drying, and place air themperature hygrometer Real Time Observation,
Subsequently, from accepting electrode surface, film being taken off by standard scraper blade coating, to be placed in baking oven in 60 DEG C of dry out solvent, subsequently the film of drying to be placed in absolute ethyl alcohol and to soak 1.5h, then put into vacuum drying oven and dry 2.5h, obtained electric energy energy storage film.
The electric energy energy storage film that the embodiment of the present invention one obtains is nanometer filamentary material, with poly-metanilic acid lithium for skeleton, count by ratio of weight and the number of copies, comprise: poly-metanilic acid lithium 115 parts, thickener polyacrylic acid 10 parts of (PAA, molecular weight is 2000 ~ 3500), binding agent polyethylene 10 parts (PE, molecular weight is 5000 ~ 6000).The thickness of described electric energy energy storage film is 0.1mm.
By this electric energy energy storage film for the preparation of electric energy storage device, comprise the following steps:
Get Delanium and the obtained electric energy energy storage film of the embodiment of the present invention one, cover Delanium in these electric energy energy storage film both sides and apply 8Mpa constant pressure by tablet press machine, obtained electric energy storage device, the particle diameter of described Delanium is 10 ~ 20 μm, crystal layer spacing is 0.336nm ~ 0.362nm, tap density is 0.90 ~ 1.21g/ml, and specific area is 5.0 ~ 9.5m
2/ g.
Described electric energy storage device is made up of the plus plate current-collecting body set gradually, electric energy energy storage film and negative current collector.Described electric energy energy storage film with poly-metanilic acid lithium for skeleton, count by ratio of weight and the number of copies, comprise: poly-metanilic acid lithium 115 parts, thickener polyacrylic acid 10 parts of (PAA, molecular weight is 2000 ~ 3500), binding agent polyethylene 10 parts (PE, molecular weight is 5000 ~ 6000).The compacted depth of described electric energy storage device is 1mm.
Electric energy storage device chemical property detects
Adopt logical (the Auto Lab Station) electrochemical workstation of Switzerland ten thousand to detect electric energy storage device chemical property, electrochemical impedance spectroscopy frequency range is 10Hz ~ 10KHz, and amplitude is for being 10mHz, 71 Frequency points of sampling; Use cyclic voltammetry to judge electric energy storage device capacity and voltage platform scope, voltage set range is between-9V ~ 9V; Described decision method comprises the judgement of constant current and constant-resistance.
After tested, it is as shown in table 1 that the electric energy storage device obtained by the present embodiment one detects data.
Electric energy storage device obtained by table 1. the present embodiment one detects data
| Method | E(J cm -2) | Q(C cm -2) | C(F/cm 2) |
| Constant current | 0.28 | 0.35 | 0.22 |
| Constant-resistance | 0.29 | 0.33 | 0.19 |
As can be seen from Table 1, the electric energy storage device obtained by the present embodiment one based on its distinctive film activity feature as exclusive energy storage material, its every 1cm
2on to have high typical energy storage value be 0.22F; Compare down, although ultracapacitor has the electric capacity of 0.5F ~ 5F, the nano active electrode material needed forms its energy storing structure with highly consistent electrolyte.
Electric energy storage device obtained by the present embodiment one can be applicable in secondary cell, is assembled into a complete secondary cell as the positive pole of the barrier film of secondary cell and secondary cell, negative pole.Electric energy storage device in the embodiment of the present invention is based on bulk polairzed area mechanism stored energy, energy per unit area is large, voltage platform is relatively high, improves the electric energy energy storage capacity of secondary cell, makes secondary cell can tackle the special occasions such as power station to high power, high-octane requirement.
Embodiment two
A preparation method for electric energy energy storage film, comprises the following steps:
In molar ratio for the ratio of 10:12 gets metanilic acid and lithium compound LiClO
4be mixed with mixed solution, be that the hydrochloric acid of 1mol/L regulates the pH value of described mixed solution to be 2 by adding concentration, be under the protection of the nitrogen flow of 99.99% in 20ml/min purity, by electrochemical polymerization work station, three-electrode system polymerization is carried out to mixed solution, applying voltage is-0.5V, and polymerization time is 2h, at the obtained poly-metanilic acid lithium of working electrode surface;
The work electrode of described three-electrode system is artificial graphite electrode sheet, is platinum plate electrode to electrode, and reference electrode is saturated calomel electrode;
Count by ratio of weight and the number of copies, get poly-metanilic acid lithium 110 parts respectively, thickener sodium carboxymethylcellulose 1 part of (CMC, molecular weight is 80000 ~ 150000), polyfluortetraethylene of binding element 1 part of (PTFE, molecular weight is 100000 ~ 150000), and solvent N-methyl pyrilidone (NMP) 80 parts;
Thickener 1 part is dissolved in 30 parts of solvents, in mixer, stirs 30min, then add 30 parts of stirring solvent 15min, then add 20 parts of stirring solvent 45min, obtained sizing material;
110 parts of poly-metanilic acid lithiums are stirred 1h with 10HZ revolution in de-airing mixer, add 20% of above-mentioned obtained sizing material, 30min is stirred with 10HZ revolution, add 60% of above-mentioned obtained sizing material again, stir 30min with 50HZ revolution and rotation stirring 10min, then add remaining above-mentioned obtained sizing material, each 100min is stirred with 55HZ revolution and rotation, finally add 1 part of binding agent, stir 60min with 50HZ rotation, the obtained miscible body of stream-like;
With aluminium foil for accepting electrode, by the mode of electrostatic spinning miscible for described stream-like body is sprayed on and describedly accepts electrode surface film forming, 25ml syringe and supporting syringe needle is selected in electrostatic spinning process, high-voltage DC power supply regulation voltage is 14.5kv, syringe needle is 25cm with the distance accepting electrode, spinning flow is 0.2 ml/hour, both positive and negative polarity terminals to be connected on syringe needle and at a distance of 5cm simultaneously, the even ground connection of whole process system, be placed in the glass box of electric field shielding, the inside is placed solid silicone particle and is kept environmental drying, and place air themperature hygrometer Real Time Observation,
Subsequently, from accepting electrode surface, film being taken off by standard scraper blade coating, to be placed in baking oven in 60 DEG C of dry out solvent, subsequently the film of drying to be placed in absolute ethyl alcohol and to soak 1.5h, then put into vacuum drying oven and dry 2.5h, obtained electric energy energy storage film.
The electric energy energy storage film that the embodiment of the present invention two obtains is nanometer filamentary material, with poly-metanilic acid lithium for skeleton, count by ratio of weight and the number of copies, comprise: poly-metanilic acid lithium 110 parts, thickener sodium carboxymethylcellulose 1 part of (CMC, molecular weight is 80000 ~ 150000), polyfluortetraethylene of binding element 1 part (PTFE, molecular weight is 100000 ~ 150000).The thickness of described electric energy energy storage film is 0.1mm.
By this electric energy energy storage film for the preparation of electric energy storage device, comprise the following steps:
Get native graphite and the obtained electric energy energy storage film of the embodiment of the present invention two, cover native graphite in these electric energy energy storage film both sides and apply 8Mpa constant pressure by tablet press machine, obtained electric energy storage device, the particle diameter of native graphite is 10 ~ 30 μm, include the low-crystallinity turbostratic carbon shell of coated natural graphite, crystal layer spacing is 0.335nm ~ 0.346nm, and tap density is 0.95 ~ 1.05g/ml, and specific area is 4.0 ~ 7.5m
2/ g.
Described electric energy storage device is made up of the plus plate current-collecting body set gradually, electric energy energy storage film and negative current collector.Described electric energy energy storage film with poly-metanilic acid lithium for skeleton, count by ratio of weight and the number of copies, comprise: poly-metanilic acid lithium 110 parts, thickener sodium carboxymethylcellulose 1 part of (CMC, molecular weight is 80000 ~ 150000), polyfluortetraethylene of binding element 1 part (PTFE, molecular weight is 100000 ~ 150000).The compacted depth of described electric energy storage device is 1mm.
Electric energy storage device chemical property detects
Adopt logical (the Auto Lab Station) electrochemical workstation of Switzerland ten thousand to detect electric energy storage device chemical property, electrochemical impedance spectroscopy frequency range is 10Hz ~ 10KHz, and amplitude is for being 10mHz, 71 Frequency points of sampling; Use cyclic voltammetry to judge electric energy storage device capacity and voltage platform scope, voltage set range is between-9V ~ 9V; Described decision method comprises the judgement of constant current and constant-resistance.
After tested, it is as shown in table 2 that the electric energy storage device obtained by the present embodiment two detects data.
Electric energy storage device obtained by table 2. the present embodiment two detects data
| Method | E(J cm -2) | Q(C cm -2) | C(F/cm 2) |
| Constant current | 0.30 | 0.33 | 0.18 |
| Constant-resistance | 0.32 | 0.35 | 0.19 |
As can be seen from Table 2, the electric energy storage device obtained by the present embodiment two based on its distinctive film activity feature as exclusive energy storage material, its every 1cm
2on to have high typical energy storage value be 0.19F; Compare down, although ultracapacitor has the electric capacity of 0.5F ~ 5F, the nano active electrode material needed forms its energy storing structure with highly consistent electrolyte.
Electric energy storage device obtained by the present embodiment two can be applicable in secondary cell, is assembled into a complete secondary cell as the positive pole of the barrier film of secondary cell and secondary cell, negative pole.Electric energy storage device in the embodiment of the present invention is based on bulk polairzed area mechanism stored energy, energy per unit area is large, voltage platform is relatively high, improves the electric energy energy storage capacity of secondary cell, makes secondary cell can tackle the special occasions such as power station to high power, high-octane requirement.
Embodiment three
A preparation method for electric energy energy storage film, comprises the following steps:
In molar ratio for the ratio of 10:15 gets metanilic acid and lithium compound LiOH, be mixed with mixed solution, the pH value of described mixed solution is regulated to be 5, be under the protection of the nitrogen flow of 99.99% in 20ml/min purity, by electrochemical polymerization work station, three-electrode system polymerization is carried out to mixed solution, applying voltage is 1.0V, and polymerization time is 1.5h, at the obtained poly-metanilic acid lithium of working electrode surface;
The work electrode of described three-electrode system is Ti electrode sheet, is platinum plate electrode to electrode, and reference electrode is saturated calomel electrode;
Count by ratio of weight and the number of copies, get poly-metanilic acid lithium 120 parts respectively, thickener polyacrylic acid 15 parts of (PAA, molecular weight is 2000 ~ 3500), binding agent butadiene-styrene rubber breast 15 parts of (SBR, molecular weight is 150000 ~ 200000), and solvent N-methyl pyrilidone (NMP) 150 parts;
Thickener 15 parts is dissolved in 80 parts of solvents, in mixer, stirs 30min, then add 50 parts of stirring solvent 15min, then add 20 parts of stirring solvent 45min, obtained sizing material;
120 parts of poly-metanilic acid lithiums are stirred 1h with 10HZ revolution in de-airing mixer, add 20% of above-mentioned obtained sizing material, 30min is stirred with 10HZ revolution, add 60% of above-mentioned obtained sizing material again, stir 30min with 50HZ revolution and rotation stirring 10min, then add remaining above-mentioned obtained sizing material, each 100min is stirred with 55HZ revolution and rotation, finally add 15 parts of binding agents, stir 60min with 50HZ rotation, the obtained miscible body of stream-like;
With aluminium foil for accepting electrode, by the mode of electrostatic spinning miscible for described stream-like body is sprayed on and describedly accepts electrode surface film forming, 10ml syringe and supporting syringe needle is selected in electrostatic spinning process, high-voltage DC power supply regulation voltage is 13kv, syringe needle is 20cm with the distance accepting electrode, spinning flow is 0.15 ml/hour, negative pole end is connected on syringe needle, positive terminal is connected on and accepts on electrode, the even ground connection of whole process system, be placed in the glass box of electric field shielding, the inside is placed solid silicone particle and is kept environmental drying, and place air themperature hygrometer Real Time Observation,
Subsequently, from accepting electrode surface, film being taken off by standard scraper blade coating, to be placed in baking oven in 60 DEG C of dry out solvent, subsequently the film of drying to be placed in absolute ethyl alcohol and to soak 1.5h, then put into vacuum drying oven and dry 2.5h, obtained electric energy energy storage film.
The electric energy energy storage film that the embodiment of the present invention three obtains is nanometer filamentary material, with poly-metanilic acid lithium for skeleton, count by ratio of weight and the number of copies, comprise: poly-metanilic acid lithium 120 parts, thickener polyacrylic acid 15 parts of (PAA, molecular weight is 2000 ~ 3500), binding agent butadiene-styrene rubber breast 15 parts (SBR, molecular weight is 150000 ~ 200000).The thickness of described electric energy energy storage film is 0.15mm.
By this electric energy energy storage film for the preparation of electric energy storage device, comprise the following steps:
Get Graphene and the obtained electric energy energy storage film of the embodiment of the present invention three, cover Graphene in these electric energy energy storage film both sides and apply 7.5Mpa constant pressure by tablet press machine, obtained electric energy storage device, Graphene is of a size of 20nm ~ 2 μm, for multi-layer graphene, the number of plies is 3 ~ 5 layers.
Described electric energy storage device is made up of the plus plate current-collecting body set gradually, electric energy energy storage film and negative current collector.Described electric energy energy storage film with poly-metanilic acid lithium for skeleton, count by ratio of weight and the number of copies, comprise: poly-metanilic acid lithium 100 parts, thickener polyacrylic acid 2.5 parts of (PAA, molecular weight is 2000 ~ 3500), binding agent butadiene-styrene rubber breast 15 parts (SBR, molecular weight is 150000 ~ 200000).The compacted depth of described electric energy storage device is 1mm.
Electric energy storage device chemical property detects
Adopt logical (the Auto Lab Station) electrochemical workstation of Switzerland ten thousand to detect electric energy storage device chemical property, electrochemical impedance spectroscopy frequency range is 10Hz ~ 10KHz, and amplitude is for being 10mHz, 71 Frequency points of sampling; Use cyclic voltammetry to judge electric energy storage device capacity and voltage platform scope, voltage set range is between-9V ~ 9V; Described decision method comprises the judgement of constant current and constant-resistance.
After tested, it is as shown in table 3 that the electric energy storage device obtained by the present embodiment three detects data.
Electric energy storage device obtained by table 3. the present embodiment three detects data
| Method | E(J cm -2) | Q(C cm -2) | C(F/cm 2) |
| Constant current | 0.29 | 0.314 | 0.17 |
| Constant-resistance | 0.27 | 0.32 | 0.19 |
As can be seen from Table 3, the electric energy storage device obtained by the present embodiment three based on its distinctive film activity feature as exclusive energy storage material, its every 1cm
2on to have high typical energy storage value be 0.19F; Compare down, although ultracapacitor has the electric capacity of 0.5F ~ 5F, the nano active electrode material needed forms its energy storing structure with highly consistent electrolyte.
Electric energy storage device obtained by the present embodiment three can be applicable in secondary cell, is assembled into a complete secondary cell as the positive pole of the barrier film of secondary cell and secondary cell, negative pole.Electric energy storage device in the embodiment of the present invention is based on bulk polairzed area mechanism stored energy, energy per unit area is large, voltage platform is relatively high, improves the electric energy energy storage capacity of secondary cell, makes secondary cell can tackle the special occasions such as power station to high power, high-octane requirement.
Claims (12)
1. a preparation method for electric energy energy storage film, is characterized in that, comprises the following steps:
In molar ratio for the ratio of 10:12 ~ 15 gets metanilic acid and lithium compound LiOH, LiClO
4or Li
2cO
3be mixed with mixed solution, the pH value of described mixed solution is regulated to be 2 ~ 5, under nitrogen protection, by electrochemical polymerization work station, three-electrode system polymerization is carried out to described mixed solution, applying voltage is-0.5 ~ 1.0V, and polymerization time is 1.5 ~ 2h, at the obtained poly-metanilic acid lithium of working electrode surface;
Count by ratio of weight and the number of copies, get poly-metanilic acid lithium 110 ~ 120 parts respectively, thickener 1 ~ 15 part, binding agent 1 ~ 15 part, and solvent 80 ~ 150 parts, be mixed with the miscible body of stream-like after mixing, by method of electrostatic spinning, miscible for described stream-like body is carried out film forming process, obtained electric energy energy storage film.
2. the preparation method of electric energy energy storage film as claimed in claim 1, it is characterized in that, the work electrode of described three-electrode system is natural electrode sheet, artificial graphite electrode sheet or Ti electrode sheet, and be platinum plate electrode to electrode, reference electrode is saturated calomel electrode.
3. the preparation method of electric energy energy storage film as claimed in claim 1, it is characterized in that, described thickener is polyacrylic acid or sodium carboxymethylcellulose, described binding agent is polytetrafluoroethylene, polyethylene, carboxylic propyl methocel, butadiene-styrene rubber breast, polyvinyl alcohol or polyethylene glycol oxide, and described solvent is 1-METHYLPYRROLIDONE.
4. the preparation method of electric energy energy storage film as claimed in claim 1, it is characterized in that, be mixed with the miscible body of stream-like after described mixing to comprise: thickener is dissolved in solvent and prepares sizing material, after adding poly-metanilic acid lithium and binding agent stirring, obtain the miscible body of stream-like.
5. the preparation method of electric energy energy storage film as claimed in claim 2, it is characterized in that, be mixed with the miscible body of stream-like after described mixing to comprise: thickener is dissolved in solvent and prepares sizing material, after adding poly-metanilic acid lithium and binding agent stirring, obtain the miscible body of stream-like.
6. the preparation method of electric energy energy storage film as claimed in claim 3, it is characterized in that, be mixed with the miscible body of stream-like after described mixing to comprise: thickener is dissolved in solvent and prepares sizing material, after adding poly-metanilic acid lithium and binding agent stirring, obtain the miscible body of stream-like.
7. the preparation method of the electric energy energy storage film as described in any one of claim 1-6, it is characterized in that, describedly by method of electrostatic spinning, miscible for described stream-like body is carried out film forming process and comprise: with aluminium foil for accepting electrode, by the mode of electrostatic spinning miscible for described stream-like body is sprayed on and describedly accepts electrode surface film forming, from accepting electrode surface, film is taken off subsequently, dry, 10ml ~ 25ml syringe and supporting syringe needle is selected in described electrostatic spinning process, high-voltage DC power supply regulation voltage is 13kv ~ 14.5kv, syringe needle is 20 ~ 25cm with the distance accepting electrode, spinning flow is 0.15 ~ 0.2 ml/hour.
8. an electric energy energy storage film, it is characterized in that, described electric energy energy storage film obtains by preparation method according to claim 1, described electric energy energy storage film with poly-metanilic acid lithium for skeleton, count by ratio of weight and the number of copies, comprise: poly-metanilic acid lithium 110 ~ 120 parts, thickener 1 ~ 15 part, and binding agent 1 ~ 15 part.
9. electric energy energy storage film as claimed in claim 8, it is characterized in that, described thickener is polyacrylic acid or sodium carboxymethylcellulose, described binding agent is polytetrafluoroethylene, polyethylene, carboxylic propyl methocel, butadiene-styrene rubber breast, polyvinyl alcohol or polyethylene glycol oxide, and described solvent is 1-METHYLPYRROLIDONE.
10. electric energy energy storage film as claimed in claim 8, it is characterized in that, the thickness of described electric energy energy storage film is 0.10 ~ 0.15mm.
11. 1 kinds of electric energy storage devices, it is characterized in that, described electric energy storage device is made up of the plus plate current-collecting body set gradually, the electric energy energy storage film obtained by preparation method according to claim 1 and negative current collector, described electric energy energy storage film with poly-metanilic acid lithium for skeleton, count by ratio of weight and the number of copies, comprise: poly-metanilic acid lithium 110 ~ 120 parts, thickener 1 ~ 15 part, and binding agent 1 ~ 15 part, described plus plate current-collecting body and negative current collector are compressing tablet native graphite, Delanium or Graphene.
12. electric energy storage devices as claimed in claim 11, is characterized in that, the compacted depth of described electric energy storage device is 1mm.
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| CN102255106A (en) * | 2011-04-29 | 2011-11-23 | 哈尔滨工业大学 | PAMPSLi fiber based polymer electrolyte membrane preparation method utilizing electrospinning method |
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| CN102255106A (en) * | 2011-04-29 | 2011-11-23 | 哈尔滨工业大学 | PAMPSLi fiber based polymer electrolyte membrane preparation method utilizing electrospinning method |
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