TW200411965A - Polymer-based nanoscale organophilic clay for gel polymer electrolytes and lithium rechargeable battery - Google Patents

Abstract

A series quaternary alkylammonium salts used in the organophilic procedure, performed on montmorillonite clay, resulting in intercalation in plasticizer between the polymer and the organophilic clay. A series of gel polymer nanocomposite electrolyte materials were successfully prepared by adding the appropriate percentage of plasticizer, organophilic clay and lithium perchlorate to polymer. The best possible ionic conductivity was 1.03x10<SP>-2</SP> S/cm and exhibited better film formation, plasticizer-maintaining capability and dimensional stability than the electrolyte film without the added organophilic clays. From the cyclic electrochemistry testing result, it is shown that adding organophilic clays significantly enhances the electrochemical stability of the gel polymer electrolyte system. The invention also concerns the lithium rechargeable battery which assembled with gel (nanocompsite polymer electrolytes. Such lithium rechargeable batteries has the stable cyclic charge-rechargeable property and potential great commercial value.

Description

200411965 V. Description of the invention (1) Summary of the invention The quality of the present invention is improved by the use of lipophilic modification for intercalation, the addition of bell salt and its ionic conductivity impregnation rate and the addition of nano-level electrolytes. It is about a colloidal polymer electrolyte containing nano-grade clay. Surfactant improves inorganic clay (montmor i 1 loni te) ’and makes the colloidal polymer and lipophilic clay intercalation. The colloidal polymer electrolyte film containing nano-grade clay can be prepared under the appropriate proportion of plasticizer, the degree can reach 1 · 03 X 1 〇-2 s / cm, and the film formation is good, and the dimensional stability of the plasticizer (dimensional stability) ) Are better than unclayed electrolyte membranes. In addition, the addition of nano-grade clay membranes also makes the electrochemical stability of its electrolyte system obvious. The present invention also relates to a lithium polymer electrolyte containing nano-semi-prepared lithium, and a colloidal polymer electrolyte of clay. The produced] secondary battery composed of the above electrolyte has a charge-discharge cycle effect of t 疋 and has excellent commercial value. BACKGROUND OF THE INVENTION With the advancement of human science and technology, the demand for information products has also greatly improved, and various electronics and research and design products have accumulated ^^. Therefore, the functionality of products has been improved, and can be carried and lightened. , Thin, short, force targets. Among them, the wireless of products is a match for the power source of products. ~battery. It must also comply with safety and weight i ^ srs 200411965 V. Description of the invention (2) Light, thin, and environmentally friendly. Therefore, high-performance lithium polymer secondary batteries have been developed. The polymer electrolyte material has both the electrolyte and the separator between the anode and the anode (separa t 〇r) in the Zhongmao secondary battery system. Therefore, the ionic conductivity, dimensional stability and electrochemical stability must all reach a certain level. standard. The first research on polymer electrolytes was made by Wright et al. In 1973. They added KSCN to pOiy (efhylene oxide) (PE0) by mixing and swapping. The experimental results were crystalline. Complex. Then in 1975 Wright et al. Further proved that these complexes have a conductivity of 10-4 s / cm or higher at high temperatures (above 100 ° C). Since then, many research institutes have actively invested in the research on the conductivity of polymer electrolytes, hoping to improve the shortcomings of low conductivity at room temperature. Among the polymer bodies currently studied, the conductivity of poliacrylnitrile (PAN) is the most valuable. The first to propose such polymer electrolytes was Reich and Michaeli, and since then many research institutions have attracted investment in this area. A 1994 study by Scrosati et al. Found that a colloidal polymer electrolyte (Ge Type Polymer

Electrolytes), its conductivity can reach 10-3 s / cm or more at 25 ° C. Among the newly synthesized polymer themes, poly [2- (2-methoxyethoxyethoxy)] phosphazene (MEEP) has the most potential for development, and the solid polymer electrolytes made by it have a conductivity of 10-5 S / Cm or more. Although the conductivity is high, the dimensional stability is relatively reduced. Therefore, A1 lcock et al. Used r-radiat ion to make the MEEP molecular chain part

Page 7 V. Description of the invention (3) Parent affiliation to improve machinability. Near homochain length ether group substituents = good use

Abraham's size son-in-law. The K · M. Properties, but because of the combination of PEO and ML, the processing of 7MEEP is improved. The original conductivity is 1; = ^^ The purpose of the invention is to improve the colloidal polymer electrolyte material by using ==, = =; 丨 Blending of plasticizers with nano-grade clay and electric number of feet, 8-foot: I ί quality f film, to improve the thermal stability of polymer electrolyte thin film: the electrical properties of the film r ΐ ΐ, ionic conductivity And colloidal polymer electrolytes are thin and non-toxic. This electrolyte has a tritium charge-discharge cycle effect on lithium secondary batteries and has excellent commercial value. / 、 Detailed description of the invention of the invention The present invention is to use a surfactant to make lipophilic modification of inorganic clay, and to make polymer and lipophilic intercalation in plasticizer. Then, a lithium salt was added to the plasticizer at the same ratio to prepare a nano-grade clay-containing polymer electrolyte film. The surfactants referred to in the present invention can be used in the present invention, as long as they have long-chain alkyl / aromatic group = surface activity, for example, long-chain alkyl quaternary ammonium long-chain quaternary quaternary salt (quaternary alkylamm). niuni t) Moonlight is sodium L, lauryl triethanolamine, lauryl amine 200411965 V. Description of the invention (4) Sodium, chlorinated stearic acid bismuth ^ ^ ^ ^ ^ ^ ^ T-bismuth Benzylammonium chloride, Diammonium chlorostearate, Dimethyl methanoate, Dimethylamino laurate trimethylammonium acetate lactone, Polyammonium stearylamine, Dimethyl stearate Amine lactam lactam, polyoxyethylene norazine oil, fatty amine, coconut oil fatty acid monoethanolamine, stearic acid diethanolamine, stearic acid monoethanolamine, stearic acid diethanolamine Amine, C12H25N (CH3) 3Br ^ C14H29N (CH3) 3Br'C16H33N (CH3) 3Br [CH3 (CH2) ii 2 3 2NBr, C12H25S〇4Na, ci4H29S04Na, C16H33S04Na, C18H37S04Na ^ C12H4N9; C12H25S. CH3) 3C12H25 ^ C12H25CH (C00 ^ N (CH3) 3. (C4H9) 2CHCH2 (0C2H4) 90H ^ n-C12H25 (ΟΚΗ4) ^ 〇H, etc., preferably a long-chain alkyl quaternary ammonium salt, especially '^ (CH3) 3Br ^ C14H29N (CH3) 3Br ^ C16H33N (CH3) 3Br ^ [CH3 (CH2) n] 2 (CH3) 2NBr, etc.) The colloidal polymers referred to in the present invention include all colloidal polymers. Modification of the present method, for example, polyvinylidene fluoride (p VdF), polyvinylidene fluoride (PVdF-HFP), polypropylene (PAN), polyoxyethylene (PE0), polymethyl Methyl acrylate (pMMA), of which polypropylene is also suitable for 'polyvinylidene difluoride ^ ethylene, the molecular weight of the polymer used varies according to different polymers. The choice of molecular weight must have both good mechanical properties and easy Intercalation 'Take polyvinylidene fluoride as an example, it can be about 10,000 to 1 million. The plasticizer referred to in the present invention is that anyone who can dissolve the colloidal polymer and has a plastic effect can be the plasticizer of the present invention, for example, dimethylene carbonate (DMC), diethylethylene carbonate (Diethylene carbonate, DEC), 1 N, dimethylformamide (MF), propylene carbonate

200411965 V. Description of the invention (5) carbonate, PC) / ethylene carbonate (EC) co-plasticizer, etc., and a mixture of the above plasticizers, among which dimethylformamide and / or (propylene Carbonate / Ethylene Carbonate) (PC / ec) co-plasticizer. s

The lithium salt referred to in the present invention is not particularly limited, and may be lithium salts commonly used in the preparation of lithium batteries, for example, Li PF6 &gt; L1CF3SO3, UN (CF3S02) 2, LiBF4, LiSCN, LiAsF6, LiC104, etc. LiPF6 and LiC104 are preferred. 'The nano-grade clay used in the present invention is a clay with a product number of PK802 for impact-resistant products and a clay with a product number of ρκ800 and the like for electronic-grade products.' 8 0 2, 0-PK 8 0 5 and other editing records are not available. The surfactant selected by the present invention undergoes lipophilic modification with inorganic clay PK-805, ρκ ~ 802, which not only expands the distance between clay layers, but also contributes to large molecular weight polymers (PVdF, MW: 1 000 00 0) into the clay layer to intercalate (intercalati0I1) to form a colloidal nano ^ complex electrolyte material, this finding helps to reduce the process and time, suitable for molecular weights below 1 0 0 0 0 0 0 0 Other polymer materials. ; The specific implementation method of the present invention, the lipophilic treatment of clay will contain an appropriate amount of cationic surfactants Ci2H25N (C {^) 3Br, C14H29N (CH3) 3Br, C16H33N (CH3) 3Br, [CH3 (CH2) U ] 2 (CH3)

V. Description of the invention (6) sNBr and clay are respectively filtered and mixed with deionized water for lipophilic treatment. Next, the salt (N a B r) ^ methanol ’is used to wash the excess surfactant in the clay. Among them, the following clays are dried and ground. The weight of the surfactant is calculated in milligrams. The score of active agent U) = cation exchange equivalent (CEC) χΙΟ—3 The weight of the coefficient at the X interface x coefficient If the opening distance between the clay layers is related, it is better to &quot; between -1.5 'and its Intercalation effect of polymer and polymer chain Φ, firstly make the modified clay uniformly dispersed in DMF4pC / EC plasticizer μ 1. Give the polymer with additional leaf amount, and stir evenly on the glass plate after 1 2 hrs And, drying in a vacuum oven; the PC / EC ratio is about • to · 1. Finally, the x-ray diffraction analyzer is used to identify the change of state. Preparation of colloidal polymer electrolyte: polyvinylidene fluoride (MW = 53 0 0 0 0), modified clay and lithium salt (UCIO4) measured according to F value, added in DMf or pc / EC (l: l) The plasticizer is heated (approximately 30 ° C-100 ° C) and uniformly stirred to make the solution homogeneous (homogenous), which takes about 6 hrs. After forming a film on a glass plate, the temperature is controlled to make the film The content of DMF or PC / EC plasticizer is in a certain range (about ~ 60%), and a colloidal polymer electrolyte film is prepared. Where F = Molar number of lithium salt / (grams of polymer / repeated unit molecular weight)

200411965 V. Description of Invention (7) ^ —

The composition and formulation of specific examples of the present invention are shown in Tables 丨 and 2 and a colloidal polymer electrolyte was prepared according to the above method. X The analysis method of the present invention uses the X-ray diffraction analyzer D / Max-3C 0D-2988N) to analyze the clay layer, and uses the impedance analyzer (Impedence Analyser HP4192A) to measure the ion conductivity of the polymer electrolyte. Electron microscopy (JEOL- 20 0FX) to observe the microscopic phenomena in clay-dispersed polymer electrolyte materials, using a cyclic voltammetry tester (Eco Chemie BV model PGSTAT3〇) to measure the oxidation cycle potential and oxidative breakdown potential of the electrolyte Using a thermomechanical analyzer, (Perkin-Elmer DMA 7e analyzer) to measure the thermal expansion coefficient of the polymer electrolyte, understand the size of the material in the use temperature range 2 = material properties. Using the battery assembled by the electrolyte of the present invention, a lithium secondary battery charge-discharge test was performed using an Arbin® 2000 battery charge-discharge device. Effect of the invention Lipophilic modification of clay First, the lipophilic treatment of inorganic clay is performed. The clay is an inorganic silicate, and the hydrophilic end of the surfactant is required. : The purpose of ion exchange of% ions is to make the K group of the surfactant enter the layers of the clay to achieve the effect of expanding the distance between the layers. Second, the molecular chain and the lipophilic end of the surfactant existing between the clay layers are produced: 200411965 V. Explanation of the invention (8) The effect can be further improved. Under the same operating conditions, it can be known from the X_ray diffraction analysis spectrum that the change in the distance between layers will be changed due to different types of surfactants. As shown in Table 4, the distance supported by DidOdeCyldimethyl ammonium bromide, [CH3 (CH2) u] 2 (CH3) 2NBr is the largest, may be the structure and bond angle of the double long chain alkyl group, so that the double long chain The interlayer between the alkyl and the inorganic clay showed a jack type, which effectively increased the interlayer distance to 22 Angstroms. 'The original interlayer distance of the clay was 12 Angstroms. In addition, we also use the aromatic quaternary ammonium salt and perform experiments with AR〇_S as a representative. Its structural composition is shown in Table 5. The modification test results show that AR〇-S makes inorganic clay PK 8 The distance between 0.2 layers was enlarged to 21 · 54 Angstroms, and after the modification of ρ κ 805, the distance between layers could also be enlarged to 18.71 Angstroms. The mixing effect of colloidal polymer and oleophilic clay. Take polyvinylidene fluoride as an example. After preparing a polyvinylidene fluoride solution and measuring 3% of the modified clay, the two are evenly mixed into a transparent solution. A thin film with a thickness of 0.2 mm was made on it. It was found on the x-ray diffraction pattern that the lipophilic clay f originally located at 4 · 2 2 2 Θ angle has disappeared, this is because of polyvinylidene fluoride

Dilute two-molecule bonds are possible between clay layers; &gt; Human μA I · θ intersperses this Dafanquan dispersion, the so-called exfoliation. In order to prove this statement, different (2% 3% 5% 7 :.) lipophilic clays are individually dissolved in polyisocyanate to make a film of a certain thickness, and [ray diffraction analysis is performed, such as: a night: As the clay content increases, the map changes significantly. It is often similar to 'there are no absorption peaks at 2Θ angles found on the map. Second, the mixed material formed by these two ratios shows a peeling state.

Page 13 200411965 V. Description of the invention (9) (exfoliat10n), but if the clay content increases to ⑽, it is found that a small wave peak is gradually formed around 2 / -3 degrees. When the content of clay increases to 7 / 〇, this peak is more obvious, showing that the polyvinylidene fluoride molecular chain is still intercalation between the layers of clay, so that the 20 angle is changed from 4 degrees f to 3 degrees to indicate polyisopropyl The content of lipophilic clay in fluoroethylene is more than ⑽ $ * The organic-inorganic mixed state may show 丨 n ^ erca 1 a ^ 丨 0 n. To observe the october shape of inorganic clay dispersed in the polymer chain through a transmission electron microscope, take polyvinylidene fluoride containing 5% c 1 ay for testing, and the results are shown in Figure 2. 'Specifically for some areas Partially enlarged, the delamination phenomenon of the interlaminar destruction of the inorganic clay is clearly seen in the picture, as shown in Figure 3, and a part of the intercalation phenomenon, as shown in Figure 4, so polyvinylidene fluoride and 5 The mixing effect of% inorganic clay has both exfoliation and intercalation. This result also confirms the test results of X-ray. Plasticizer impregnation properties The greatest difference between a knee-type polymer electrolyte and a solid polymer electrolyte is the presence or absence of a plasticizer in the polymer system. Relevant literature indicates that the presence of a 'plasticizer can increase its ionic conductivity, but also cause its negative effects on dimensional stability, mechanical strength, and poor film formation. Designed to add 3% inorganic clay to polyvinylidene fluoride and add LiC104 with different F-values to prepare a series of colloidal polymer electrolytes. The thickness of the film is controlled to 50 ～ 100% // m. Film formation of polymer electrolyte thin film of inorganic clay

Page 14 200411965 V. Description of the invention (ίο) Significantly better than the unadded polymer electrolyte film. In order to understand whether the inorganic clay helps the plasticizer to stay in the polymer electrolyte film, there will be those with and without added inorganic clay. The polymer electrolyte film was simultaneously placed in a vacuum oven of 0.1 Torr and maintained at 50 X :, and the amount of plasticizer reduction was observed. The results are summarized in Figure 5. The results show that with time, when the colloidal polymer electrolyte film increases, When the inorganic clay is contained, the impregnation rate of the plasticizer is helpful. The addition of PK805 has better results because the amount of plasticizer reduced is the smallest. &lt; After the conductive first electrolyte is shaped in the polymer's large conductive molecular chain, the migration between the attracted lithium is shown in Table 67. The amount of f, the inorganic clay, measured in inches and meters, is added to the colloidal polyisocyanate. The effect of the degree of vinyl fluoride is shown in Figure 6. 'When nano-grade clay / Lego is added, its electrical conductivity is significantly better than that of the non-added: II / 犋, and its conductivity can be improved approximately. Up to 1.03 x l0-2 s / cm, the induction factor is _ ^ Kou Shan is scattered in the helmet. She pulls τ Π. The prisoners are as follows. (1) 咼 helps i to separate from the two, and helps the polymer form to tend to The positive charge force between the inorganic clay layers makes the bell ion have a faster velocity than the perchlorate ion. The related data is compiled from the data that π can increase lithium ions. It is known that the conductivity is related to the observed conductivity as lithium_content = 3 罝. From the figure, it is the same as the lithium salt content # =; Electrical conductivity, its conductive sound, but the lithium salt content begins to decrease when it exceeds one electrical degree. The reason is the polymer electrolyte system

Page 15 200411965 V. Description of the invention (11) The conductivity is caused by ion conduction. Excessive lithium salt exists under the system. 'It may cause the following two conditions. (1) There is still a strong ionic attraction between anions and cations. Force 'is not easily dissociated by the plasticizer in the system. (2) The concentration of yin and yang in the system is too high, and the migration process in the system may be combined again. Based on the above two reasons, the number of ions that can carry a charge in the system is reduced ^: makes; ^ conductivity is reduced. By further changing the content of plasticizer, from the appearance, the content of plasticizer is more than that of film, but the sound of film does not seem to be A, but in terms of its strength and film-forming property, film with higher plasticizer content is worse. As shown in Figure 8, 'As the plasticizer content increases, there is a significant increase in electrical conductivity.' Especially in PC / EC plasticizer systems, when the plasticizer content is 45% and 15%, the electrical conductivity can be compared. The increase is about 5 times, but if the amount is greater than the above, its polymer electrolyte and the problem of plasticizer oozing, due to the study of the variability of the electrical value, the stability of the polymer electrolyte material in the lithium secondary battery system The two functions, when the battery is charged and discharged, may produce = discharge = shell ',, and this may cause the polymer electrolyte film: Sueda may reduce the battery charge and discharge cycle efficiency 1 This way, the polymer electrolyte material must have excellent size =. Select nanometer grade: soil content is 3%, Licl04 measurement value is Bu Sheng. The r # I plasticizer contains * 15%, ~ prepared polyvinylidene fluoride electrolyte 仃 Thermomechanical analysis (TMA) test, observe the heat in a temperature range

Page 16 V. Explanation of the invention (12) The expansion coefficient is compared with the colloidal polyvinylidene fluoride electrolytic shell without nano-grade clay. The results are shown in Figure 9. Polyvinylidene gas electrolytes have a thermal expansion coefficient in the range of -50 ~ 8 (rc temperature range, the octave value is 1 54 · 4 X 10 mm / C, and the results are significantly better than the colloidal polymer without the addition of nano-grade clay. The value of vinylidene difluoride electrolyte film is 180.9 × 10 6 r, which is a very good junction * 'The results show that the size of the nano-scale viscous complex electrolyte film is stable, even at 80 ° C. "Nanwenxia's supply is only for females w [m 1 Nai ..., maintaining good dimensional stability, it is speculated that 1 Shun B !, when rice-grade clay is uniformly dispersed in polyvinylidene fluoride electrolyte film, its delamination Phenomenon of rupture is the layer of fluoroethylene polymer molecular chain, and the molecule = partial: there may be a stable molecular gate 栳 田 ', the stability of the size of the disintegration between rice glutinous materials is improved to make the colloidal Electro-electrochemical stability of polyvinylidene fluoride. The colloidal polymer prepared was electrolytically tested to assemble half of the electricity. Cell test element Li / Gp ^: Electrochemical measurement corresponding electrode, a platinum sheet as 电极 1 as a working electrode and a slot, connected to the current-electricity h 'pole, put a nitrogen-filled corrosion bite 々L Isopotentiostat from the storage of lithium from lice: the redox effect, our ladies test 'understand that its chemical damage potential can reach 4. 2V, adding nano-grade clay in the oxidation ^: nano-grade clay chapter indeed Help glue to gather people :: The results of the test found that the reduction and reduction cycle 'may be caused by deprivation; m solution quality makes the fun ion oxygen agent' exist in the electrolyte film, which has high; more plasticity &quot; number of more electricity The plasticizer was in 200411965 V. Description of the invention (13) Lithium salts were dissociated and the ions were uniformly divided, ^, f polymer electrolysis station +, when lithium ions gain or lose electrons ,,,, == Beijing's system helps charge and discharge lithium polymer secondary batteries. This phenomenon has a “% effect”. Lithium secondary batteries charge and discharge the dry box materials prepared previously. Tested with LiMn204. Lithium secondary charge, until the voltage reaches the current reduced to 40 As the discharge current, the charging and discharging test results of the component method are shown in Fig. 10 3 · 9V — 2 · 7V-The charging and discharging voltage and capacitor stage and discharge platform are lowered and tend to stabilize the electrical test of polymer electrolyte materials (in the assembled coin-type electricity: &quot; Second), in the automatic drying 彳 f ^ I i cell, lithium metal is used as the anode ^ ^ He Diao into the 充 charge and discharge cycle of the battery charge and discharge conditions set as follows. η Bu · 疋 current 9 0 X 1 〇-2 When ma reaches 3. 9 volts, Vera q Q &amp; inch will hold, 3.9 hooters continue to charge when X 1 0'2mA, charge your bud, day, 丨 μ,

Applicable to the enemy's electricity test, with the voltage of 4.5 × 10-2mA until the voltage drops to 2 · 7 V, the report will be reported and the taxi will be charged. Test with this cycle. As shown in 〃, the charge-discharge cycle shows a steady trend from \ 3 · 9ν ............ cycled more than 100 times in sequence. The relationship between 如图 is shown in Figure 11. It is obvious that the capacity of the coin-type battery is gradually increased from 5.74 mAh / g to the charge level. 5. Conclusion This study added lipophilic modified nano-grade clay to improve colloidal polymerization. The related properties of bioelectrolytic shellfish, the results show that the use of surfactants successfully extended the inter-layer distance of nano-scale clay to more than 22 angstroms, allowing colloidal polymers to enter the clay layers and even reach the phenomenon of delamination. Organic series

Page 18 200411965 V. Description of the Invention (u) Inorganic hybrid materials. He + 炚 can take human, and mouth-sized clay can help to extend the six different rubber cores ♦ a material electrolyte system, 『month』 The fragments that exist in the cracked inorganic layer are divided into two; = 22, when it is broken due to the delamination phenomenon, its electrochemical stability and ionic conductivity are separated from it; there is 10-2 S / cm 'because the main reason is nano-grade clay J =…, machine layer The material structure has the force to destroy the bell ion and the peroxyacid ion j, and the bell ion has a large migration speed. Its ionic conductivity can reach 1.03 × 10-2 s / cm, and its film formation, solvent impregnation and dimensional stability are better than those of electrolyte films without nanometer clay added. According to cycl ic vo 1 tmmetry test, it is known that the electrochemical stability of the electrolyte system is significantly improved by adding nano-grade clay. The lithium secondary battery using this electrolyte has a stable charge-discharge cycle effect and has excellent commercial value. _

Page 19 200411965 Schematic description of the table Description: Table 1, composition formula Table 1, Table 2, composition formula 2, Table 3, composition formula with different plasticizer content Table 4, different types of quaternary ammonium salt PK — 8 05 Modified 20 and d-space (A °) Table 5: Aromatic quaternary ammonium salt Modified PK-805 and PK-802 20 and d-space (A °) Table 6 Nanometer The numerical value of the conductivity of the composite colloidal polyvinylidene fluoride electrolyte is briefly explained: Figure 1. X-ray diffraction absorption peaks of PVdF added with different amounts of PK-80 5 in PVdF. 2. Adding 5% wt of PVdF Transmission electron microscope image Figure 2. Partially enlarged (A) area showing intercalation (intercalation phenomenon) Figure 4. Partially enlarged ") area showing mouth; [〇141 ^ 011 (delamination phenomenon) Figure 5. PVdF addition Comparison of impregnation ability of plasticizers after nano-grade clay Figure 6. Comparison of conductivity of nano colloidal polyvinylidene fluoride electrolytes Figure 7. Difference of plasticizers for nano-colloidal polyvinylidene fluoride electrolytes Figure 8. Impact of nanoplastic colloidal polyvinylidene fluoride with different plasticizer impregnation Differences' quality of conductivity

Page 20 200411965 Brief description of the diagrams Figure IX: Thermal expansion ratio of nano colloidal polyvinylidene fluoride electrolyte film Comparison Figure 10: Charge-discharge cycle test Figure 11: Relationship between charge-discharge voltage and capacitance

Claims (1)

200411965 6. Scope of patent application 1. A colloidal electrolyte containing nano-scale inorganic clay, which uses a surfactant to lipophilicize and modify colloidal polymers and lipophilic clays. It is prepared by intercalation (interca 1 ati ο η) in the agent. 2. The colloidal electrolyte according to item 1 of the scope of the patent application, wherein the colloidal polymer includes polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polypropylene polyoxyethylene, polymethacrylate ester. 3. The colloidal electrolyte according to item 1 of the scope of the patent application, wherein the colloidal polymer is polypropylene to polyvinylidene fluoride. 4. The colloidal electrolyte according to item 1 of the scope of the patent application, wherein the surfactant is a surfactant having a long-chain sintered group / aromatic group. 5. The colloidal electrolyte described in item 1 of the scope of patent application, wherein the molecular weight of the polymer used varies with different polymers, and the choice of molecular weight must have both good mechanical properties and easy intercalation. 6. The colloidal electrolyte according to item 1 of the scope of patent application, wherein the molecular weight of polyvinylidene fluoride is about 10,000 to 1 million. 7. The colloidal electrolyte described in item 1 of the scope of the patent application, wherein the plasticizer is a substance that can dissolve the colloidal polymer and has a plasticizing effect. 8. The colloidal electrolyte described in item 1 of the scope of the patent application is prepared by adding a lithium salt under a suitable proportion of plasticizer to prepare a colloidal polymer electrolyte containing nano-grade clay. 9. The colloidal electrolyte according to item 1 of the scope of the patent application, wherein the surfactant is a long-chain alkyl quaternary ammonium salt and a long-chain phenyl quaternary ammonium salt. 10. The colloidal electrolyte described in item 1 of the scope of patent application, wherein Page 22 200411965 6. Scope of patent application The surfactants are C12H25N (CH3) 3Br, C14H29N (CH3) 3Br, C16H33N (CH3) 3Br, [CH3 (CH2) u] 2 (CH3) 2NBr. 11. The colloidal electrolyte according to item 1 of the scope of the patent application, wherein the plasticizer is dimethylethylene carbonate, diethylethylene carbonate, dimethylformamide, propylene carbonate (PC) / ethylene Carbonate (EC) co-plasticizer and so on. /, 1 2. The colloidal electrolyte according to item 1 of the scope of the patent application, wherein the plasticizer is dimethylformamide and / or a propylene carbonate / ethylene carbonate (PC / EC) co-plasticizer. Among them, lithium 1 3. The colloidal electrolyte described in item 1 of the scope of patent application, the salt is one: one and one is used to prepare bell salts for bell batteries. Among them, lithium 14, such as the scope of patent application! In the π colloidal electrolyte described in the item, the salts are LiPF6, LiCF3S03, LiN (CF3S02) 2, LiBF4 LiSCN, Li ASF6, LiC104, and the like. Among them, lithium 15. The colloidal electrolyte described in item 1 of the scope of patent application, and the salts are LiPF6 and LiCl04. ^ Please refer to the gelled electrolyte described in item 1 of the patent scope. In 1, the battery for impact products and / or electronic grade products is used as the battery for one person. State of the electrolyte. One month away Page 23 200411965 6. Scope of Patent Application Page 24