TW586248B - 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<-2> 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

Bing 6248 ------- Amendment No. 91137412 dated on May 5, V. Description of the invention (1) Summary of the invention The invention relates to the electrolysis of a colloidal polymer containing nano-grade clay. The clay (montmor i 1 loni te) is ordered to be lipophilic and modified, and the colloidal polymer and the lipophilic clay are intercalated in a plasticizer. Adding bell salt under a suitable proportion of plasticizer to prepare a colloidal polymer electrolyte film containing nano-grade clay, which has an ion conductivity of 1.03 × ι_2_2 s / cm, has good film-forming properties, and is plastic-impregnable The rate and dimension stability are better than those of electrolyte films with nanoscale clay. And, add nano-grade sticky

= Electrolyte film also makes the electrochemical stability of the electrolyte system obvious. The present invention also relates to a prepared secondary battery, which has a stable charge and discharge cycle of colloidal state containing nano-grade clay = a lithium secondary battery made of an excellent polymer electrolyte with a ring effect. Commercial value. BACKGROUND OF THE INVENTION With the advancement of human science and technology, the demand for bio-informatics products has also greatly increased. That is, researchers and designers are actively working hard. It is portable and light, thin, short, and small as a source of product power. Improve the goals of various electronics and therefore, product functional improvements. Among them, the wireless of products is expected by the consumer market. Pool. Must also meet safety, weight

586248

Light, thin and environmentally friendly secondary batteries have been developed. The polymer pool system has both electrolyte and yin and yang functions, so the ionic conductivity and scale must meet certain standards. Therefore, high-performance lithium polymer electrolyte materials have two kinds of stability and electrochemical stability in the separator between lithium polymer secondary electrodes. The first research on polymer electrolytes was made by Wright et al. It was proposed by people in 1973 that they added KSCN to poly (ethylene oxide) (PE0) by mixing, and the experimental results obtained a crystalline complex. Then in 1975 Wright et al. Further proved that these complexes have a conductivity of more than 10_4 s / cm at high temperatures (above io ° 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 Polyacrylonitrile (PAN) is the most valuable. Reich and Michael i were the first to propose such polymer electrolytes, and since then they have attracted the field of research into the early morning research. A 1994 study by Scrosati et al. Found that Gel-Type Polymer Electrolytes with PAN as the main body can have an electrical conductivity of more than 10-3 S / cm 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 more than 10-5 S / cm. Although the conductivity is high, the dimensional stability is relatively reduced. Therefore, Al 1 cock et al. Used r-radiation to make the MEEP molecular chain part

Page 8 586248 Amendment a Case No. 91137412 V. Description of the invention (3) Cross-linking to improve the machinability. In recent years, Aucoc et al. Have improved the dimensional stability of MEEP with the same chain length ether group substituents. However, κ and Abraham et al. Used PEO and MEEP to improve the M. properties of fluorene, but because of the crystalline structure of PEO, the migration of cations hindered the original conductivity of MEEP to have a negative effect. OBJECTS OF THE INVENTION The purpose of the present invention is to change the colloidal polymer electrolyte material by using a blend of a plasticizer with a high dielectric constant and nano-grade clay to shape the gel electrolyte film to improve the thermal stability of the polymer electrolyte film. ： Dimensional stability, film formation, ionic conductivity and electrochemical stability of colloidal polymer electrolyte membrane. This electrolyte has a stable charge-discharge cycle effect on lithium secondary batteries and has excellent commercial value. DETAILED DESCRIPTION OF THE INVENTION The present invention utilizes a surfactant to lipophilicly modify inorganic clay (montmorillonite), and to intercalate polymers and lipophilic clays in plasticizers (intercalation). Then, a lithium salt was added under an appropriate proportion of a plasticizer to prepare a colloidal polymer electrolyte film containing nano-grade clay. · The surfactants referred to in the present invention can be used in the present invention, such as long-chain alkyl quaternary ammonium salts and long-chain phenyl quaternary ammonium salts. alkyUmmomium salt), sodium lauryl sulfate, triethanolamine lauryl sulfate, lauryl amine

Page 9 586248

Trimethylammonium stearate, trimethylammonium stearate, benzyl ammonium stearate, dimethyl benzyl ammonium stearate, trimethylammonium laurate dimethylaminoacetate, polyoxyethyl Diamine stearic acid, dimethylamine stearic acid lactam acetate, polyoxyethylene nodular oil fatty acid amide, coconut oil fatty acid monoethanolamine, stearic acid diethanolamine, stearic acid monoamine Ethanolamine's diethanolammonium stearate, c i2H25N (CH3) 3Br ^ C14H29N (CH3) 3Br ^ C16H33N (CH3) 3Br [CH3 (CH2) n] 2 (CH3) 2NBr, C12H25S04Na, C14H29S04Na, C16H33S04Na, Na, C12H25S04N (C4H9) 4, C12H25S04N (CH3) 3C12H25, C12H25 CH (々COO) N (CH3) 3, (C4H9) 2CHCH2 (OC2H4) 9OH and n_C12H25 (OC2H4) 31 OH, etc., preferably long chain alkane Quaternary ammonium salts, especially ^ 2 ^ ((: 113) 3, C14H29N (CH3) 3Br, C16H33N (CH3) 3Br and [CH3 (CH2) n] 2 (CH3) 2NBr, etc.) Polymers, including all colloidal polymers, can be modified by the method of the present invention, for example, polyvinylidene fluoride (PVdF), polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP polypropylene, PAN), Polyoxyethylene (PE0), Methyl methacrylate (PMMA), of which polypropylene and polyvinylidene fluoride are preferred. The molecular weight of the polymer used varies with different polymers. The choice of molecular weight must have good mechanical properties and be easy to intercalate. The effect, taking polyvinylidene fluoride as an example, can be about 10,000 to 100,000.

The plasticizer referred to in the present invention is that anyone who can dissolve the colloidal polymer and has a plasticizing effect can be the plasticizer of the present invention, for example, dimethylene carbonate (DMC), diethylethylene carbonate (Diethylene carbonate, DEC), dimethylformamide (N-N'dimethylformamide, DMF), propylene ester

Page 10 586248 -SS__9U37412 V. Description of the invention (5) carbonate, PC) / ethylene carbonate

, It can be converted thEthylene carbonate ^ EC i = guangshang f second plastic, the mixture ... preferably the second plastic co-plastic 3 acetonitrile / acetic acid carbonate (PC / EC) of the present invention Refers to Wei Bg, Youxi borrows aluminum and other materials, such as miscellaneous materials, and the dish is not particularly limited. It can be a bell salt commonly used in the preparation of clock batteries, for example, L 彳 ρ ρ S〇2) 2 ^ LiBF4 .use LiA 6 ^ 1 ^ 8 ° 3

LiPF &gt; lSCN UAsF6, LiC104, etc. Among them, LU ^ 6 and LiC104 are preferred. Edited, the nano-grade clay used is a commodity for impact-resistant products 溆 = ",, one, and the product number for electronic grade products is PK805, etc., and the modified clay is 〇-PK802 , ◦—ρκ800, etc. The lipophilic modification of the surface-active agent selected in the present invention with inorganic clay ρκ_805, ^ -802, in addition to expanding the distance between clay layers, ' Polymers of molecular weight (PVdF, Mw · 10000) enter the clay layer and intercalate (intercalati) to form colloidal nano polymer electrolyte materials. This finding helps to reduce the process and time. Can be suitable for other polymer materials with molecular weights below loooooo.

Specific implementation method of the present invention The lipophilic treatment of clay will include an appropriate amount of a cationic surfactant Ci2jI25N (CH3) 3 containing a long carbon chain.

Br, ci4H29N (CH3) 3Br, C16H33N (CH3) 3Br, [CH3 (CH2) U] 2 (CH3)

Page 11 586248 _ Case No. 91137412 V. Description of the invention (6): Correction pBr is filtered separately from the clay aqueous solution and treated with deionized water and nail: homogeneous stirring 'for lipophilic treatment. Then m mr \ i fresh ’to clean the excess surfactant and salt in the clay, and dry and grind the modified clay. Tian; ^ ,, winter h Α 〇 ten different surfactant required grams. The heavy summer (g) = the cation exchange equivalent (CEC) x 10-3 x the molecular weight of the surfactant x the weight of the clay x the coefficient is between 1-2, preferably 12-15 It is related to the desired distance between the clay layers. The intercalation of the two molecular chains of the polymer first makes the modified clay uniformly dispersed in DMF or pc / EC plasticizer ', and then adds a metered polymer, uniformly stirs for about 2 hrs to form a film on a glass plate 'And put it in a vacuum oven to dry; the PC / EC ratio is about 1: 1 to 8: 1. Finally, the x_ray diffraction analyzer is used to identify the change of its structural type. Preparation of colloidal polymer electrolyte: Polyvinylidene fluoride (MW = 530000), modified clay and lithium salt (LiCl〇4) measured according to ρ value, added in DMF or PC / EC (1: 1 ) The plasticizer is heated (approximately 30 C -1 0 0 C) and uniformly mixed to make the solution appear homogeneous f (homogenous), about 6 hrs. After forming a film on a glass plate, the temperature is controlled to make DMF in the film Or the content of PC / EC plasticizer is in a certain range (about 30% to 60%), and a colloidal polymer electrolyte film is prepared. Where F = Molar number of lithium salt / (grams of polymer / repeated unit molecular weight) _

Page 12 586248 _ Case No. 91137412 _ Year and month Amendment __ V. Description of the invention (7) The composition and formulation of the specific examples of the present invention are shown in Tables 1 and 2, and a colloidal polymer electrolyte is prepared according to the above method. The analysis method of the present invention uses an X-ray diffraction analyzer (Rigaku D / Max-3C 0D-2988N) to analyze the clay layer, and uses an impedance meter (Impede nee Analyser HP4 192A) to measure the ion conductivity of the polymer electrolyte. The transmission electron microscope (JEOL-200FX) was used to observe the microscopic phenomenon of clay dispersed in the polymer electrolyte material, and the cyclic voltammetry (Eco Chemie BV model PGSTAT30) was used to detect the redox cycle potential and oxidative breakdown potential of the electrolyte. Using a Perkin-Elmer DMA 7e analyzer to measure the thermal expansion coefficient of polymer electrolyte materials, to understand the dimensional stability of the materials in the use temperature range. The battery assembled using the electrolyte of the present invention was subjected to a charge and discharge test of a clock secondary battery using an Arbi η-BT-200 battery charge-discharge device. Effect of the invention Lipophilic modification of clay First, the lipophilic treatment of inorganic clay is performed. Clay is an inorganic silicate with a layered f-like structure, which requires the hydrophilic end of the surfactant and the cation in the clay ^ The purpose of ion exchange is to make the long-chain alkanes of the surfactant enter the layers of the clay to achieve the effect of expanding the distance between the layers, so that the molecular chain and the lipophilic end of the surfactant existing between the clay layers generate a phase. Rong ·

Page 13 586248 Case No. 91137419 V. Description of the invention (8) I !: 4 ί: ί to the modification under the same operating conditions, “by X_ray around, = catty” It is known that the change in the distance between layers will vary depending on the interface The type of active agent varies. As shown in Table 4, the distance i ^: a ^ in ^ nium br ^ injde, [CH3 (CH2) ij2 (CH3) 2NBr, and the distance i ^: the structure and bond angle of the double-chain double-chain alkyl group are used to make the double The layers of the long-chain burned clay show a jack type, which effectively expands the layer distance to 22 angstroms. The original inter-layer distance of the surveyed soil is i 2 angstroms. In addition, we also use the aromatic quaternary ammonium salt and perform experiments with the heart of 0-3 as its representative. Its 1 composition is shown in Table 5. The modification test results show that AR0_S…, the distance between the layers of organic clay PK802 is enlarged. It is 2154 Angstroms, and the ρκ805 interlayer distance can be expanded to 18.7 Angstroms after modification. The mixing effect of colloidal polymer and lipophilic clay: Take polyvinylidene fluoride as an example, prepare a polyvinylidene fluoride solution, and after 3% modified clay, the two are evenly mixed into a transparent solution. Form a 0.2mm thickness film. Send on the X_ray diffraction pattern = this is located at 4. The 2-2 angle of Θ has disappeared. This is because the molecular chain of poly (vinylidene difluoride) ethylene may be completely dispersed between the clay layers, so-called exfoliation (L). In order to prove this statement, X-ray diffraction analysis is performed after dissolving lipophilic clays with different amounts of 3%, ^%, 7%) in polyvinylidene fluoride solution to make a thickness of ^, as shown in the figure. As shown in the figure, with the increase of clay content, the map has obvious changes, 1% and 3% are not =, no absorption peak at 20 angles is found on the map, that is, the mixed material formed by these two ratios appears Peeling state

Page 14 586248 Amendment 91137419 V. Description of the invention (9) (ΓΓ = 1η) ’However, if the clay content is increased to 5%, a small wave peak is gradually formed at 2 7» /. When the content of clay is increased to + 〇Μ ® Μ &amp; it is more obvious, showing that polyvinylidene fluoride molecular chain is still intercalation between the layers of clay, so that the angle of 20 is changed from 4 degrees to 3 degrees. When the content of lipophilic clay in vinylidene oxide is above 3%, the organic-inorganic mixed state may be intercalation. A transmission electron microscope was used to observe the dispersion of inorganic clay in the polymer chain. Polyvinylidene diacetate containing 5% cUy was used for testing. The results are shown in Fig. 1. Partial enlargement is shown for some areas. It is obvious that the interlayer destruction and delamination phenomenon of inorganic clay is shown in Figure 3, and a part of the intercalation phenomenon is shown in Figure 4, so the mixing effect of polyvinylidene fluoride and 5% inorganic clay, It has both exfoliation and intercaia interlayer. This result also confirms the test results of X-ray. Plasticizer impregnation properties

The biggest difference between a gel-type polymer electrolyte and a solid polymer electrolyte is the presence or absence of a plasticizer in the polymer system. Relevant literature points out that the presence of plasticizers 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 to add a series of colloidal polymer electrolytes with different F-valued Licl〇4 to control the thickness of the film to 50 ~ 100 // m. It was found that inorganic clay was added. Polymer electrolyte thin film formation,

Page 15 586248 ___Case No. 9137412_Year__Fifth, the description of the invention (10) '___ is significantly better than the unadded polymer electrolyte film, in order to help the plasticizer stay in the polymer electrolyte ^ Learn about inorganic In the polymer electrolyte membrane with and without inorganic clay added, the vacuum oven with Tim Itorr was maintained at 50 ° c, and the observable can be placed at the same time as the 0. The results are arranged in Figure 5, and the results show that with the When the amount of plasticizer is reduced, when the polymer electrolyte film contains inorganic clay, the increase of ^ is helpful when the colloidal rate is helpful, so the addition of PK805 has a good amount of plasticizer that is less impregnated with plasticizer. least. "~ Because of the reduced conductive properties, the polymer is first amorphous in the electrolyte, and then the polymer conductivity is measured. The molecular chains of the polymer are amorphous, and the charge attracts the clock between the clocks. As a result of the measurement of the conductivity of Nai, the degraded film can reach 1.03 dispersed in the over-power which does not contribute to the positive salt, making the speed. According to the phase data, it is found that the conductivity of the lithium salt does not affect the conductivity of the lithium salt in the order of meters. It is found that the conductance of the acid ion of the X 1〇-2 organic layer ion from the lithium ion is closed, and the conductivity starts with the increase in the content of the clock. When organic clay is added to colloidal polyvinylidene fluoride, as shown in the figure, when the nano-grade adhesive i is added, its electrical conductivity is significantly better than that of the non-added clay, which can be increased by about 2 to 3 times. S / cm can be summarized as follows: (1) the 'helps the polymer form to be more conductive; (2) the positron between the inorganic clay layers' destroys the ions and the peroxy acid radicals, and has a greater degree of freedom. Lithium can be improved according to Table 6. The degree is related to the content of the bell salt. It varies from the salt content in the figure. The conductivity increases and increases, but the lithium salt content decreases. The reason is the polymer electrolyte system

Page 16 586248

V. Description of the invention (Π) — The electrical conductivity is caused by ion conduction. Excessive lithium salt is present under the following conditions, which may cause the following conditions: (the anion and cation still have a sub-attractive force, and it is not easy to be plasticizer in the system. Dissociation. (II) System: The ion concentration is high, and it may be combined again during the migration process of the system. The beauty = the two reasons, the number of ions that can be carried in the system is reduced, and the conductivity is reduced. Further changes to the plasticizer The content, from the appearance to the content of the film seems to have little effect on the film, but in terms of the film formation of its mechanical film, the film with a higher plasticizer content is worse. 2 As shown in Figure 8, along with the plasticizer The increase of the content will increase the conductivity t, especially in the PC / EC plasticizer system. Compared with the plasticizer content d and 15%, the conductivity can be increased by about 5 times. However, if the content of the second agent is greater than 45, When it is above%, its polymer electrolyte film is poorer than 2 and there is a problem of plasticizer oozing out. Therefore, the heterogeneity is large. I Research on the size and stability of polymer electrolytes and the separation membrane Generate one May make the road, so that the polymer selected nanoscale 0 · 25, containing plasticizer thermal mechanical analysis study

Materials in lithium secondary battery systems are also used for electrolysis ^ When the battery is charged and discharged, heat may be generated and the polymer electrolyte film may be deformed. For example, the battery charge and discharge cycle efficiency is reduced, and even short electrolyte materials must be excellent The dimensional stability clay content is 3%, the LiC104 measurement value is f = the amount is 15%, and the prepared polyvinylidene fluoride electrolyte (TMA) is tested to observe the heat in a temperature range

586248 37412 修正 Modified V. Description of the invention (12) Expansion coefficient, and compared with colloidal polyvinylidene fluoride electrolyte without nano-grade clay 'The result is shown in Figure IX, with the addition of nano-grade clay. The thermal expansion coefficient of vinylidene fluoride electrolyte is in the temperature range of _50 ~ 800 ° C, and its value is ϋ 4 X i 0-6 delete / I, and the result is obviously better than that without adding nano-grade clay. The colloidal polyvinylidene fluoride electrolyte film has a value of 180. 9 X 1 0-6 legs / C ', which is a fairly good result. The result indicates that nano-grade clay is added. It has improved the dimensional stability of the polymer electrolyte film, and still maintains good dimensional stability even at a high temperature of 80 ° C. It is speculated that the reason is that nano-grade clay is uniformly dispersed in the polyvinylidene fluoride electrolyte film. The nano-layers that are broken by the delamination phenomenon are evenly dispersed between the polymer molecular chains of poly (vinylidene) ene, and there may be a stable intermolecular force between the molecular chains and the nano-layers. It can improve the size stability of colloidal polyvinylidene fluoride electrolytic tincture. Electrochemical test: Corresponding tank, adding lithium ionizing agent to reduce ionization, and stably assemble the assembled electrode connector oxygen-degraded nanometer to the qualitatively obtained colloidal polymer electrolyte film, and perform electrochemical measurement on half of the battery test element Li. / GPEs / Li was used as the working electrode and the lightning film was used as the reference electrode. A nitrogen-filled storage motor-voltage potentiostat was used for the cyclic voltammetry test. The effect of the J-coat was reduced and we found that nano-grade clay was added. The film position can reach 4 · 2V. In the redox cycle test results, the clay does help the colloidal polymer electrolyte. Lithium ion oxygen can cause more plasticity in the electrolyte film. Medium 1 has a plastic effect with a high dielectric constant. W 586248 Case No. 91137412 V. Description of the invention (13) The phenomenon of the mass system dissociates the chain salt and disperses the ions uniformly in the polymer electrolysis. Or the reversibility improvement when electrons are lost contributes to the charge-discharge cycle effect of lithium polymer secondary batteries. Charge and discharge test of doorbell secondary battery ¥ The polymer electrolyte material (thin film) prepared above is used to assemble a coin-type battery in a dry box, using lithium metal as the material and LiMhO4 or LiCo〇2 as the material Cathode material, charge and discharge μ

test. The charge and discharge conditions of the lithium secondary battery are set as follows: constant current mA charging, after the voltage reaches 3.9 volts, maintain 3.9 volts and continue to charge and charge when the charging current is reduced to 40x 10-2 mA, perform a discharge test to 4 &amp; ( -2mA is used as the discharge current. When the voltage drops to 2. 7V, recharge. The charge and discharge cycle test is performed in this condition. The test results are shown in Figure 10. 'The charge and discharge cycle shows a stable trend from 3.9V-2.7V-3.9 V ............ cycled more than 100 times in sequence. The relationship between charge and discharge voltage and capacitance is shown in Figure 11, which clearly shows the charging platform and the discharging platform. 5.74 mAh / g decreases by sea and stabilizes.

In this study, lipophilic modified nano-grade clay was added to improve the related properties of colloidal polymer electrolytes. The results showed that the use of surfactants successfully extended the inter-layer distance of nano-grade clay to more than 22 Angstroms, making Colloidal polymers can enter between clay layers and even reach delamination, becoming a series of organic

P.19 586248, Amendment No. 911370 5. Description of the invention (14) Inorganic hybrid materials. Adding pure clay can help to extend the content and time in the colloidal polymer electrolyte system. When the fragments of the inorganic layer that are broken due to delamination are dispersed in the colloidal polymer electrolyte

2 Electricity S, stability and ionic conductivity, its ionic conductivity can reach 1 machine, material structure cm. The main reason is that the nano-scale clay disintegrates the inorganic layer, the structure, and has the ability to destroy lithium. The bell ions between ions and peroxyacid ions have a large migration speed. Its ionic conductivity can reach U3X 10-2 s / cm, and it has better film formation, solvent impregnation and dimensional stability (diDlensionaal stabiuty) are better than electrolyte films without nano-grade clay. Through cyclic voltammetry (cycUc ITT ^ test), the electrochemical stability of the electrolyte system was significantly improved by adding nano-scale clay. The bell secondary battery composed of this electrolyte has stable charging and discharging cycles. Effect, with excellent commercial value. Page 20 586248 __Case No. 91137412_ Year Month Day Article _ Schematic simple description Table Description: Table 1, composition formula Table 1 Table 2, composition formula 1 Table 3, plasticizer Composition formula table with different contents Table IV. 20 and d-space (A °) of different kinds of quaternary ammonium salts modified PK-805 Table 5. Aromatic quaternary ammonium salts PK-805 and PK-802 2 錾 d-space (A) 1C after modification Table 6: The numerical diagram of the conductivity of the nano-composite colloidal polyvinylidene fluoride electrolyte is not explained briefly. Figure 1. Adding different amounts of PK-805 in PVdF X-ray diffraction absorption peak in Figure 2. Transmission electron microscope image of PVdF added with 5% wt. 2. Partially enlarged (A) region 'intercaiatioli (intercalation image). Figure 4. Partially enlarged (B The area ”shows exf〇iiati〇n (delamination phenomenon) Figure 5. PVdF after adding nano-grade clay Comparison chart of the impregnation ability of plasticizers /, Comparison of the conductivity of nano-colloidal polyimide's gaseous electrolytes Figure 7. The influence of different plasticizers on the conductive sound of nano-colloidal polyvinylidene fluoride ^ Difference in conductivity of nano colloidal polyvinylidene fluoride electrolytes with different plasticizer impregnations

586248 Case No. 91137412 Date Modified Brief Description Figure 9: Thermal expansion ratio of nano colloidal polyvinylidene fluoride electrolyte film Figure 10: Charge and discharge cycle test Figure 11: Relationship between charge and discharge voltage and capacitance

Page 22 586248 _Case No. 9137412_Year Month and Day Revised Schema Table 1 F 値 PVdFfe) LiC104 (g) day 0 wt% fe) PCffiC ^ Ear ratio 1Λ) 35wt% fe) 02 1 0.33 0 0.72 0.225 1 0.37 0 0.74 0.25 1 0.41 0 0.76 0.275 1 0.45 0 0.78 0.3 1 0.5 0 0.81 F 値 PVdF (g) LiC104 (g) 〇Hpk805 3wt% fe) FG / BC® ear ratio 1/1) 35wt% (e) 0.2 1 0.33 0.03 0.73 0.225 1 0.37 0.03 0.75 0.25 1 0.41 0.03 0.78 0.275 1 0.45 0.03 0.80 0.3 1 0.5 0.03 0.82 F 値 PVdF (g) LiC104 (g) op! S8Q2 3wt% fe) VCJECm% it 1Λ) 35wt% fe) 0.2 1 0.33 0.03 0.73 0.225 1 0.37 0.03 0.75 0.25 1 0.41 0.03 0.78 0.275 1 0.45 0.03 0.80 03 1 0.5 0.03 0.82 Table 2 F 値 PVdF (g) LiC104 (g) day Owt% fe) PC / K ^ Ear ratio 4Λ) 35wt% fe) 02 1 0.33 0 0.72 0.225 1 0.37 0 0.74 0.25 1 0.41 0 0.76 0.275 1 0.45 0 0.78 0.3 1 0.5 0 0.81 F 値 PVdF (g) LiC104 (g) o-pkS05 3wl% fe) PG / K ^ Ear ratio 4Λ) 35wt% fe) 0.2 1 0.33 0.03 0.73 0.225 1 0.37 0.03 0.75 0.25 1 0.41 0.03 0.78 0.275 1 0.45 0.03 0.80 0.3 1 0.5 0.03 0.82 F 値 PVdF (g) LiC104 (g) o ^ Is8Q2 3wt% fe) PC / K® ear 4Λ) 35wt% fe) 0,2 1 0.33 0.03 0.73 0.225 1 037 0.03 0.75 0.25 1 0.41 0.03 0.78 0.275 1 0.45 0.03 0.80 0.3 1 0.5 0.03 0.82 Page 586248 Case No. 91137412 Revised Schema Table III PVdF (g ) LiCl〇4 (g) F = OZ75 〇Hpk805 3 wt% (g) PC / EC (X%) FC / BC ^ Ear ratio 1Λ) ω 1 0.45 0.03 15% 0.26 1 0.45 0.03 25% 0.49 1 0.45 0.03 35 % 0.80 1 0.45 0.03 45% 1.21 PVdF (g) LiCl〇4 (g) F = OZ75 o-pk805 3wt% (g) DMF (XX) DMF (g) 1 0.45 0.03 15% 0.25 1 0Λ5 0.03 35% 0.80 1 0.45 0.03 45% 1.21 1 0.45 0.03 55% 1.81 Table 4 quaternary ammonium bromide 2Θ d -space (A) none 7.48 12.00 Ci2H25N (CH3) 3Br 5.28 16.73 Ci4H2gN (CH3) 3Br 4.92 17.95 C16H33N (CH3) 3Br 4.70 18.79 [CH3 ( CH2) ii] 2 (CH3) 2NBr 4.02 22.00 Page 586248 _Case No. 91137412_ Year, month, day, and amendment

Aromatic quaternary ammonium bromide 2Θ d -space (A) none 7.48 12.00 ARO-S / PK805 4.72 18.71 ARO-S / PK802 4.10 21.54

Table six

F value GFEs 0.2 0.225 0.25 0.275 0.3 PVdF + IiC104 + PC / EC (l / lX35 H) 3.6 xlOJ 5.7 xlO-3 5.5 xlO-3 2.2 xl0J PVdF4t7-PK805 + IiC104 + PDEC (1 / 1X35% &gt; 3.2 xlOJ 6 2 xl (H 1-01 xl (H 1_03 8.3 xl0J PVdF ^ -PKBOZ + UClO ,, + PC / EC (1/1) (35W) 3.7 xlOJ 475 xlO-3 3.8 xl0J 3.0 xl0J 2.5 xl0J PVdF + IiC10 ^ + PC / EC (4 / lX35 W) 3.0 xlO-3 4J xl0J 3.8 xl0J 3.5 xlO-3 3.4 xl0J PVdF4t? -PK »05 + LiC104 + POEC (4 / lX35H) 46 xlO-3 5.8 xl0J 7.1 xl0J 7.35 xl0J 5.2 xl0J PVdF ^ -PK802 + IiCl〇4 + PC / EC (muscle) (35¾) 7.8 xl0J 1.01 xl0J 9.6 xl0J 9.1 xl0J 7.9 xl0J

Claims (1)

586248 Modified colloidal electrolyte containing nano-scale inorganic clay, which is characterized by inclusion of inorganic clay and colloidal polymer, wherein the inorganic clay system uses an interface ^^ biogenic agent for lipophilic modification, and then the gel A colloidal electrolyte made by a polymer in the presence of a plasticizer and intercalation with an inorganic clay. 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 (Polyacrylonitrile, PAN), Polyoxyethylene, polymethyl acrylate. 3. The colloidal electrolyte according to item 1 of the scope of the patent application, wherein the colloidal polymer is polyacrylonitrile (PAN), 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 alkyl / 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 plastic effect. 8. The colloidal electrolyte described in item 1 of the scope of the patent application is prepared by adding bell salt under a suitable proportion of plasticizer to prepare a colloidal polymer electrolyte containing nano-grade clay. Page 23 586248 ---- Serial No. 91137412 __ ^^^ ------ ^ VI. Application for patent scope 9. The colloidal electrolyte described in item 1 of the patent application scope, wherein the surfactant is a long chain Alkyl quaternary ammonium salt, long chain phenyl quaternary ammonium salt. 10. The colloidal electrolyte according to item i in the scope of the patent application, wherein the surfactant is C12H25N (CH3) 3Br, C14H29N (CH3) 3Br, C16H33N (CH3) 3 Br, [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, acrylic carbonate (PC) / Ethylene carbonate (EC) co-plasticizer, etc. 0 1 2. The colloidal electrolyte described in item 1 of the scope of patent application, wherein the plasticizer is dimethylformamide and / or propylene carbonate / ethylene carbonate (PC / EC) co-plasticizer. 1 3. The colloidal electrolyte according to item 1 of the scope of the patent application, wherein the lithium salt is a lithium salt commonly used in the preparation of lithium batteries. 14. The colloidal electrolyte described in item 1 of the scope of the patent application, wherein the lithium salt is LiPF6, LiCF3S03, LiN (CF3S02) 2, LiBF4, I iSCN, LiASF6, LiC104, and the like. 15. The colloidal electrolyte according to item i in the scope of the patent application, wherein the lithium salt is LiPF6, LiCl04. 16. The colloidal electrolyte according to item 1 of the scope of patent application, wherein the nano-grade clay is a clay for impact-resistant products and / or for electronic-grade products. 17. A lithium secondary battery, characterized in that a colloidal electrolyte such as item 1 of the scope of patent application is used as a main content filler in the lithium secondary battery.