TW382826B - Solid state electrolyte cell and method for producing same - Google Patents

Abstract

A solid electrolyte cell in which the state of electrical contact between the solid electrolyte and the layers of active materials of the positive and negative electrodes and the inter-particulate distance in the layers of active materials of the positive and negative electrodes can be optimized to assure superior load characteristics, and a method for manufacturing the cell. The method for manufacturing a solid electrolyte cell includes a step of applying a paint containing an active material and a binder to a current collector to form a layer of an active material, and a step of impregnating a solid electrolyte in the layer of the active material formed by the active material layer forming step. The impregnating step includes applying the paint comprised of the solid electrolyte dissolved in a solvent on the layer of the active material to allow the paint to be permeated into the layer of the active material, and subsequently drying the solvent.

Description

V. Description of the invention < A7 B7 BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a solid electrolyte battery, 'a solid electrolyte is filled in a positive electrode active material or a negative electrode active material #, and a method of manufacturing the battery method.

A f related technology said that recently,% of the built-in cameras in the industry are used for this battery, and they are also working on thin batteries. The electrolyte will contact the electrodes and move to the state of the battery. It affects many types of portable electronic video recorders: mobile phones or a stage, and attempts are being made to reduce the size of some portable electronic equipment. Research and conditioning of the electrolyte I is actively carried out by coagulation. In particular, the polymer solid electrolytes are attracting attention. The thickness of the battery is more significant. No battery solid electrolyte is used in a liquid, so in a reasonable percentage because ions pass through the solid state. : So the nature of solid-state batteries is huge. If it is between, for example, a study of the size and weight of a laptop computer, the lithium battery check is obtained by conducting the electrolyte, has a lithium salt, or contains one: already in this volume at the same time , Especially the battery, which is the most positive. The solid electrolyte obtained can be reduced in high plasticizers with reduced gelatinity compared to the danger of using liquid contents to leak. P batteries: it is not in the desired state. • It has almost no electrolyte or gel electrode. Contact between the solid electrolyte and the electrode Between the solid electrolyte and the electrode. --- ^ ----- 1--pack -------- order ------ line ί (诮 read the note on the back first (Remarks on this page) The paper team states the state storehouse standard (CNS) A4 specification (210X297 mm) -4-A7 — _B7 5. The description of the invention (2) The contact status is crude, then The contact resistance between the solid electrolyte and the electrode will increase, which increases the internal resistance of the battery. In addition, ions cannot be moved between a solid electrolyte, and the ideal state between the electrode and the battery thus reduces the capacity of the battery. Words: It is critical to have a sufficient dense contact with the active material of a layer of electrodes / It is disclosed in Japanese published patent H-2-4 0 8 6 7 that a positive electrode composition is used: Obtained from the activity of adding a solid electrolyte to the positive electrode Material layer to improve the contact state between the solid electrolyte and the electrodes interposed. Among the batteries disclosed in this publication: a part of the solid electrolyte is mixed with an active material layer of the positive electrode to improve the state of electrical contact between the solid electrolyte and the electrode. For the battery disclosed in this publication, because the positive electrode plate is made of a positive electrode composition mixed with a solid electrolyte, and a solid * electrolyte is laid on the positive electrode plate \ The ideal contact state between the electrode plate and the solid electrolyte is difficult. In particular, if a solid electrolyte having a rough and rough surface is laid on the electrode layer, then the two are combined in only a poor contact state, thereby increasing the internal resistance, and thus deteriorating its load characteristics. .. In addition, a positive electrode composition mixed with a solid electrolyte, or a negative electrode composition: cannot be sufficiently squeezed because it is suitable for the stretchability of the solid electrolyte, and increases the distance between particles in the composition: and therefore Increased internal resistance; then again deteriorated load characteristics / In addition, positive electrode composition mixed with solid electrolyte: or negative electrode composition, needs to be manufactured in low humidity to prevent inclusion in solid electrolyte --- I- -: ------ install ------ order ------- line—1 * ΐ (" Read the precautions on the back first ^-(1 :? this page) This paper The scale passed the state '丨' around the national standard (CNS) A4 specification (210X297 mm) -5- A7 _B7___ V. Description of invention 6) Deterioration of electrolytic salt. This not only increases the difficulty in quality control, but also significantly increases costs. The invention is thus described. It is an object of the present invention to provide a solid electrolyte battery in which electrical contact between the solid electrolyte and the active material layer of the positive and negative electrodes, and the active material layer between the positive and negative electrode active materials. The distance between particles can be optimized to determine excellent load characteristics, and a method of manufacturing a solid electrolyte battery. In one aspect, the invention provides an electrode including a current collector and a layer formed on the current collector. An active material layer is on the top, and contains an active material and a binder, wherein an electrolytic layer is formed by filling a solid electrolyte dissolved in a solvent on the active material layer. In the solid electrolyte battery of the present invention, since the solid electrolyte is filled in the active material layer, the bonding between the electrolyte and the active material is improved. In another aspect, the present invention provides a method for manufacturing a solid electrolyte battery, comprising the steps of using a coating material containing an active material and a binder on a current collector to form a layer of active material and charging a solid state The electrolyte is in the active material layer formed in the active material layer forming step. 2. The filling step includes using a coating composed of a solid electrolyte dissolved in a solvent on the active material layer to allow the coating to be penetrated into the active material layer, and then drying the solvent in this paper. KS standard (CNS) A4 specification (210X297 mm) —.------- ^ ------ ir ------ ^ J! Page) A7 ___ _B7__ 五 、 Explanation of invention #) In the method for manufacturing a solid electrolyte battery according to the present invention, a coating material containing an active material and a binder is applied on a current collector to form a layer of active material for active During the material layer forming step. In the charging step (, a coating composed of a solid electrolyte dissolved in a solvent is used on the active material layer to allow its coating to penetrate into the active material layer: the solvent is then dried to charge the solid electrolyte In its active material layer, in the method for manufacturing a solid electrolyte battery according to the present invention, a solid electrolyte is charged into the active material layer; the combination between the solid electrolyte and the active material is improved. The contact performance between the active material and the electrolyte is improved, so that the internal resistance is reduced to achieve a battery with excellent load characteristics. 0 Brief description of the figure Figure 1 is a legend showing a solid electrolyte battery according to the present invention A side cutaway view of the structure. Figure 2 is a schematic perspective view showing only the basic part of another solid / salt electrolyte battery according to the present invention. The main components are shown in Table 1. Positive electrode plate. La 正Electrode current collector. Lb An active material layer for the positive electrode. The size of this paper is inconsistent with Sichuan National Standard (CMS) A4 (210X2 97 mm) ---- I ------- install ------ order ------- line ί (诮 1 read the notes on the back and write this page again) A7 --- ---------------- 5. Description of the invention) 1 G solid electrolyte layer 2 negative electrode plate 2 3 negative electrode current collector 2 b active material layer of negative electrode 2 C solid electrolyte Layer 3 Separator 4 Sheath material 5 Sheath material 6 Hot melt material

I. Description of the preferred embodiment. A schematic structure of a solid electrolyte battery according to the present invention is shown in FIG. The solid electrolyte battery includes a positive electrode plate 1, which is composed of an active material layer 1b of a positive electrode and a solid electrolyte layer formed on a positive electrode current collector 1a, and a negative electrode plate 2 ' The electrode is composed of a layer of active material 2 b and a solid electrolyte layer formed on a negative electrode current collector 2 a, and a separator 3 for separating the positive electrode plate 1 from the negative electrode plate 2. The solid electrolyte battery also contains a sheath material 4 to fix the positive electrode plate 1., a sheath material 5 to fix the negative electrode plate 5., and a hot-melt material 6 to join the sheath materials 4 and 5. The positive electrode plate 1 is composed of a metal sheet, such as an aluminum sheet, and a positive electrode mixture containing a positive electrode active material, and a binder coated thereon. : And dried there to form the active material layer of the positive electrode ----- " --- „--------------------- line | is f '{^ fJlw · Read the precautions on the back of the book S) This paper size violates the National Park Standard (CNS) A4 size (210X297 mm) -8-This paper size ii State Prisoner's National Standard (CNS) Α4 size (2 丨 0X297 mm) A7 _______B7__ V. Description of the invention) • v 1 b. A solid electrolyte layer 1 c is also formed on the active material layer 1 t > of the positive electrode at the same time, as will be explained next> / For the active material of the positive electrode: metal oxide, "the polymer material specified by metal sulfide g can be used according to the type of battery under consideration. For example, for the construction of a lithium ion battery, metal sulfide or Oxides such as T i s2 \ Mo s2 or ν2〇5 can be used as the active electrode At the same time, the lithium composite oxide formed mainly by Li x M02, where M represents one or more transition metals and X is usually not less than 0.05 and not more than 1.10, which is based on the battery charge / Among the transition metals M constituting the lithium composite oxide,% C, Ni, or Mη is more suitable. Specific examples of the lithium composite oxide include LiCo〇2, LiNiOa ^ LiNiyCOi-yOz, Among them, 0 < y < l., And L iMn204, these lithium composite oxides which can generate high voltage, can be used as a positive electrode active material with excellent energy density. Many kinds of positive electrode active materials Can be mixed and used to form a positive electrode *, as a binder for a mixture of positive electrodes, any suitable known junction < ·, ί: a mixture can be used, and a conductivity agent or any suitable known additive The agent can be added to the positive electrode mixture. As for the negative electrode plate 2? a negative electrode mixture containing a negative electrode active material and a binder. 1? The negative electrode mixture is smeared on a metal sheet, such as a copper I sheet ., As one The negative electrode current collector 2 a, and in V configuration where it is dried to the negative electrode active material layer 2B .. in the negative electrode active material layer (blame read back surface of another power considerations clever page) - loaded.

, 1T line A7 ___ _B7 V. Description of the invention 0) It is expected to contain a plasticizer: and it is in a gel state. By using the solid electrolyte of the gel, it is possible to improve the contact state between the electrolyte and the active material and make the battery flexible: in the following explanation%

A gelled solid electrolyte containing a plasticizer is called a gel electrolyte. For plasticizers: esters; ethers or carbonates can be used alone or as a component of plasticizers. The amount of plasticizing static | is preferably based on the amount of gel electrolyte, not less than 10 wt% and not more than 80 wt%. If the amount of plasticizer is more than 80 wt%, the mechanical force cannot be maintained, even if its ionic conductivity is so high: if the amount of plasticizer is less than 1 Owt%, the ionic conductivity is low: Even if its mechanical force is very high "For the best agreement between ionic conductivity and mechanical force, the amount of its plasticizer is preferably based on the amount of gel electrolyte, not less than 1 Ow t% and not more than 80. wt%. ; Y Plasticizer also contains lithium salt. As the lithium salt used in the electrocoagulation of knee gels according to the present invention; those used as liquid electrolytes in general batteries can also be used. Examples of lithium salts include L i PF6: L i BF4,

LiAsF6: LiCl04, LiCFaF03, LiN (S02CF3) 2, LiC (S02CF3) 3, LiAlCl4 and LiSiFe. Among them, .LiPF6 and Li BF are better for oxidative stability: although the lithium salt concentration of not less than 0.1 mo 1 / 彡 and not more than 3. Omo 1 / z is acceptable, but not Less than 0.5mol / ί and no more than 2.0 m ο 1 is more desirable: as a polymer array material used in the gel of the above-mentioned plasticizer, > CNS) A4 specification (2 丨 0X297 mm) · ~~~ '-----

V A7 ___B7_ 5. Description of the invention (10) In the layer 2 b, and finally the solvent is removed to gel the electrolyte: the resulting gelled matter is filled with an active material to prepare a solid electrolyte layer 1 c > 2 c: The positive electrode plate 1 and the negative electrode plate 2 prepared here: the positive electrode sheath material 4 and the negative electrode sheath material 5, which are embedded therein. The positive electrode sheath material 4 covering the positive electrode plate 1 and the negative electrode sheath material 5 covering the negative electrode plate 2 are formed into a layer by a separator 3 such that the gel electrolyte layer 1 c and the gel electrolyte layer 2 c will face each other through the separation 3. Finally, the outer edge portion of the sheath material of the positive electrode and the sheath material of the negative electrode are thermally fused together by the hot melt 6: and tightly sealed together to complete the solid electrolyte battery. / Separator 3 represents a separation insulator provided between the positive and negative electrodes. Any suitable known breathable film that is used as a battery separator. For example, polyethylene, polypropylene, polyamide or vinylidene polyfluoride can be used as a separator 3 / although the breathable film It is used as a separator in the above embodiment, but the present invention is not limited thereto, and a solid electrolyte layer formed on the active material layer can be used as a separator, as shown in FIG. 2 It can be noted that the thickness of the solid electrolyte layer is not less than 1 # m and not more than t 3 0 0 A m 'If the thickness of the solid electrolyte layer is less than 1 // m., The effect of the solid electrolyte on the electrode surface is easy. Internal cracking occurs due to cracking. / If the thickness of the solid electrolyte layer is greater than 300 A m, the solid electrolyte layer is liable to reduce the energy density of the solid electrolyte battery due to the increase in volume. This paper & (CNS) A4 specifications (2 丨 0X297 mm) (iA first read the back; i-think the matter and then 桢 r- :? this page)-installed., 11 lines ________B7____ 5 'Invention Description (11). .If the thickness of the solid electrolyte layer is not less than 1 and not more than 3 0 0. # m: The positive and negative electrodes can be more reliably isolated and insulated from each other to prevent internal short circuits and not reduce the energy density of the solid electrolyte battery. .. The thickness of the solid electrolyte layer is preferably not less than 5 / zm and not more than 50. The thickness of the solid electrolyte layer is the thickness of the solid electrolyte layer formed on the active material layer of the positive electrode and the active material layer formed on the negative electrode. The total thickness of the solid electrolyte layer: and can be adjusted by adjusting the amount of electrolyte solution applied on the active material layer. The thickness of the solid electrolyte layer is preferably not less than 5 // m and not more than 50, as described above: by setting the thickness of the solid electrolyte layer to be not less than 5, the interior of the solid electrolyte battery as a product The short-circuit ratio can be suppressed to not more than 10%: In addition, 'by setting the thickness of the solid electrolyte layer to not more than 5 0 // m., It is determined that the energy density of a measured volume is not less than 3 0 0 wh / " It is possible.. The shape of the solid electrolyte battery of the present invention is not limited because it can be designed as a cylinder: a coin-shaped or button-shaped * with edges and corners, and it can be any suitable different size, such as a Small size or a large size. Example A plate-shaped gel electrolyte battery having the above structure was prepared. I n .. nn "I n I line-~ {« 51 Read the precautions on the back of the book again. N) This paper scale follows "The prisoner's family sample ([? ^} 戍 4 size (2 丨 0 乂 297 Mm) 14-

^] ;;-'!, lG wlv'-; i-fA ;: "-印 V A7 B7 Five 'invention description (12) Example 1 A positive electrode was prepared as follows: First, lithium carbonate and cobalt Carbonate is mixed at a ratio of 0.5 mo 1 to 1 mo 1, and the resulting mixture is burned in the air at 900 ° C for five hours to produce li C 0 02 as a positive electrode The active material, 91 parts by weight of Li C 002 thus obtained, 6 parts by weight of a conductive agent and 10 parts by weight of the binder were mixed to prepare a positive electrode mixture. As a conductive agent and as a binder, graphite and a polymer of polyethylene fork fluoride and hexafluoropropylene are used individually. Finally, the positive electrode mixture was dispersed in N-methyl-2-pyrrolidone to provide a slurry: it was then spread evenly on one surface of a 20-thick aluminum sheet to become a positive electrode current collector. And it is dried in place to form an active material layer of the positive electrode. The resulting product is compression molded into a roller stamper to prepare a positive electrode. A negative electrode was prepared as follows: First, 42.5 parts by weight of ethylene carbonate, 4 2.5 parts by weight of propylene carbonate, and 15 parts by weight of Li PF6 were mixed in -To prepare a plasticizer *. Then, the above-mentioned plastic portion of 30 parts by weight of an ethylidene fluoride and a polymer of hexafluoropropylene by weight of 10 parts and 60 parts by weight of tetrahydrofuran are mixed together to Prepare-a gel electrolyte solution. — „— ^ ------ install ------ order ------ line < 〆 {诮 read the precautions on the back first "-? 1page) Zhongjia Standard (CNS > A4 specification (210X297mm) -15- 5. Description of the invention (13) An active material layer on the positive electrode and an active material layer on the negative electrode are evenly coated with the above-mentioned gel electrolyte Solution: The resulting combination is allowed to continue at room temperature for eight hours to allow the gel electrolyte solution to be filled into the active material layer of the positive electrode and the active material layer of the negative electrode. Finally, the tetrahydromethylene oxide : As a solvent for the gel electrolyte solution: it is evaporated to form a gel electrolyte layer on top of the active material layers of the positive and negative electrodes. The positive electrode was placed face to face and pressed together on its gel electrolyte side to produce 'a flat-type gel electrolyte battery having an area of 2.5 cm x 4.0 cm and a thickness of 0.3 mm. Example 2 A The gel electrolyte battery was prepared in the same manner as in Example 1. It uses a polymer of ethylene fork fluoride and hexafluoropropylene and polyethylene fluoride as a positive electrode binder and a negative electrode binder. Example 3 A gel electrolyte battery is the same as in Example 1. Method I was prepared, except that a polymer using polyethylene fork fluoride and an ethylene fork fluoride and hexafluoropropylene was used as a positive electrode binder and a negative electrode binder. Example 4 A gel electrolyte battery Prepared in the same way as in Example 1, except that it uses a polyethylene fork fluoride as a binder for the positive and negative electrodes. -16- (Please read the precautions on the back for details. Ball-κ- 本(Page) This paper is a standard-sized storehouse in the flood season (CNS > A4 size (210X297 mm) A7 B7 V. Description of the invention (14) In the following examples 5 and 6, a gel electrolyte was filled In the active material layer of one of the electrodes, a gel electrolyte was added to the electrode mixture of the other electrode in advance. Example 5 A positive electrode was prepared as follows: First, lithium carbonate and cobalt carbonate were 5mo 1 to 1 mo 1 ratio mix Together and burn in air at 900 ° C for five hours to prepare L i C 002 as an active material for the positive electrode. 42.5 parts by weight of ethylene carbonate: 42 by weight of propylene carbonate 5 parts and 15 parts by weight of Li PF6 are mixed together to prepare a plasticizer, 8 parts by weight of Li C 002, 6 parts by weight of conductive agent, A binder in 3 parts by weight and a plasticizer in 8 parts by weight are mixed together and dispersed in tetrahydrofuran to form a slurry. As a conductive agent and as a binder, graphite and polyethylene fork fluoride are used individually. This slurry was evenly spread on one surface of a 20-thick strip of aluminum foil to become a positive electrode current collector, and was dried in place to form an active material layer of the positive electrode: The product is compressed and molded into a roller stamper to prepare a positive electrode. A negative electrode was prepared as follows: First, 90 parts by weight of the ground graphite powder and a junction IU-n h--LI —-_ n I nmn T n I n In I •, va shift · < i (Please read the notes on the back of the song, please continue%: 'This page) This paper is the arc size of this paper; 丨 丨 China Prison Garden Home Standard Feng (CNS) A4 Specification (2 丨 0X297 mm) · 17 A7 _________B7_ 5 2. Description of the invention (15) The 10 parts of the mixture by weight are mixed together to prepare a negative electrode mixture. As a binder, a polymer of ethylene fork fluoride and hexafluoropropylene was used. The binder is dispersed in N-methyl-2-pyrrolidone to form a slurry. It is evenly spread on one surface of a 10-thick strip of copper foil to become a negative electrode current collector.

I and dried in situ to form an active material layer for the negative electrode. The resulting product was compression molded into a roller stamper to prepare a negative electrode. A gel electrode solution was prepared as follows: First, the ethylene carbonate was 40. 5 parts by weight, and the propylene carbonate was acidified. 4 2.5 parts by weight and 15 parts by weight of Li PF6 were mixed together to prepare a plasticizer. Then the above plasticizer is 30 minutes by weight. A vinylidene fluoride and a polymer of hexafluoropropylene are added by 10 parts by weight and 60 parts by weight of oxytetrafluoride are mixed together. Prepare a gel electrolyte solution on top of an active material layer of the negative electrode. The gel electrolyte solution described above is evenly applied. The resulting combination is allowed to continue at room temperature for eight hours to allow the gel electrolyte solution to be washed. Filled in one of the active material layers of the negative electrode. Finally, Tetrahydromethane: a solvent that is a solution of a gel electrolyte, is distilled off to form a gel electrolyte layer on the negative electrode layer. The negative electrode and the positive electrode filled with the gel electrolyte were placed face to face and pressed together to produce a flat-type gel electrode having an area of 2.5 cm x 4.0 cm and a thickness of 0.3 mm. 18- (" ^ Notes for reading the back 4 " this S) This paper describes the standard of the home garden in China (CNS) A4 specification (210X297 mm) A7 _______B7_ 5. Description of the invention (16) Degraded battery .. Example 6 A positive electrode was prepared as follows ^ First, lithium carbonate and cobalt carbonate were mixed together at a ratio of 0.5mo 1 to 1 mo 1 and burned in the air at a temperature of 900 ° C. Hours to prepare L i C 〇02 as an active material of the positive electrode Li C 002 2 parts by weight. 9 parts by weight of the conductive agent and 10 parts by weight of the binder are mixed Together to prepare a positive electrode mixture. As a conductive agent and as a binder, graphite and polyethylene fork fluoride are used independently. Finally: The positive electrode mixture was dispersed in N-methyl-2-pyrrolidone to provide a slurry. It was then smeared uniformly on a single side of a 20 β m-thick aluminum sheet to become a positive electrode. The electrode current collector is dried in place to form a positive electrode active material layer. The resulting product is compressed and molded into a roller stamper to prepare a positive electrode and a negative electrode is prepared as follows: First, the ethylene carbonate by weight 42.5 parts: propylene carbonate by weight Parts 42 · 5 and 15 parts by weight of Li PF6 were mixed together to prepare a plasticizer. Then, the ground graphite 6 parts by weight / 10 parts by weight of polyethylene fork fluoride, as a binder / and the above mentioned plasticizer parts by 2 5 parts are mixed together and dispersed in Oxytetrafluoride iic, please read the notes on the back before reprinting). Packing. Binding paper size: State prisoner ’s car (CNS > A4 size (210X297 mm) -19- A7 ____ ___B7__ 5. Description of the invention (17) to prepare a slurry ... Finally, the slurry is evenly spread on a surface of a 10 Am thick strip of copper foil, which acts as a negative electrode current collector And it is dried in place to form an active material layer of the negative electrode. The product obtained is compressed and molded in a roller stamper to prepare a negative electrode. A gel electrode solution is prepared as follows:-First, 42.5 parts by weight of ethylene carbonate, 4 2.5 parts by weight of propylene carbonate, and 15 parts by weight of Li PFe are mixed together to prepare a plasticizer ... Then, The above plasticizer is 30 parts by weight. 10 parts by weight of a polymer of ethylene fork fluoride and hexafluoropropylene and 60 parts by weight of tetrahydromethylene oxide are mixed together to prepare a gel electrolyte solution ~ an active material at the positive electrode Above the layer, the gel electrolyte solution was uniformly applied. ≪ The resulting combination was allowed to continue at room temperature for eight hours to allow the gel electrolyte solution to be filled in one of the active material layers of the positive electrode. Middle: Tetrahydromethane, as a solvent for the gel electrolyte solution, is evaporated to form a gel electrolyte layer on top of the active material layer of the positive electrode / 负 negative electrode filled with gel electrolyte and 塡The positive electrodes filled with the gel electrolyte were placed face to face and pressed together to produce a flat-type gel electrolyte battery having an area of 2.5 cm × 4.0 cm and a thickness of 0.3 mm:. ^. II n " — Order II! I line (Notes on the back of 诮 1, and then the sharp edge of the paper) This paper size / 彳 1 National Prisoner (CNS) A4 size (210X297 mm) -20- A7 B7, ΎΛ 叫小; Ji ·广 ， ·· w-?., &Quot;7.iv; f 合 Μ,; Γ-ίΓν: * V. Description of the invention (18) Example 7 A gel electrolyte battery was prepared in the same manner as in Example 1 "" Except that it arranges a polyethylene breathable film between the positive and negative electrodes as a kind of separator. In the equivalent example 1 shown below, a gel electrolyte is sandwiched between an active material of the positive electrode Between the layer and an active material layer of the negative electrode to prepare a battery, without the need to charge the active material layer with a gel electrolyte. In the equivalent example 2: a gel electrolyte is mixed into the electrode mixture in advance: in the equivalent example 3, the gel electrolyte is sandwiched between an active material layer of a positive electrode and an activity of a negative electrode To prepare a battery, a gel active material was mixed into the electrode mixture in advance. «In \ Equivalent Example 1 — A positive electrode was prepared as follows. First, lithium carbonate and cobalt carbonate were An active material L i C which is mixed together at a ratio of 0.5 mo 1 to 1 mo 1 and burned in air at a temperature of 900 ° C. for five hours to prepare L i C 〇 02 as a positive electrode. 0.02 2 parts by weight, 6 parts by weight of the conductive agent, and 10 parts by weight of the binder were mixed together to prepare a positive electrode mixture. As a conductive agent and as a binder, graphite and a polymer of ethylene fork fluoride and hexafluoropropylene are used individually. Finally, the positive electrode mixture was dispersed in N-methyl-2-pyrrolidine {诮 read the precautions on the back first " «? This page)-binding-bookbinding paper size in this state 1¾¾ house standard (CNS) Α4 Specifications (210X297 mm) -21-A7 _____. ___B7___ 5. Description of the invention (19) Ketone is used to supply a slurry i, which is then evenly spread on a single side of a 20 am thick aluminum sheet and acts as a Positive electrode current collector, and dried in place. The resulting product is compressed and molded into a roller stamper to prepare a positive electrode. A negative electrode is prepared as follows. First: 90 parts by weight of ground graphite powder and 10 parts by weight of a binder. Parts were mixed to prepare a negative electrode mixture. "As a binder: a polymer of ethylene fork fluoride and hexafluoropropylene is used. The binder is dispersed in N-methyl-2-pyrrolidone to form a slurry? This slurry is spread evenly on a single surface of a 10-thick strip of copper foil. It acts as a positive electrode collector and is dried in place to form an active material layer for the negative electrode! It is then compression-molded to form a negative electrode. A kind of gel electrolyte is manufactured as follows ^ First, 42.5 parts by weight of ethylene carbonate, 42.5 parts by weight of propylene carbonate and 15 parts by weight of Li PF6 are Mix together to prepare a plasticizer. 30 parts by weight of the plasticizer, 10 parts by weight of a vinylidene fluoride and a polymer of hexafluoropropylene and 60 parts by weight of oxygen tetrafluoride are mixed together and dissolved to prepare A gel electrolyte * Gel electrolyte is applied on a Teflon sheet to supply a gel electrolyte film, which is sandwiched between an active material layer of a positive electrode and an active material layer of a negative electrode and is pressed Join together to prepare a tool with-, .--------- install ------ order ------ line I ί {«You must read the notes on the back and write this page again. ) This paper recognizes the scale of this / 彳] National Prisoners' National Building Rate (CNS) Α4 is present (210X297 mm) -22- A7 A _____ ____B7_____ 5. The description of the invention has an area of 2.5cmx5. A flat-type gel electrolytic lean cell having a thickness of 3 mm ^ Equivalent Example 2 A positive electrode was prepared as follows: First, lithium carbonate and cobalt carbonate were mixed at a ratio of 0.5 to 1 mo 1, And the resulting mixture was burned in the air at 900 t for five hours to produce L i C 〇 2 An active material for the positive electrode ~ 42.5 parts by weight of ethylene carbonate, 4 2.5 parts by weight of propylene carbonate and 15 parts by weight of Li PFe are mixed together to prepare A plasticizer / L i C 〇02 2 by weight 8 3 parts / conductor by weight 6 parts, binder 3 parts by weight and plasticizer 8 parts by weight are mixed together and dispersed In tetrahydrofuran to provide a slurry. Graphite and polyethylene fork fluoride are used individually as a conductive agent and as a binder. Finally, the slurry is spread evenly on one surface of a 20-thick strip of aluminum foil: it acts as a positive electrode current collector, and is dried in place to form an active material layer for the positive electrode. ? The resulting product was compressed and molded into a roller stamper to prepare a positive electrode. A negative electrode was prepared as follows: 42.5 parts by weight of vinyl carbonate! Acrylic carbonate with ------ r ---.--------------------- order ~~ ί (¾Read the precautions on the back first, and then use this page) This paper The standard of prisoners in Zhangzhou (fNS> A4 size (210X297mm) -23 · A7 B7 V. Inventor woman) 42.5 parts by weight and 15 parts by Li PF6 by weight Mix together to prepare a plasticizer. · Then, grind the fork fluoride with the weight of plasticizer and the weight of the oxygen oxide to the final, the one of this mud-shaped copper sheet and the product dried in place is rolled with a positive electrode and negative to form a There are 65 parts by weight of graphite powder in one part, 10 parts in polyethylene sheet: as a binder: and 25 parts, can be mixed together and dispersed in PTFE to prepare a slurry . The slurry is evenly spread on a 10-thick strip surface. Its function is to dry a positive electrode collector to form an active material layer for the negative electrode. The resulting barrel stamper was compression molded to prepare a negative electrode *. The electrodes are placed face-to-face and are pressed and bonded together to a flat-type gel electrolyte battery of an area and thickness of 2.5 cmx4 · 0 cm. {Read the precautions on the back of the page first, then 本页 -it? This page) • Equipped the equivalent example 3 wire 丨. A positive electrode was prepared as follows: First, lithium carbonate and cobalt carbonate were prepared with a 0.5mo 1 to * The ratio of 1 mo 1 is mixed, and the resulting mixture is burned in the air at a temperature of 900 ° C for five hours to produce L i C 〇02 as an active material of positive electrode A fi 巧 卬 ethylene carbonate 42.5 parts by weight of salt, 4 2.5 parts by weight of propylene carbonate and 15 points by weight of Li PF6 are mixed together to prepare a plasticizer ... L i C 〇〇 2 Part 8 by weight 3, The paper size by conductivity meter Quzhou 屮 S prisoner Biaofeng (CNS} A4 size (210X297 mm> -24- A7 _ B7____ V. Description of the invention) (Notes on the back of You especially- »Qiao Ben Ai) 6 parts, 3 parts by weight of the binder and 8 parts by weight of the plasticizer are mixed together and dispersed in tetrahydrofuran to For the formation of a mud .. Graphite and polyethylene fork fluoride are used as a conductivity agent and as Mixing ... The slurry is evenly spread on one surface of a 20-m-thick strip of aluminum foil, which acts as a positive electrode current collector, and is dried in place to form a positive electrode An active material layer. The product obtained is compressed and shaped by a roller stamper to prepare a positive electrode. A negative electrode is prepared as follows: 4 2. 5 parts by weight of ethylene carbonate, propylene carbonate 42.5 parts by weight of salt and 15 parts by weight of Li PF6 are mixed together to prepare a plasticizer. Then, the ground graphite powder is 6 parts by weight. Polyethylene «Fork 10 parts by weight of fluoride / as a binder, and 25 parts by weight of plasticizer, are mixed together and dispersed in oxytetrafluoride to prepare a slurry / the slurry is uniform Ground on a single surface of a 10 Am thick strip of copper foil, it acts as a negative electrode current collector and is dried in place to prepare a negative electrode. A gel electrolyte is prepared as follows :, First, 42.5 parts by weight of ethylene carbonate, 42.5 parts by weight of propylene carbonate, and 15 parts by weight of LiPF6 were mixed together to prepare a plasticizer. Plasticizer 30 parts by weight. A vinylidene fluoride and six paper-grade iW'Sl national standards (CNS) Λ4 specifications (210X297 mm) -25- A7 B7 V. Description of the invention) 10 parts by weight of the polymer and 60 parts by weight of tetrahydromethane were mixed together and dissolved to prepare a gel electrolyte. Gel electrolyte is applied on a Teflon sheet to form a gel electrolyte film which is sandwiched between an active material layer of a positive electrode and an active material layer of a negative electrode to prepare a flat gel Electrolyte batteries. 0 Evaluation of characteristics For each of the batteries prepared above: a theoretical capacity was found, and a time-rate discharge was performed to evaluate its discharge capacity. • »Evaluations were performed at room temperature 2 3 ° C. First, for each • battery, the upper limit of a charging voltage is set to 4 ·? -Y: and under a charging current of 6 η A, a fixed-current constant-voltage charging is performed. Each charged battery is then discharged at a constant current until an electrode voltage of 2.5 V is reached. The discharge current is 10 hours, 2 hours, and 1 hour. Set to 3 mA, 16 mA, and 30 mA. From the average voltage at the moment of discharge, one output was found during each time rate discharge. Table 1 shows a theoretical capacity and a discharge output of each battery of Examples 1 to 7 and equivalent Examples 1 to 3: --- Λ ---; --- r--installation ------ order ------- Line ί ί (Notes on the back of TSiL for reading, please continue on this page) This paper is the size of this paper; 1] t storehouse standard (CNS) A4 specification (210X297 mm) -26- A7 B7 »y · i 1. ΛΙΆΠ AM Λ? V. Description of the invention 刼) Theoretical capacity discharge output (mWh) Amount (mAh) l / cl / 5c l / 2c. 1 c Example l 30.0 108.0 107.5 104.4 89.9 Example 2 30.0 107.9 107.5 104.1 90.1 Case 3 29.8 107.9 106.8 103.6 88.5 Case 4 29.8 107.2 106.9 103.3 88.2 Case 5 29.9 1.7.1 104.9 100.8 84.1 Case 6 30.0 107.7 106.7 102.2 85.4 Case 7 29.9 107.6 106.5 103.5 88.8 Equivalent Case I 30.0 37.4 13.2 3.4 < 1.0 Equivalent Example 2 29.9 106.6 103.3 88.9 70.1 Equivalent Example 3 29.9 106.1 95.4 74.2 43.3 As can be seen from Table 1, in Examples 1 to 6, in which the gel electrolyte is filled in at least one of the two electrodes Among the active material layers: the battery has a high discharge output and excellent load characteristics are obtained. At the same time, from Example 7, it can be seen that a battery with a high discharge output and excellent load characteristics can be obtained even when a separator is arranged between the positive and negative electrodes. In the equivalent example 1, in which the gel electrode is not filled in an active material layer of the electrode, but is sandwiched between the active material layers, the discharge output is low, however, In the equivalent example 2, in which the gel electrolyte is added to the electrode mixture in advance, a sufficient output cannot be achieved ------------------------------ -.1Τ ------- 0J ---!-(诮 1Read the precautions on the back again " This page} This paper music scale this M ten "Prison House Standard Soap (CNS) A4 Specification (210X297) (Centi) -27-A7 B7 V. Description of the invention 鲊) To 'In the equivalent of Example 3, part of the gel electrolyte was added to the electrode mixture and the gel electrolyte / and sandwiched between the active material layer., (1) The discharge output cannot be improved. Therefore, it has been found that by using a gel electrolyte solution on an active material layer of the electrode and by filling the gel electrolyte on an active material of the electrode Among the layers, a battery having excellent contact properties between the active material layer and the electrolyte and a high discharge output can be obtained. ^ ΙΡ4 ·-In i-—1 * n I f (" Read the precautions on the back first, and then clever this page) Order ---- ^ ---. ^ This paper rule A is being retired 1¾¾ standard (CNS) A4 specifications (210X297 mm) -28-

Claims (1)

Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives ^ 8ίύ626 β | Ιο m 6. The scope of patent application 1. A solid electrolyte battery includes: an electrode with a current collector and a layer formed on the current collector An active material layer containing an active material layer and a binder;% a solid electrolyte layer formed by filling a solid electrolyte dissolved in a solvent on the active material layer. 2 # The solid electrolyte battery according to item 1 of the scope of patent application: wherein the solid electrolyte contains a polymer array material and is in a gel state. ♦ 3 '. The solid electrolyte battery according to item 2 of the patent application, wherein the polymer array and the binder in the active material layer are the same composite. Y. For example, the solid electrolyte battery according to item 3 of the patent application, wherein the polymer array material and the binder are a fluorine-based polymer material. 5 'The solid electrolyte battery according to item 4 of the patent application, wherein the fluorine-based polymer material is polyethylene fork fluoride. 6. The solid electrolyte battery according to item 4 of the patent application, wherein the fluorine-based polymer material is a polymer of ethylene fork fluoride and hexafluoropropylene. . For example, the solid electrolyte battery of item 1 of the patent application, wherein the negative electrode contains a material capable of doping / removing doped lithium / 8. For solid electrolyte battery of the item 7 of patent application, which can be doped / removed The lithium-doped material is a carbon material. 9. If the solid electrolyte battery of item 1 of the patent application scope, in which the paper XJt is applicable to the BJ® Home Standard (CNS) A4J% # · (210X297 mm): 29 2 '-(Please read the precautions on the back before (Fill in this page) Printed by the Central Bureau of the Ministry of Economic Affairs of the Central Government Bureau of the Kindergarten Consumer Cooperative Co., Ltd. *. DS ^ 628 b | D8 7T, patent application scope The positive electrode contains a lithium composite oxide and a conversion metal. 10. The solid electrolyte battery according to item 1 of the scope of patent application '*, wherein the solid electrolyte layer is formed on an active material layer of each positive electrode and an active material layer of a negative electrode: and the solid electrolyte layers thereof are mutually The solid electrolyte battery is in contact with each other 1 as in the first patent application, wherein the solid electrolyte layer is formed on each of an active material layer of a positive electrode and an active material layer of a negative electrode: and its The solid electrolyte layers face each other with a separator in between. 1 2. A method for manufacturing a solid electrolyte battery includes the following steps: using a coating material containing an active material and a binder to a current collector to form an active material layer; and filling a solid electrolyte with the solid electrolyte In the active material layer formed in the active material layer forming step, the filling step includes using a coating composed of the solid electrolyte dissolved in a solvent on the active material layer to allow the coating to be penetrated into the active material. Material layer, and then the solvent is dried. 13. The method according to item 12 of the scope of patent application, wherein the electrolyte contains a polymer array material and wherein the polymer array material and the binder are the same composite. 14. The method according to item 13 of the scope of patent application, wherein the polymer array material and the binder are fluorine-based polymer materials. 1 5. As for the method of item 14 in the scope of patent application, where --r --- ^ --- ^ j — ^-(Please read the precautions on the back before filling this page) * 1T line The size of this paper is applicable to Chinese National Standard (CNS) A4 specification (2IO × 297 mm) 30- A8 38 ^ 826 b8 D8 Six: The polymer material for patent application is polyethylene fork fluoride. % 1 6. The method according to item 14 of the scope of patent application; wherein the fluorine-based polymer material is a polymer of ethylene fork fluoride and hexafluoropropylene —.------- j --- Packing ------ order --f ----line _ I (Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs -31-This paper size applies to China National Kung Fung (CNS) A4 Washer (210X297 mm)