TWI504039B - Power storage device and method for producing the same and power storage apparatus - Google Patents
Power storage device and method for producing the same and power storage apparatus Download PDFInfo
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- TWI504039B TWI504039B TW102148219A TW102148219A TWI504039B TW I504039 B TWI504039 B TW I504039B TW 102148219 A TW102148219 A TW 102148219A TW 102148219 A TW102148219 A TW 102148219A TW I504039 B TWI504039 B TW I504039B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
本發明是有關於一種蓄電元件的製造方法,特別是有關於一種製作步驟經簡略化、低成本且長期穩定性優異的製造蓄電元件的方法。The present invention relates to a method of manufacturing an electric storage device, and more particularly to a method for manufacturing an electric storage device which is simplified in construction, low in cost, and excellent in long-term stability.
以往為了使用了以筆記型個人電腦或行動電話等各種便攜型機器為代表的電池的一般電氣機器的小型化與輕量化,正在進行小型電池的開發。為了各種便攜型機器等的一般電氣機器的小型化與輕量化,作為電源的電池的能量密度高(高容量化)是不可缺少的。另外,除了小型電池以外,亦進行大型電池的開發來作為電動車或混合動力車所搭載的汽車用的蓄電裝置、或作為組合有太陽電池或風力發電等新能量系統而成的電力儲藏用蓄電池。對如此的大型電池要求更高的能量密度或高輸出密度。In the past, in order to reduce the size and weight of a general electric device using a battery such as a notebook type personal computer or a mobile phone, a small battery has been developed. In order to reduce the size and weight of general electric equipment such as portable devices, it is indispensable that the battery as a power source has a high energy density (high capacity). In addition to the small-sized battery, the development of a large-sized battery is also used as a power storage device for an automobile mounted on an electric vehicle or a hybrid vehicle, or as a battery for power storage in which a new energy system such as a solar battery or a wind power generation is combined. . Such large batteries require higher energy density or high output density.
作為滿足上述要求者,正活躍地進行鋰離子二次電池或電雙層電容器(electric double layer capacitor)等蓄電裝置的研究開發。具體而言,例如於專利文獻1中記載有一種具有層狀結構 的碳質材料,上述碳質材料於(002)面分散有多個非晶部,非晶部的平均面積為1.5nm2 以上。並且專利文獻1中揭示有在將該碳質材料使用於蓄電裝置的正極(負極為石墨)的情況下,可實現該蓄電裝置的高容量化。As a person who satisfies the above requirements, research and development of power storage devices such as lithium ion secondary batteries or electric double layer capacitors are actively being carried out. Specifically, for example, Patent Document 1 discloses a carbonaceous material having a layered structure in which a plurality of amorphous portions are dispersed on a (002) plane, and an average area of the amorphous portion is 1.5 nm 2 or more. . Further, in Patent Document 1, it is disclosed that when the carbonaceous material is used for the positive electrode of the electrical storage device (the negative electrode is graphite), the capacity of the electrical storage device can be increased.
另外,專利文獻2中記載有一種非水電解液二次電池的充電方法,上述非水電解液二次電池至少由正極、負極以及非水電解液所構成,上述正極主要含有嵌入、脫離陰離子的碳質材料,上述負極含有可嵌入、脫離金屬鋰或鋰離子的碳質材料,上述非水電解液是將鋰鹽溶解於非水溶劑中而成,上述非水電解液二次電池的充電方法是在將金屬鋰作為參照電池來表示正極的充電終止電壓的情況下,於非水電解液二次電池中充電至表示5.3V~5.6V的電壓為止。並且,專利文獻2揭示有可實現該非水電解液二次電池的高容量化。Further, Patent Document 2 describes a method for charging a nonaqueous electrolyte secondary battery, wherein the nonaqueous electrolyte secondary battery is composed of at least a positive electrode, a negative electrode, and a nonaqueous electrolyte, and the positive electrode mainly contains an anion and a detachment agent. In the carbonaceous material, the negative electrode contains a carbonaceous material capable of intercalating or desorbing metallic lithium or lithium ions, and the nonaqueous electrolytic solution is obtained by dissolving a lithium salt in a nonaqueous solvent, and charging method of the nonaqueous electrolyte secondary battery When metal lithium is used as a reference battery to indicate the charge termination voltage of the positive electrode, it is charged in a nonaqueous electrolyte secondary battery to a voltage of 5.3 V to 5.6 V. Further, Patent Document 2 discloses that the capacity of the nonaqueous electrolyte secondary battery can be increased.
[先前技術文獻][Previous Technical Literature]
[專利文獻][Patent Literature]
[專利文獻1]日本公開專利公報「日本專利特開2010-254637號公報(公開日:2010年11月11日)」[Patent Document 1] Japanese Laid-Open Patent Publication No. 2010-254637 (Publication Date: November 11, 2010)
[專利文獻2]日本專利公報「日本專利第4569126號公報(公告日:2010年10月27日)」[Patent Document 2] Japanese Patent Publication "Japanese Patent No. 4569126 (Announcement Date: October 27, 2010)"
然而,於製造上述專利文獻1所記載的蓄電裝置時,必須進行如下步驟:首先,為了製作正極,分別組裝電極製作用的單元,例如在以2.25V~3.5V進行至少一次充放電的事前處理(充 放電)來製作正極後,分解單元而取出正極,使用所得到的正極以及負極來組裝蓄電裝置用的單元。同樣地,於製造專利文獻2所記載的非水電解液二次電池(蓄電裝置)時,必須進行如下步驟:首先,為了製作正極,分別組裝電極製作用的單元,例如在以5.3V~5.6V(金屬鋰基準)進行至少一次充放電的事前處理來製作正極後,分解單元而取出正極,使用所得到的正極以及負極來組裝非水電解液二次電池用的單元。進而,在上述兩製造方法中,關於負極亦必須進行如下步驟:分別組裝電極製作用的單元,進行預先使鋰離子吸附的事前處理(鋰的預摻雜)來製作負極後,分解單元而取出負極。However, when manufacturing the power storage device described in Patent Document 1, it is necessary to perform the following steps: First, in order to fabricate a positive electrode, a unit for electrode production is separately assembled, for example, pre-treatment for at least one charge and discharge at 2.25 V to 3.5 V. (Charge After the positive electrode was produced by the discharge, the positive electrode was taken out and the positive electrode was taken out, and the obtained positive electrode and negative electrode were used to assemble the unit for the electrical storage device. In the same manner, in the case of producing the nonaqueous electrolyte secondary battery (electric storage device) described in Patent Document 2, it is necessary to perform the following steps: First, in order to fabricate the positive electrode, units for electrode production are separately assembled, for example, at 5.3 V to 5.6. V (metal lithium standard) A pretreatment of at least one charge and discharge is performed to prepare a positive electrode, and then the positive electrode is taken out by a decomposition unit, and a unit for a nonaqueous electrolyte secondary battery is assembled using the obtained positive electrode and negative electrode. Further, in the above two manufacturing methods, it is necessary to perform a step of separately assembling a unit for electrode production, performing pre-treatment (pre-doping of lithium) for adsorbing lithium ions in advance, and preparing a negative electrode, and then decomposing the unit and taking out the negative electrode. negative electrode.
亦即,在現有的蓄電裝置的製造方法中,在組裝該蓄電裝置用的單元前,為了製作正極以及負極,由於必須進行分別組裝電極製作用的單元來進行事前處理,分解單元而取出該些正極以及負極的作業,因此製造步驟繁雜,具有生產性差的問題。另外,為了使蓄電裝置作為各種便攜型機器等的一般電氣機器、或者電動車或混合動力車的電源而普及,從預想電池的市場進而大幅地擴大的觀點來看,雖然謀圖成本的低減化是重要的,但是由於現有的蓄電裝置的製造步驟繁雜,因此亦具有難以低成本化的問題。因此,深切盼望製造步驟經簡略化且低成本的蓄電裝置,亦即製造蓄電裝置的方法。In other words, in the conventional method of manufacturing a power storage device, in order to fabricate the positive electrode and the negative electrode, it is necessary to separately assemble the cells for electrode fabrication before performing the unit for the electrode storage device, and to disassemble the cells and take out the components. Since the positive electrode and the negative electrode work, the manufacturing steps are complicated and the productivity is poor. In addition, in order to make the power storage device widely used as a general electric device such as various portable devices or a power source for an electric vehicle or a hybrid vehicle, the market for the battery is expected to be greatly expanded, and the cost of the drawing is reduced. Although it is important in the manufacturing process of the conventional electrical storage device, it is difficult to reduce the cost. Therefore, there is a deep desire for a power storage device having a simplified and low-cost manufacturing process, that is, a method of manufacturing a power storage device.
本發明是鑒於上述問題而成者,其主要目的在於提供一 種製造步驟經簡略化且低成本的蓄電裝置的製造方法。The present invention has been made in view of the above problems, and its main object is to provide a A manufacturing method of a power storage device with a simplified manufacturing process and a low cost.
本發明人等為了達成上述目的,反覆地積極研究,結果發現在蓄電元件的製造方法中,藉由進行在蓄電元件用單元內配置隔著間隔物而積層正極及負極而成的積層體與鋰離子供給源,並且注入非水電解液的蓄電元件用單元製作步驟來製作該蓄電元件用單元後,可進行在正極與鋰離子供給源之間進行充放電的充放電步驟,以及在負極與鋰離子供給源之間進行電化學接觸,以使鋰離子吸附於負極的吸附步驟,亦即在製作蓄電元件用單元後,可進行正極及負極的處理(充放電),以至於完成了本發明。In order to achieve the above object, the inventors of the present invention have repeatedly conducted active research. As a result, in the method of manufacturing a storage element, it has been found that a laminate in which a positive electrode and a negative electrode are laminated with a spacer interposed therebetween is disposed in a cell for a storage element. The ion storage source and the unit for fabricating the storage element for injecting the non-aqueous electrolyte are used to produce the storage element unit, and then a charge and discharge step of charging and discharging between the positive electrode and the lithium ion supply source, and a negative electrode and lithium are provided. The present invention has been completed by electrochemically contacting the ion supply sources to adsorb the lithium ions to the negative electrode, that is, after the cells for the storage element are fabricated, the positive electrode and the negative electrode can be processed (charge and discharge).
亦即,本發明的蓄電元件的製造方法的蓄電元件包括:正極,其包含碳質材料作為正極活性物質,上述碳質材料具有形成於具有貫通孔的正極集電體上且可嵌入、脫離陰離子的層狀結構;負極,其包含選自由碳質材料、吸附鋰的金屬材料及合金材料所組成的群組的一種以上的材料作為負極活性物質,上述材料具有形成於具有貫通孔的負極集電體上且可嵌入、脫離鋰離子的層狀結構;以及包含鋰鹽的非水電解液,上述蓄電元件的製造方法的特徵在於包括:蓄電元件用單元製作步驟,在蓄電元件用單元內配置隔著間隔物而積層上述正極及負極而成的積層體與鋰離子供給源,並且注入上述非水電解液;充放電步驟,於正極與鋰離子供給源之間進行充放電;以及吸附步驟,於負極與鋰離子供給源之間進行電化學接觸而使鋰離子吸附於負極。In other words, the electric storage device of the method for producing an electric storage device of the present invention includes a positive electrode including a carbonaceous material as a positive electrode active material, and the carbonaceous material having a positive electrode current collector having a through hole and capable of being embedded and detached from the anion a layered structure; a negative electrode comprising one or more materials selected from the group consisting of a carbonaceous material, a metal material adsorbing lithium, and an alloy material as a negative electrode active material, the material having a negative electrode current collector formed in a through hole a layered structure in which a lithium ion is embedded and removed, and a nonaqueous electrolyte containing a lithium salt, wherein the method for producing a storage element includes a step of fabricating a unit for storing an electric element, and disposing a unit in the unit for accumulating element a laminate obtained by laminating the positive electrode and the negative electrode and a lithium ion supply source, and a non-aqueous electrolyte solution; a charge and discharge step of charging and discharging between the positive electrode and the lithium ion supply source; and an adsorption step; Electrochemical contact between the negative electrode and the lithium ion supply source causes lithium ions to be adsorbed to the negative electrode.
藉由本發明的蓄電元件的製造方法,在製作蓄電元件用單元後,可進行充放電步驟與吸附步驟。亦即,在製作蓄電元件用單元後,可進行正極及負極的處理(充放電)。因此,在與分別組裝電極製作用的單元來進行事前處理(充放電),從而製作正極及負極的現有的蓄電元件的製造方法相較下,可使製造步驟簡略化。另外,由於並沒有必要分別組裝電極製作用的單元,因此可減少該作業等所耗費的成本。因此,若藉由本發明的蓄電元件的製造方法,則發揮以下效果:可製造製作步驟經簡略化、低成本(生產性優異)且長期穩定性優異的蓄電元件。According to the method for producing an electric storage device of the present invention, after the cell for the storage element is produced, the charge and discharge step and the adsorption step can be performed. That is, after the cell for the storage element is produced, the treatment of the positive electrode and the negative electrode (charge and discharge) can be performed. Therefore, the manufacturing process can be simplified in comparison with the conventional method of manufacturing a conventional storage element in which a positive electrode and a negative electrode are produced by performing pre-treatment (charge and discharge) on a unit for electrode production. Further, since it is not necessary to separately assemble the unit for electrode production, the cost of the work or the like can be reduced. Therefore, according to the method for producing an electric storage device of the present invention, it is possible to produce an electric storage device having a simplified production process, low cost (excellent productivity), and excellent long-term stability.
1‧‧‧正極1‧‧‧ positive
2‧‧‧負極2‧‧‧negative
3‧‧‧間隔物3‧‧‧ spacers
4‧‧‧金屬鋰4‧‧‧metal lithium
5‧‧‧鋰離子供給源5‧‧‧Lithium ion supply source
6‧‧‧積層體6‧‧‧Layer
7‧‧‧組裝構件7‧‧‧Assembled components
8‧‧‧蓄電元件用單元8‧‧‧Units for electrical storage components
9‧‧‧非水電解液9‧‧‧ Non-aqueous electrolyte
10‧‧‧蓄電元件10‧‧‧Power storage components
圖1為表示藉由本發明的蓄電元件的製造方法而製造的蓄電元件的構成的一例的概略剖面圖。FIG. 1 is a schematic cross-sectional view showing an example of a configuration of an electric storage device manufactured by a method of manufacturing an electric storage device according to the present invention.
以下對本發明的一實施形態進行詳細說明。於本說明書中引用本說明書中所記載的學術文獻及專利文獻全部來作為參考。另外,本說明書中只要沒特別註記,表示數值範圍的「A~B」意指「A以上、B以下」。Hereinafter, an embodiment of the present invention will be described in detail. The academic documents and patent documents described in the present specification are hereby incorporated by reference in their entirety. In addition, unless otherwise noted in this specification, "A~B" which shows the numerical range means "A or more and B or less."
<A.蓄電元件><A. Power storage element>
本發明的蓄電元件包括:正極,其包含碳質材料作為正極活性物質,上述碳質材料具有形成於具有貫通孔的正極集電體上且可嵌入、脫離陰離子的層狀結構;負極,其包含選自由碳質材料、 吸附鋰的金屬材料及合金材料所組成的群組的一種以上的材料作為負極活性物質,上述材料具有形成於具有貫通孔的負極集電體上且可嵌入、脫離鋰離子的層狀結構;以及包含鋰鹽的非水電解液。該蓄電元件更具有隔著正極及負極的間隔物或電極部、組裝構件等。以下說明該些各種構成要件。The electric storage device of the present invention includes a positive electrode including a carbonaceous material as a positive electrode active material, the carbonaceous material having a layered structure formed on a positive electrode current collector having a through hole and capable of intercalating and desorbing an anion, and a negative electrode including Choose free carbon materials, One or more materials selected from the group consisting of a metal material and an alloy material that adsorbs lithium as a negative electrode active material having a layered structure formed on a negative electrode current collector having through holes and capable of intercalating and desorbing lithium ions; A nonaqueous electrolyte containing a lithium salt. The electric storage device further includes a spacer or an electrode portion, an assembly member, and the like which are interposed between the positive electrode and the negative electrode. The various constituent elements are described below.
<1.正極><1. Positive electrode>
<1-1.正極所含有的碳質材料><1-1. Carbonaceous material contained in the positive electrode>
作為上述正極所含有的正極活性物質的碳質材料具有可嵌入、脫離陰離子的層狀結構,較佳為滿足下述(i)、(ii)的任一者的碳質材料。The carbonaceous material of the positive electrode active material contained in the positive electrode has a layered structure in which an anion can be inserted or removed, and is preferably a carbonaceous material satisfying any of the following (i) and (ii).
(i)於(002)面分散有多個非晶部,且上述非晶部的平均面積為1.5nm2 以上的碳質材料,或者(i) a carbonaceous material having a plurality of amorphous portions dispersed on a (002) plane and having an average area of the amorphous portion of 1.5 nm 2 or more, or
(ii)於(002)面分散有多個非晶部,且上述(002)面內的上述非晶部的總面積相對於(002)面內的上述非晶部及結晶部的面積的合計的比例為30%以上的碳質材料。(ii) a plurality of amorphous portions are dispersed on the (002) plane, and the total area of the amorphous portion in the (002) plane is larger than the total area of the amorphous portion and the crystal portion in the (002) plane The proportion of carbonaceous materials is more than 30%.
例如,由於上述(i)的碳質材料在具有層狀結構的碳質材料的(002)面分散有多個適當的面積的非晶部,因此可使陰離子的嵌入、脫離位置增大。並且,該些非晶部於放電後亦殘留。因此,於將該碳質材料用作蓄電元件的電極的情況下,由於在碳質材料的非晶部優先且容易地嵌入、脫離電解質的離子,因此可使碳質材料的嵌入、脫離量增大,且可使蓄電元件的放電容量增加。For example, since the carbonaceous material of the above (i) has a plurality of amorphous portions of a suitable area dispersed on the (002) plane of the carbonaceous material having a layer structure, the position of insertion and removal of anions can be increased. Further, the amorphous portions remain after discharge. Therefore, when the carbonaceous material is used as an electrode of an electric storage device, since the amorphous portion of the carbonaceous material preferentially and easily intercalates and desorbs ions of the electrolyte, the amount of embedding and detachment of the carbonaceous material can be increased. It is large and can increase the discharge capacity of the storage element.
另外,若為上述(ii)的碳質材料,則在具有層狀結構 的碳質材料的(002)面分散有多個適當的比例的非晶部,其面積比例亦達30%以上,因此可使電解質的陰離子的嵌入、脫離位置增大。並且該非晶部於放電後亦殘留。因此,於將該碳質材料用作蓄電元件的電極的情況下,於碳質材料的非晶部優先且容易地嵌入、脫離電解質的陰離子,因此可使碳質材料的嵌入、脫離量增大,且可使蓄電元件的放電容量增加。Further, in the case of the carbonaceous material of the above (ii), it has a layered structure. The (002) plane of the carbonaceous material is dispersed in a plurality of amorphous portions in an appropriate ratio, and the area ratio thereof is also 30% or more, so that the insertion and removal positions of the anions of the electrolyte can be increased. Further, the amorphous portion remains after discharge. Therefore, when the carbonaceous material is used as an electrode of the electric storage device, the amorphous portion of the carbonaceous material preferentially and easily intercalates and desorbs the anion of the electrolyte, so that the amount of insertion and removal of the carbonaceous material can be increased. And the discharge capacity of the electric storage device can be increased.
作為滿足上述(i)、(ii)的任一者的碳質材料,較佳為石墨(市售品)。石墨於(002)面具有層狀結構。此處,所謂「(002)面」是指藉由X射線繞射測定的碳002面(與石墨層水平的面)。As the carbonaceous material satisfying any of the above (i) and (ii), graphite (commercially available) is preferred. Graphite has a layered structure on the (002) plane. Here, the "(002) plane" means a carbon 002 surface (a surface horizontal to the graphite layer) measured by X-ray diffraction.
另外,作為正極所含有的具有層狀結構的碳質材料,雖然石墨較佳,但並不限於石墨,只要為具有層狀結構的碳質材料且滿足上述(i)、(ii)的任一者的碳質材料,則可適當地使用。例如,作為上述碳質材料,亦可利用日本專利特開2010-254537號公報中所記載的碳質材料。於本發明中,作為上述正極所含有的碳質材料,於製作蓄電元件用單元前,並沒有必要使用預先進行充放電處理的碳質材料。Further, the carbonaceous material having a layered structure contained in the positive electrode is preferably graphite, but is not limited to graphite, and is a carbonaceous material having a layered structure and satisfies any of the above (i) and (ii). The carbonaceous material of the person can be suitably used. For example, as the carbonaceous material, a carbonaceous material described in JP-A-2010-254537 can also be used. In the present invention, as the carbonaceous material contained in the positive electrode, it is not necessary to use a carbonaceous material which is subjected to charge and discharge treatment in advance before the cell for the storage element is produced.
<1-2.正極的製造方法><1-2. Method of Manufacturing Positive Electrode>
正極可藉由在具有貫通孔的正極集電體上塗布上述碳質材料來形成。具體而言,可藉由在作為正極集電體的電極板的與負極對向的表面(單面或兩面)塗布上述碳質材料而披覆該表面來形成正極。The positive electrode can be formed by applying the above-described carbonaceous material to a positive electrode current collector having through holes. Specifically, the positive electrode can be formed by coating the surface with the carbonaceous material coated on the surface (single or both sides) of the electrode plate as the positive electrode current collector opposite to the negative electrode.
作為上述電極板,較佳為具有貫通表面、背面的貫通孔 的鋁板,具體而言,更佳為厚度為10μm~40μm且開口率為20%~40%的多孔鋁箔(市售品)。另外,作為正極集電體,並不限於鋁板,只要為可用作鋰離子電池的正極用電極板且具有貫通表面、背面的貫通孔的金屬板,則可適當地使用。As the electrode plate, a through hole having a through surface and a back surface is preferable. Specifically, the aluminum plate is more preferably a porous aluminum foil (commercially available) having a thickness of 10 μm to 40 μm and an opening ratio of 20% to 40%. In addition, the positive electrode current collector is not limited to an aluminum plate, and can be suitably used as long as it is a metal plate which can be used as a positive electrode plate for a lithium ion battery and has a through hole penetrating through the front surface and the back surface.
作為藉由上述碳質材料披覆電極板的表面的方法,較佳為例如調配於使黏合劑溶解的溶劑中使碳質材料與視需要的導電輔助材料分散而成的分散液(漿料),使用刮刀等塗布機(橫型塗布機以及縱型塗布機)將該分散液塗布於電極板的表面後,使溶劑乾燥(揮發)的方法。另外,作為藉由上述碳質材料披覆電極板的表面的方法,並不限於上述方法,可較佳地採用公知的方法。另外,乾燥後的碳質材料的厚度,亦即正極的厚度(單面)可根據該正極的大小(面積)等而適當設定即可,但較佳為30μm~150μm,更佳為50μm~90μm。As a method of coating the surface of the electrode plate with the carbonaceous material, for example, a dispersion (slurry) prepared by dispersing a carbonaceous material and an optional conductive auxiliary material in a solvent for dissolving the binder is preferably used. A method in which the dispersion liquid is applied to the surface of the electrode plate by a coater (a horizontal coater or a vertical coater) such as a doctor blade to dry (volatate) the solvent. Further, the method of coating the surface of the electrode plate with the carbonaceous material is not limited to the above method, and a known method can be preferably employed. In addition, the thickness of the carbonaceous material after drying, that is, the thickness of the positive electrode (single side) may be appropriately set depending on the size (area) of the positive electrode, etc., but is preferably 30 μm to 150 μm, more preferably 50 μm to 90 μm. .
作為上述黏合劑,較佳為羧基甲基纖維素與苯乙烯-丁二烯橡膠(styrene-butadiene rubber,SBR)樹脂的混合物、聚偏二氟乙烯、聚醯胺醯亞胺、聚醯亞胺、聚四氟乙烯等,更佳為聚偏二氟乙烯。正極中所含有的黏合劑的量較佳為1wt%~20wt%。As the above binder, a mixture of carboxymethyl cellulose and styrene-butadiene rubber (SBR) resin, polyvinylidene fluoride, polyamidimide, polyimine , polytetrafluoroethylene, etc., more preferably polyvinylidene fluoride. The amount of the binder contained in the positive electrode is preferably from 1% by weight to 20% by weight.
作為上述溶劑,較佳為N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮、水等,更佳為N-甲基-2-吡咯啶酮。The solvent is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, water or the like, more preferably N-methyl-2-pyrrolidone.
<2.負極><2. Negative electrode>
<2-1.負極所含有的碳質材料等材料><2-1. Materials such as carbonaceous materials contained in the negative electrode>
作為上述負極所含有的負極活性物質的碳質材料為具有可嵌 入、脫離鋰離子的層狀結構的碳質材料。作為負極所含有的碳質材料,較佳為石墨、難石墨性碳、天然石墨、人造石墨、難石墨化碳、易石墨化碳、低溫煅燒碳、活性碳等,更佳為石墨、難石墨性碳、或人造石墨。The carbonaceous material as the negative electrode active material contained in the negative electrode has an insertable A carbonaceous material having a layered structure of lithium ions. The carbonaceous material contained in the negative electrode is preferably graphite, refractory carbon, natural graphite, artificial graphite, non-graphitizable carbon, easily graphitizable carbon, low-temperature calcined carbon, activated carbon, etc., more preferably graphite or hard graphite. Carbon, or artificial graphite.
另外,作為負極所含有的具有層狀結構的碳質材料,並不限於上述例示的碳質材料,只要為具有層狀結構的碳質材料,且可嵌入、脫離鋰離子的碳質材料,則可適當地使用。例如,作為上述碳質材料,可利用日本專利特開2009-260187號公報所記載的碳質材料。於本發明中,作為上述負極所含有的碳質材料,並沒有必要使用於製作蓄電元件用單元前預先進行鋰離子的吸附處理(鋰的預摻雜)的碳質材料。In addition, the carbonaceous material having a layered structure contained in the negative electrode is not limited to the above-exemplified carbonaceous material, and may be a carbonaceous material having a layered structure and capable of embedding or removing a carbonaceous material of lithium ions. Can be used as appropriate. For example, as the carbonaceous material, a carbonaceous material described in JP-A-2009-260187 can be used. In the present invention, as the carbonaceous material contained in the negative electrode, it is not necessary to use a carbonaceous material in which lithium ion adsorption treatment (pre-doping of lithium) is performed before the cell for storage element.
另外,亦可使用吸附鋰的金屬材料或合金材料來代替碳質材料。亦即,作為負極所含有的負極活性物質,可列舉選自由碳質材料、吸附鋰的金屬材料及合金材料所組成的群組的一種以上的材料。In addition, a metal material or an alloy material that adsorbs lithium may be used instead of the carbonaceous material. In other words, the negative electrode active material contained in the negative electrode may be one or more selected from the group consisting of a carbonaceous material, a metal material that adsorbs lithium, and an alloy material.
作為吸附上述鋰的金屬材料,可列舉矽、錫、鍺、鉛、銻、鋁、銦、鋅、鉍等。另外,作為吸附上述鋰的合金材料,可列舉矽合金或錫合金。作為矽合金,可列舉於矽中含有選自由鐵、鈷、銻、鉍、鉛、鎳、銅、鋅、鍺、銦、錫及鈦所組成的群組中的至少一種異種元素的合金。作為錫合金,可列舉於錫中含有選自由鎳、鎂、鐵、銅及鈦所組成的群組中的至少一種異種元素的合金。Examples of the metal material for adsorbing the lithium include antimony, tin, antimony, lead, antimony, aluminum, indium, zinc, antimony, and the like. Further, examples of the alloy material for adsorbing the lithium include a ruthenium alloy or a tin alloy. The niobium alloy may be an alloy containing at least one different element selected from the group consisting of iron, cobalt, rhodium, ruthenium, lead, nickel, copper, zinc, bismuth, indium, tin, and titanium. The tin alloy may be an alloy containing at least one different element selected from the group consisting of nickel, magnesium, iron, copper, and titanium.
以下,為了方便,列舉「碳質材料」來說明「選自由碳質材料、吸附鋰的金屬材料及合金材料所組成的群組的一種以上的材料」。Hereinafter, for convenience, a "carbonaceous material" will be described to describe "one or more materials selected from the group consisting of a carbonaceous material, a metal material that adsorbs lithium, and an alloy material."
<2.2負極的製造方法><2.2 Manufacturing method of negative electrode>
負極可藉由在具有貫通孔的負極集電體上塗布上述碳質材料來形成。具體而言,可藉由在作為負極集電體的電極板的與正極對向的表面(單面或兩面)塗布上述碳質材料而披覆該表面來形成負極。The negative electrode can be formed by coating the above-described carbonaceous material on a negative electrode current collector having through holes. Specifically, the negative electrode can be formed by coating the surface with the carbonaceous material on the surface (single or both sides) of the electrode plate as the negative electrode current collector facing the positive electrode.
作為上述電極板,較佳為具有貫通表面、背面的貫通孔的銅板,具體而言,更佳為厚度為10μm~40μm且開口率為20%~40%的多孔銅箔(市售品)。另外,作為負極集電體,並不限於銅板,只要為可用作鋰離子電池的負極用電極板且具有貫通表面、背面的貫通孔的金屬板,則可適當地使用。The electrode plate is preferably a copper plate having a through hole penetrating the front surface and the back surface, and more preferably a porous copper foil (commercially available) having a thickness of 10 μm to 40 μm and an opening ratio of 20% to 40%. In addition, the negative electrode current collector is not limited to a copper plate, and can be suitably used as long as it is a metal plate which can be used as a negative electrode electrode plate for a lithium ion battery and has a through hole penetrating through the front surface and the back surface.
作為藉由上述碳質材料披覆電極板的表面的方法,較佳為例如調配於使黏合劑溶解的溶劑中使碳質材料與視需要的導電輔助材料分散而成的分散液(漿料),使用刮刀等塗布機(橫型塗布機或縱型塗布機)將該分散液塗布於電極板的表面後,使溶劑乾燥(揮發)的方法。另外,作為藉由上述碳質材料披覆電極板的表面的方法,並不限於上述方法,可較佳地採用公知的方法。另外,乾燥後的碳質材料的厚度,亦即負極的厚度(單面)可根據該負極的大小(面積)等而適當設定即可,但較佳為30μm~150μm,更佳為50μm~90μm。As a method of coating the surface of the electrode plate with the carbonaceous material, for example, a dispersion (slurry) prepared by dispersing a carbonaceous material and an optional conductive auxiliary material in a solvent for dissolving the binder is preferably used. A method in which the dispersion is applied to the surface of the electrode plate by a coater (a horizontal coater or a vertical coater) such as a doctor blade to dry (volatate) the solvent. Further, the method of coating the surface of the electrode plate with the carbonaceous material is not limited to the above method, and a known method can be preferably employed. In addition, the thickness of the carbonaceous material after drying, that is, the thickness (single side) of the negative electrode may be appropriately set depending on the size (area) of the negative electrode, etc., but is preferably 30 μm to 150 μm, more preferably 50 μm to 90 μm. .
作為上述黏合劑,較佳為羧基甲基纖維素與苯乙烯-丁二烯橡膠樹脂的混合物、聚偏二氟乙烯、聚醯胺醯亞胺、聚醯亞胺、聚四氟乙烯等,更佳為聚偏二氟乙烯。負極中所含有的黏合劑的量較佳為1wt%~20wt%。The binder is preferably a mixture of carboxymethylcellulose and a styrene-butadiene rubber resin, polyvinylidene fluoride, polyamidimide, polyimine, polytetrafluoroethylene, etc. Good for polyvinylidene fluoride. The amount of the binder contained in the negative electrode is preferably from 1% by weight to 20% by weight.
作為上述溶劑,較佳為N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮、水等,更佳為N-甲基-2-吡咯啶酮。The solvent is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, water or the like, more preferably N-methyl-2-pyrrolidone.
<3.非水電解液><3. Non-aqueous electrolyte>
上述非水電解液包含作為電解質的鋰鹽。亦即,上述非水電解液為含有作為溶解於有機溶劑的電解質(溶質)的鋰鹽的有機電解液。非水電解液亦可視需要包含鋰鹽以外的其他電解質。The above nonaqueous electrolytic solution contains a lithium salt as an electrolyte. In other words, the nonaqueous electrolytic solution is an organic electrolytic solution containing a lithium salt as an electrolyte (solute) dissolved in an organic solvent. The non-aqueous electrolyte may also contain other electrolytes other than the lithium salt as needed.
作為上述鋰鹽,較佳為選自由LiPF6 、LiBF4 、LiCIO4 、LiN(CF3 SO2 )2 、LiN(SO2 C2 F5 )2 、LiCF3 SO3 、LiC(SO2 CF3 )3 、LiAsF6 以及LiSbF6 所組成的群組的一種以上的鹽。更佳為LiPF6 。另外,非水電解液的鋰鹽的濃度(電解質濃度)理想的是更高者,具體而言,較佳為0.5mol/L~5.0mol/L(0.5M~5.0M),更佳為1.0mol/L~1.5mol/L。The lithium salt is preferably selected from the group consisting of LiPF 6 , LiBF 4 , LiCIO 4 , LiN(CF 3 SO 2 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiCF 3 SO 3 , LiC (SO 2 CF 3 ). 3 ) More than one salt of the group consisting of LiAsF 6 and LiSbF 6 . More preferably LiPF 6 . Further, the concentration (electrolyte concentration) of the lithium salt of the nonaqueous electrolytic solution is desirably higher, and specifically, it is preferably 0.5 mol/L to 5.0 mol/L (0.5 M to 5.0 M), more preferably 1.0. Mol/L~1.5mol/L.
上述有機溶劑較佳為碳酸伸乙酯(ethylene carbonate)、碳酸伸丁酯(butylene carbonate)、碳酸二甲酯、碳酸乙基甲酯、碳酸二乙酯、環丁碸(sulfolane)、二甲氧基乙烷等。該些有機溶劑可作為單獨溶劑來使用,亦可作為兩種以上的混合溶劑來使用。作為混合溶劑,較佳為碳酸伸乙酯與碳酸二甲酯的混合溶劑,更佳為將碳酸伸乙酯與碳酸二甲酯以重量比1:1混合而成的混合 溶劑。The above organic solvent is preferably ethylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, sulfolane, dimethoxy Ethylene and the like. These organic solvents can be used as a single solvent or as a mixed solvent of two or more types. As the mixed solvent, a mixed solvent of ethyl carbonate and dimethyl carbonate is preferred, and a mixture of ethyl carbonate and dimethyl carbonate in a weight ratio of 1:1 is more preferred. Solvent.
另外,作為上述鋰鹽以及有機溶劑,亦可使用上述例示的化合物以外的公知的鋰鹽以及有機溶劑(並不限制使用上述例示的化合物以外的化合物)。In addition, as the lithium salt and the organic solvent, a known lithium salt other than the above-exemplified compounds and an organic solvent (a compound other than the above-exemplified compounds are not limited) may be used.
<4.其他構成><4. Other composition>
作為在蓄電元件中隔著上述正極及負極的間隔物,較佳為包括纖維素系或聚乙烯等聚烯烴系等的聚合物的多孔質的膜,更佳為包括纖維素系的聚合物的多孔質的膜。The separator containing the above-mentioned positive electrode and negative electrode in the storage element is preferably a porous film including a polymer such as a cellulose-based or polyethylene-based polymer, and more preferably a cellulose-based polymer. A porous membrane.
作為在蓄電元件中將上述正極及負極導出至外部的外部取出電極的電極部,可使用公知的電極部。As the electrode portion of the external extraction electrode that leads the positive electrode and the negative electrode to the outside in the storage element, a known electrode portion can be used.
作為在蓄電元件中構成單元(蓄電元件用單元)的組裝構件,較佳為包括鋁的積層膜。因此,蓄電元件的單元較佳為包括鋁的積層組裝。As an assembly member of a constituent unit (a unit for an electric storage device) in the electric storage device, a laminated film including aluminum is preferable. Therefore, the unit of the electricity storage element is preferably a laminated assembly including aluminum.
另外,作為上述間隔物及組裝構件,亦可使用上述例示的物質以外的公知的間隔物及組裝構件(並不限制使用上述例示的物質以外的物質)。Further, as the spacer and the assembly member, a known spacer and an assembly member other than the above-exemplified materials may be used (the substances other than the above-exemplified substances are not limited to be used).
並且,本發明的蓄電元件在其製作時,在藉由組裝構件來構成組裝的蓄電元件用單元內,更具有與隔著間隔物而積層上述正極及負極而成的積層體鄰接配置的鋰離子供給源。亦即,本發明的蓄電元件在其製作時,在蓄電元件用單元內配置有金屬鋰。上述鋰離子供給源為壓接或貼合有金屬鋰的銅箔(市售品)或鎳箔等的金屬箔。鋰離子供給源具有將包括上述金屬箔的金屬 鋰電極導出至外部的作為外部取出電極的電極部。鋰離子供給源是以不直接與正極及負極接觸的方式配置在蓄電元件用單元內。另外,鋰離子供給源只要在蓄電元件用單元內的一個積層體配置至少一個即可,但亦能夠以夾著積層體的方式配置兩個以上。另外,鋰離子供給源的金屬鋰於蓄電元件使用時全部成為鋰離子,並不以金屬的狀態存在。In the battery storage device of the present invention, the lithium ion source disposed adjacent to the laminated body in which the positive electrode and the negative electrode are laminated via the spacer is further provided in the cell for the electric storage device to be assembled by the assembly member. Supply source. In other words, in the electric storage device of the present invention, metallic lithium is disposed in the cell for storage element. The lithium ion supply source is a metal foil such as a copper foil (commercially available) to which metal lithium is bonded or bonded, or a nickel foil. The lithium ion supply source has a metal to include the above metal foil The lithium electrode is led to the external electrode portion as an external extraction electrode. The lithium ion supply source is disposed in the cell for storage element so as not to be in direct contact with the positive electrode and the negative electrode. In addition, the lithium ion supply source may be disposed in at least one of the laminates in the cell for storage elements, but two or more of them may be disposed so as to sandwich the laminate. Further, the lithium metal of the lithium ion supply source is all lithium ions when used as a storage element, and does not exist in a metal state.
相對於作為負極活性物質的碳質材料可吸附的鋰離子的最大重量(理論重量),金屬鋰的重量較佳為50wt%~90wt%,更佳為60wt%~80wt%,進而佳為70wt%。The weight of the metal lithium is preferably from 50% by weight to 90% by weight, more preferably from 60% by weight to 80% by weight, even more preferably 70% by weight, based on the maximum weight (theoretical weight) of lithium ions which can be adsorbed as the carbonaceous material as the negative electrode active material. .
另外,可在負極與鋰離子供給源之間進行電化學接觸,而將吸附有鋰離子的負極用作對於正極的鋰離子供給源。Further, electrochemical contact may be performed between the negative electrode and the lithium ion supply source, and the negative electrode to which lithium ions are adsorbed may be used as a lithium ion supply source for the positive electrode.
<5.蓄電元件的構成><5. Configuration of power storage element>
以下一面參照圖1,一面說明藉由本發明的蓄電元件的製造方法而製造的蓄電元件(藉由蓄電元件用單元製作步驟而製作的蓄電元件)。圖1為表示藉由本發明的蓄電元件的製造方法而製造的蓄電元件的構成的一例的概略剖面圖。另外,以下的說明中,將蓄電元件具有合計積層五層正極及負極而成的積層體的情況列舉為例子。In the following, an electric storage device (an electric storage device produced by the cell manufacturing step for the electric storage device) manufactured by the method for manufacturing the electric storage device of the present invention will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view showing an example of a configuration of an electric storage device manufactured by a method of manufacturing an electric storage device according to the present invention. In the following description, a case where the electric storage device has a laminated body in which a total of five positive electrodes and a negative electrode are laminated is exemplified.
如圖1所示,本發明的蓄電元件(藉由蓄電元件用單元製作步驟而製作的蓄電元件)10是在藉由組裝構件7來構成組裝的蓄電元件用單元8內,配置有隔著間隔物3而積層正極1及負極2而成的積層體6與包括具備金屬鋰4的金屬箔的鋰離子供給 源5,且藉由注入非水電解液9來構成。蓄電元件用單元8被密封。另外,非水電解液9亦注入積層體6內。As shown in Fig. 1, the electric storage device (the electric storage device produced by the unit for manufacturing the electric storage device) 10 of the present invention is disposed in the storage element unit 8 which is assembled by the assembly member 7, and is disposed with a space therebetween. Lithium ion supply of the layered body 6 in which the positive electrode 1 and the negative electrode 2 are laminated and the metal foil including the metal lithium 4 is supplied The source 5 is constituted by injecting the nonaqueous electrolyte 9. The battery element unit 8 is sealed. Further, the nonaqueous electrolytic solution 9 is also injected into the laminated body 6.
積層體6是藉由以最外層成為負極2的方式,隔著間隔物3而合計積層五層正極1及負極2來構成。因此,正極1是在電極板的兩面塗布有碳質材料而構成。另一方面,位於內部的負極2是在電極板的兩面塗布有碳質材料而構成,位於最外層的負極2是在電極板的單面塗布有碳質材料而構成。另外,積層體6的正極1及負極2可合計積層兩層以上,較佳為可積層三層以上,更佳為可積層五層以上。另外,在積層三層以上的情況下,較佳為積層體6的最外層為負極2。The laminated body 6 is formed by stacking five layers of the positive electrode 1 and the negative electrode 2 via the spacer 3 so that the outermost layer becomes the negative electrode 2 . Therefore, the positive electrode 1 is formed by coating a carbonaceous material on both surfaces of the electrode plate. On the other hand, the negative electrode 2 located inside is formed by coating a carbonaceous material on both surfaces of the electrode plate, and the negative electrode 2 located in the outermost layer is formed by coating a carbonaceous material on one surface of the electrode plate. Further, the positive electrode 1 and the negative electrode 2 of the laminated body 6 may have a total of two or more layers, preferably three or more layers, and more preferably five or more layers. Further, in the case of stacking three or more layers, it is preferable that the outermost layer of the layered body 6 is the negative electrode 2.
進而,在積層體6與鋰離子供給源5之間、積層體6與組裝構件7之間以及鋰離子供給源5與組裝構件7之間以彼此不接觸的方式***間隔物3。亦即,藉由***間隔物3,組裝構件7、正極1、負極2以及鋰離子供給源5變得彼此不接觸。Further, the spacer 3 is inserted between the laminated body 6 and the lithium ion supply source 5, between the laminated body 6 and the assembly member 7, and between the lithium ion supply source 5 and the assembly member 7 so as not to be in contact with each other. That is, by inserting the spacer 3, the assembly member 7, the positive electrode 1, the negative electrode 2, and the lithium ion supply source 5 become non-contact with each other.
<B.蓄電元件的製造方法><B. Method of Manufacturing Power Storage Element>
本發明的蓄電元件的製造方法中的蓄電元件包括:包含碳質材料作為正極活性物質的正極1,上述碳質材料具有形成於具有貫通孔的正極集電體上且可嵌入、脫離陰離子的層狀結構;包含碳質材料作為負極活性物質的負極2,上述碳質材料具有形成於具有貫通孔的負極集電體上且可嵌入、脫離鋰離子的層狀結構;以及包含鋰鹽的非水電解液9。上述蓄電元件的製造方法包括:蓄電元件用單元製作步驟,在成為蓄電元件用單元8的組裝構件7內配 置隔著間隔物而積層上述正極1及負極2而成的積層體6與鋰離子供給源5,並且注入上述非水電解液9;充放電步驟,於正極1與鋰離子供給源5之間進行充放電;以及吸附步驟,於負極2與鋰離子供給源5之間進行電化學接觸而使鋰離子吸附於負極2。The electric storage device according to the method for producing an electric storage device of the present invention includes a positive electrode 1 including a carbonaceous material as a positive electrode active material, and the carbonaceous material has a layer formed on a positive electrode current collector having a through hole and capable of intercalating and desorbing an anion. a negative electrode 2 comprising a carbonaceous material as a negative electrode active material, the carbonaceous material having a layered structure formed on a negative electrode current collector having a through hole and capable of intercalating and desorbing lithium ions; and a nonaqueous water containing a lithium salt Electrolyte 9. The method of manufacturing the electric storage device includes the step of fabricating the electric storage device, and is provided in the assembly member 7 serving as the electric storage device unit 8. The layered body 6 in which the positive electrode 1 and the negative electrode 2 are laminated via the spacer and the lithium ion supply source 5 are placed, and the nonaqueous electrolyte solution 9 is injected; and the charge and discharge step is performed between the positive electrode 1 and the lithium ion supply source 5 The charging and discharging are performed; and the adsorption step is performed to electrochemically contact the negative electrode 2 and the lithium ion supply source 5 to adsorb lithium ions to the negative electrode 2.
進行上述吸附步驟及上述充放電步驟的順序並無特別限定,可在上述吸附步驟之後進行上述充放電步驟,亦可在上述充放電步驟之後進行上述吸附步驟。The order of the adsorption step and the charge and discharge step is not particularly limited, and the charge and discharge step may be performed after the adsorption step, or the adsorption step may be performed after the charge and discharge step.
另外,在上述吸附步驟之後進行上述充放電步驟的情況下,較佳為藉由上述吸附步驟而在負極2與鋰離子供給源5之間進行電化學接觸,而使吸附有鋰離子的負極2作為鋰離子供給源而發揮作用,且之後藉由上述充放電步驟而在正極1與吸附有鋰離子的負極2之間進行充放電。藉此,在正極1與隔著間隔物3而鄰接的負極2之間分別地進行充放電,因此可使正極1的陰離子的嵌入、脫離位置的增大量的均一性提升。另外,在上述充放電步驟之後進行上述吸附步驟的情況下,藉由上述充放電步驟在鋰離子供給源5與正極1之間進行充放電,且藉由上述吸附步驟在負極2與鋰離子供給源5之間進行電化學接觸,從而使鋰離子吸附於負極2。Further, when the charging and discharging step is performed after the adsorption step, it is preferred that the negative electrode 2 is adsorbed with lithium ions by electrochemical contact between the negative electrode 2 and the lithium ion supply source 5 by the adsorption step. It functions as a lithium ion supply source, and then charges and discharges between the positive electrode 1 and the negative electrode 2 to which lithium ions are adsorbed by the above-described charge and discharge step. As a result, charge and discharge are respectively performed between the positive electrode 1 and the negative electrode 2 adjacent to each other via the spacer 3, so that the uniformity of the amount of increase in the insertion and removal position of the anion of the positive electrode 1 can be improved. Further, when the adsorption step is performed after the charging and discharging step, charging and discharging are performed between the lithium ion supply source 5 and the positive electrode 1 by the charging and discharging step, and the negative electrode 2 and the lithium ion are supplied by the adsorption step. Electrochemical contact is made between the sources 5 so that lithium ions are adsorbed to the negative electrode 2.
以下為了方便說明,列舉在充放電步驟之後進行吸附步驟的情況為例來說明該些各步驟。Hereinafter, for convenience of explanation, the steps of performing the adsorption step after the charge and discharge step will be described as an example.
<6.蓄電元件用單元製作步驟><6. Step of manufacturing unit for storage element>
首先,藉由上述方法製造含有碳質材料作為正極活性物質的 正極1,其中上述碳質材料具有形成於具有貫通孔的正極集電體上且可嵌入、脫離陰離子的層狀結構;並且藉由上述方法製造含有碳質材料作為負極活性物質的負極2,其中上述碳質材料具有形成於具有貫通孔的負極集電體上且可嵌入、脫離鋰離子的層狀結構。並且,藉由隔著間隔物3積層正極1及負極2來製作積層體6。另外,製作(或準備)非水電解液9或包括具備金屬鋰4的金屬箔的鋰離子供給源5。進而,將電極部安裝在正極1、負極2以及鋰離子供給源5。積層體6的製作方法或非水電解液9的製作方法並無特別限定,可採用公知的製作方法。First, a carbonaceous material is produced as a positive electrode active material by the above method. a positive electrode 1, wherein the carbonaceous material has a layered structure formed on a positive electrode current collector having a through-hole and capable of intercalating and desorbing an anion; and a negative electrode 2 containing a carbonaceous material as a negative electrode active material is produced by the above method, wherein The carbonaceous material has a layered structure formed on a negative electrode current collector having a through hole and capable of intercalating and desorbing lithium ions. Then, the laminated body 6 is produced by laminating the positive electrode 1 and the negative electrode 2 via the spacer 3. Further, a nonaqueous electrolyte solution 9 or a lithium ion supply source 5 including a metal foil of metal lithium 4 is prepared (or prepared). Further, the electrode portion is attached to the positive electrode 1, the negative electrode 2, and the lithium ion supply source 5. The method for producing the layered body 6 or the method for producing the non-aqueous electrolyte solution 9 is not particularly limited, and a known production method can be employed.
接著,如圖1所示,在成為蓄電元件用單元8的組裝構件7內隔著間隔物3來配置上述積層體6與鋰離子供給源5,並且注入非水電解液9。之後,藉由密閉組裝構件7來密封蓄電元件用單元8,藉此製作本發明的蓄電元件,亦即蓄電元件10(蓄電元件用單元製作步驟)。Then, as shown in FIG. 1 , the laminated body 6 and the lithium ion supply source 5 are placed in the assembly member 7 serving as the electric storage device unit 8 via the spacer 3, and the nonaqueous electrolytic solution 9 is injected. After that, the storage element unit 8 is sealed by the sealing member 7, and the storage element 10 of the present invention, that is, the storage element 10 (the storage element unit production step) is produced.
蓄電元件用單元製作步驟與公知的蓄電元件的製作方法同樣地在露點為-35℃以下,更佳為-60℃以下的乾燥環境下或惰性氣體環境下進行。The cell production step for the storage element is carried out in a dry environment having a dew point of -35 ° C or lower, more preferably -60 ° C or lower, or an inert gas atmosphere, similarly to the known method for producing a storage element.
<7.充放電步驟><7. Charge and discharge steps>
接著,在蓄電元件用單元製作步驟中所製作的蓄電元件10的正極1的電極部與鋰離子供給源5的電極部之間進行充放電(充放電步驟)。亦即,在正極1及鋰離子供給源5之間進行至少一次充放電循環,上述充放電循環是流通一定電流來進行充電,之後 進行放電。Then, charge and discharge (charge and discharge steps) are performed between the electrode portion of the positive electrode 1 of the electric storage device 10 and the electrode portion of the lithium ion supply source 5 in the electric storage device unit manufacturing step. That is, at least one charge/discharge cycle is performed between the positive electrode 1 and the lithium ion supply source 5, and the charge/discharge cycle is performed by flowing a constant current, and then charging. Discharge.
充電例如是藉由電流密度為1.85mA/cm2 的定電流直到電壓達規定電壓為止來進行。此處,充電時的規定電壓(正極電位)更佳為以金屬鋰為基準而將充電電壓設為5.0V以上、6.0V以下。另外,充放電循環進行至少一次即可,但亦可進行多次。若在正極1及鋰離子供給源5之間流通充電電流,則非水電解液9中的陽離子吸附於鋰離子供給源5的金屬鋰4,且陰離子嵌入於正極的具有層狀結構的碳質材料(例如石墨的層間)。進行充電至變成規定電壓之後,接著以金屬鋰為基準進行放電至變成3.0V為止。另外,充放電循環的具體條件並無特別限定。Charging is performed, for example, by a constant current having a current density of 1.85 mA/cm 2 until the voltage reaches a predetermined voltage. Here, the predetermined voltage (positive electrode potential) at the time of charging is more preferably set to 5.0 V or more and 6.0 V or less based on metal lithium. Further, the charge and discharge cycle may be performed at least once, but may be performed multiple times. When a charging current flows between the positive electrode 1 and the lithium ion supply source 5, the cation in the nonaqueous electrolytic solution 9 is adsorbed to the metallic lithium 4 of the lithium ion supply source 5, and the anion is embedded in the positive electrode and has a layered structure of carbonaceous material. Materials (such as interlayers of graphite). After charging until the predetermined voltage is reached, the battery is discharged to 3.0 V on the basis of metal lithium. Further, the specific conditions of the charge and discharge cycle are not particularly limited.
藉由以上方法來製造在蓄電元件用單元8內進行充放電處理(事前處理)的正極`亦即蓄電元件中所用的正極。By the above method, the positive electrode used in the electric storage device, which is a positive electrode that performs charge and discharge processing (pre-treatment) in the electric storage device unit 8 is manufactured.
藉此,可在具有層狀結構的碳質材料形成上述非晶部,可使陰離子的嵌入、脫離位置增大。另外,放電後非晶部亦殘留。因此,電解質的陰離子優先且容易地嵌入、脫離碳質材料的非晶部,因此可使碳質材料的嵌入、脫離量增大,可使蓄電元件的放電容量提升。推測這件事與例如石墨內的非晶部的形成的有無以及層間距離的擴大與嵌入、脫離量具有關聯。亦即,非晶部增加,層間距離變大,結果可以說是陰離子對非晶部優先地嵌入且容易脫離,從而蓄電量增加。Thereby, the amorphous portion can be formed in the carbonaceous material having a layered structure, and the position at which the anion can be inserted and removed can be increased. In addition, the amorphous portion remains after discharge. Therefore, since the anion of the electrolyte preferentially and easily intercalates and desorbs from the amorphous portion of the carbonaceous material, the amount of insertion and removal of the carbonaceous material can be increased, and the discharge capacity of the storage element can be improved. It is presumed that this matter is related to, for example, the presence or absence of the formation of the amorphous portion in the graphite and the enlargement of the interlayer distance, the amount of embedding and the amount of detachment. In other words, the amorphous portion is increased and the interlayer distance is increased. As a result, it can be said that the anion is preferentially embedded in the amorphous portion and is easily detached, so that the amount of stored electricity is increased.
<8.吸附步驟><8. Adsorption step>
接著,在蓄電元件用單元製作步驟中所製作的蓄電元件10的 負極2的電極部與鋰離子供給源5的電極部之間進行電化學接觸,使鋰離子吸附於負極2(吸附步驟)。此處,由電化學接觸造成的負極2的電位更佳為以金屬鋰為基準,而設為0.01V以上、0.1V以下。亦即,通過外部電路使負極2的電極部與鋰離子供給源5的電極部短路(或流通電流),藉此使負極2的具有層狀結構的碳質材料與金屬鋰4進行電化學反應。另外,吸附步驟的具體的吸附條件並無特別限定。Next, the storage element 10 produced in the cell production step manufacturing step Electrochemical contact between the electrode portion of the negative electrode 2 and the electrode portion of the lithium ion supply source 5 is performed to cause lithium ions to be adsorbed to the negative electrode 2 (adsorption step). Here, the electric potential of the negative electrode 2 by electrochemical contact is more preferably 0.01 V or more and 0.1 V or less based on metallic lithium. In other words, the electrode portion of the negative electrode 2 and the electrode portion of the lithium ion supply source 5 are short-circuited (or a current flows) by an external circuit, whereby the carbonaceous material having the layered structure of the negative electrode 2 is electrochemically reacted with the metallic lithium 4 . . Further, the specific adsorption conditions of the adsorption step are not particularly limited.
藉由以上方法來製造在蓄電元件用單元8內進行鋰的預摻雜處理(事前處理)的負極,亦即蓄電元件中所用的負極。By the above method, a negative electrode for performing pre-doping treatment (pre-treatment) of lithium in the electric storage device unit 8 is used, that is, a negative electrode used in the electric storage device.
相對於碳質材料可吸附的鋰離子的最大重量(理論重量),吸附於負極2的碳質材料的金屬鋰的重量較佳為50wt%~90wt%,更佳為60wt%~80wt%,進而佳為70wt%。若在此範圍內,與蓄電元件10的容量相較下,負極2的容量並非過小,因此,可使充分量的鋰離子吸附於負極2。另外,藉由抑制負極2的重量的增加,可防止蓄電元件10的重量增加,因此蓄電元件10的容量密度亦不降低。另外,吸附於負極2的鋰離子的量為適量,因此可維持蓄電元件10的容量密度,亦可防止浮動電荷的容量降低。The weight of the metallic lithium adsorbed to the carbonaceous material of the negative electrode 2 is preferably from 50% by weight to 90% by weight, more preferably from 60% by weight to 80% by weight, based on the maximum weight (theoretical weight) of the lithium ion adsorbable by the carbonaceous material. Good is 70wt%. Within this range, the capacity of the negative electrode 2 is not excessively small as compared with the capacity of the electric storage device 10, so that a sufficient amount of lithium ions can be adsorbed to the negative electrode 2. Further, by suppressing an increase in the weight of the negative electrode 2, the weight of the electric storage device 10 can be prevented from increasing, and thus the capacity density of the electric storage device 10 is not lowered. Further, since the amount of lithium ions adsorbed to the negative electrode 2 is an appropriate amount, the capacity density of the storage element 10 can be maintained, and the capacity of the floating charge can be prevented from being lowered.
<9.其他步驟><9. Other steps>
本發明的蓄電元件的製造方法中,更佳為在上述充放電步驟與吸附步驟之間進行交換蓄電元件用單元8內的非水電解液9的至少一部分的交換步驟。In the method for producing an electric storage device of the present invention, it is more preferable to exchange at least a part of the nonaqueous electrolytic solution 9 in the electric storage device unit 8 between the charging and discharging step and the adsorption step.
藉此補充由於上述充放電步驟時附著於(被捕捉至)正極而 減少的陰離子量(不可逆容量),亦即,可維持非水電解液中的電解質的濃度,因此可製造長期特性優異的蓄電元件。Thereby supplementing the adhesion to the positive electrode due to the above charging and discharging step The reduced anion amount (irreversible capacity), that is, the concentration of the electrolyte in the non-aqueous electrolyte solution can be maintained, so that an electric storage element excellent in long-term characteristics can be produced.
<10.變形例><10. Modifications>
於吸附步驟後進行充放電步驟的情況下,可交換進行上述<7.充放電步驟>及<8.吸附步驟>的順序,從而接著<8.吸附步驟>而進行<7.充放電步驟>。在藉由此順序進行兩步驟的情況下,更佳為在上述吸附步驟與充放電步驟之間進行交換蓄電元件用單元8內的非水電解液9的至少一部分的交換步驟。When the charge and discharge step is performed after the adsorption step, the order of the above <7. charge and discharge step> and <8. adsorption step> may be exchanged, and then <8. adsorption step> and <7. charge and discharge step> may be performed. . In the case where the two steps are performed in this order, it is more preferable to exchange the at least a part of the non-aqueous electrolyte solution 9 in the electric storage device unit 8 between the adsorption step and the charge and discharge step.
<11.充放電電壓的最高電壓><11. Maximum voltage of charge and discharge voltage>
藉由本發明的製造方法所製造的蓄電元件較佳為以該蓄電元件的操作電壓範圍(充放電電壓)的上限電壓成為5.0V以上、6.0V以下的方式進行充放電。It is preferable that the electric storage device manufactured by the manufacturing method of the present invention is charged and discharged so that the upper limit voltage of the operating voltage range (charge and discharge voltage) of the electric storage device is 5.0 V or more and 6.0 V or less.
上述構成的蓄電元件用單元(蓄電元件)中,以上限電壓成為5.0V以上、6.0V以下的方式進行充放電,藉此可產生較公知的鋰離子電池等的蓄電元件為大的蓄電容量。例如,與現有的電雙層電容器(electric double layer capacitor,EDLC)(充放電電壓範圍為0V~2.7V左右)、鋰離子電容器(充放電電壓範圍為2.2V~3.8V左右)相較下,另外,與先前的高容量型鋰離子電池(充放電電壓範圍為2.5V~4.2V左右)相較下,藉由本發明的蓄電元件,可具有容量密度、輸出密度的任一者或兩者優異的效果。In the storage element unit (storage element) having the above-described configuration, the upper limit voltage is 5.0 V or more and 6.0 V or less, and charging and discharging are performed, whereby a storage element such as a known lithium ion battery can have a large storage capacity. For example, compared with the conventional electric double layer capacitor (EDLC) (charge and discharge voltage range is about 0V to 2.7V) and lithium ion capacitor (charge and discharge voltage range is about 2.2V to 3.8V), In addition, compared with the conventional high-capacity lithium ion battery (charge and discharge voltage range of about 2.5 V to 4.2 V), the storage element of the present invention can have either or both of capacity density and output density. Effect.
通常蓄電元件隨著充放電電壓的上限電壓的值降低,則充放電容量降低。然而,在本發明的蓄電元件中,操作電壓範圍 (充放電電壓)的上限電壓為5.0V以上、6.0V以下,因此可獲得充分的充放電容量。另外,若上限電壓超過6.0V,則恐有電解液進行分解而降低特性之虞。另外,若蓄電元件的操作電壓範圍(充放電電壓)的下限電壓在3V附近,則並無特別限定。In general, when the value of the upper limit voltage of the charge/discharge voltage decreases, the charge and discharge capacity decreases. However, in the storage element of the present invention, the operating voltage range Since the upper limit voltage of (charge and discharge voltage) is 5.0 V or more and 6.0 V or less, a sufficient charge and discharge capacity can be obtained. Further, when the upper limit voltage exceeds 6.0 V, there is a fear that the electrolytic solution is decomposed to lower the characteristics. In addition, when the lower limit voltage of the operating voltage range (charge and discharge voltage) of the electric storage device is in the vicinity of 3 V, it is not particularly limited.
藉由本發明的製造方法所製造的蓄電元件為操作電壓範圍(充放電電壓)的上限電壓高至5.0V以上、6.0V以下且大容量的蓄電池。因此藉由該製造方法所製造的蓄電元件或具備該蓄電元件的蓄電裝置可廣泛地用於筆記型電腦或行動電話等的各種便攜型機器等的一般電氣機器、電動車或混合動力車所搭載的汽車用的蓄電裝置、或組合有太陽電池或風力發電等新能量系統而成的電力儲藏用蓄電池等各種領域。The electric storage device manufactured by the manufacturing method of the present invention is a battery having an upper limit voltage of an operating voltage range (charge and discharge voltage) of up to 5.0 V or more and 6.0 V or less and a large capacity. Therefore, the electric storage device manufactured by the manufacturing method or the electric storage device including the electric storage device can be widely used in general electric equipment, electric vehicles, or hybrid vehicles such as various portable devices such as notebook computers and mobile phones. Various types of power storage devices for automobiles, or batteries for power storage in which a new energy system such as a solar battery or wind power generation is combined.
另外,本發明的蓄電元件的製造方法中亦包含以下發明。Further, the method for producing an electric storage device of the present invention also includes the following invention.
1.一種非水電解液二次電池的製造方法,上述非水電解液二次電池具有下述構成:將正極與負極隔著間隔物而交互地積層三層以上而形成單元結構,並與其相對向的配置鋰離子供給源,並且在其中具備溶解有鋰鹽的非水電解液,上述正極與負極是將正極活性物質以及負極活性物質個別形成於包括貫通表面、背面的孔的正極集電體及負極集電體上而成,且使陰離子嵌入、脫離層間的碳質材料用於正極活性物質,使陽離子嵌入、脫離層間的碳質材料用於負極活性物質,其特徵在於包括:在非水電解液二次電池中,首先在鋰供給源與正極之間進行充放電的步驟; 以及之後在鋰供給源與負極之間進行電化學接觸而在負極預先嵌入作為陽離子的鋰離子的步驟。1. A method for producing a nonaqueous electrolyte secondary battery, wherein the nonaqueous electrolyte secondary battery has a configuration in which a positive electrode and a negative electrode are alternately laminated with three or more layers via a separator to form a unit structure, and a semiconductor structure is formed thereon. A lithium ion supply source is disposed, and a nonaqueous electrolytic solution in which a lithium salt is dissolved therein is provided, and the positive electrode and the negative electrode are positive electrode current collectors in which a positive electrode active material and a negative electrode active material are individually formed in a hole including a through surface and a back surface. And a negative electrode current collector, and a carbonaceous material in which an anion is intercalated or separated from the interlayer is used for the positive electrode active material, and a carbonaceous material in which the cation is intercalated or separated from the interlayer is used for the negative electrode active material, and is characterized in that: In the electrolyte secondary battery, first, a step of charging and discharging between the lithium supply source and the positive electrode; And a step of electrochemically contacting the lithium supply source and the negative electrode to intercalate lithium ions as a cation in advance in the negative electrode.
2.更佳為在進行上述鋰供給源與正極之間的充放電的步驟,以及之後在鋰供給源與負極之間進行電化學接觸而在負極預先嵌入作為陽離子的鋰離子的步驟之間,包括交換溶解有鋰鹽的非水電解液的步驟。2. More preferably, the step of performing charge and discharge between the lithium supply source and the positive electrode, and then the step of electrochemically contacting the lithium supply source with the negative electrode and preliminarily intercalating the lithium ion as a cation in the negative electrode. This includes the step of exchanging a non-aqueous electrolyte in which a lithium salt is dissolved.
3.一種非水電解液二次電池的製造方法,上述非水電解液二次電池具有下述構成:將正極與負極隔著間隔物而交互地積層三層以上而形成單元結構,且與其相對向的配置鋰離子供給源,並且在其中具備溶解有鋰鹽的非水電解液,上述正極與負極是將正極活性物質以及負極活性物質個別形成於包括貫通表面、背面的孔的正極集電體及負極集電體上而成,且使陰離子嵌入、脫離層間的碳質材料用於正極活性物質,使陽離子嵌入、脫離層間的碳質材料用於負極活性物質,其特徵在於包括:在非水電解液二次電池中,首先在鋰供給源與負極之間進行電化學接觸而在負極預先嵌入作為陽離子的鋰離子的步驟;以及之後在鋰供給源與正極之間進行充放電的步驟。3. A method for producing a non-aqueous electrolyte secondary battery, wherein the non-aqueous electrolyte secondary battery has a configuration in which a positive electrode and a negative electrode are alternately laminated with three or more layers via a separator to form a unit structure, and a semiconductor structure is formed thereon. A lithium ion supply source is disposed, and a nonaqueous electrolytic solution in which a lithium salt is dissolved therein is provided, and the positive electrode and the negative electrode are positive electrode current collectors in which a positive electrode active material and a negative electrode active material are individually formed in a hole including a through surface and a back surface. And a negative electrode current collector, and a carbonaceous material in which an anion is intercalated or separated from the interlayer is used for the positive electrode active material, and a carbonaceous material in which the cation is intercalated or separated from the interlayer is used for the negative electrode active material, and is characterized in that: In the electrolyte secondary battery, first, electrochemical contact is performed between the lithium supply source and the negative electrode, and lithium ions as a cation are preliminarily embedded in the negative electrode; and then a step of charging and discharging between the lithium supply source and the positive electrode is performed.
4.更佳為在上述鋰供給源與負極之間進行電化學接觸而在負極預先嵌入作為陽離子的鋰離子的步驟,以及之後進行鋰供給源與正極之間的充放電的步驟之間,包括交換溶解有鋰鹽的非水電解液的步驟。4. More preferably, between the step of electrochemically contacting the lithium supply source and the negative electrode, and preliminarily intercalating lithium ions as a cation in the negative electrode, and then performing a step of charging and discharging between the lithium supply source and the positive electrode, including The step of exchanging a nonaqueous electrolyte in which a lithium salt is dissolved.
5.更佳為以金屬鋰為基準,將上述鋰供給源與正極之間 的充放電設為5.0V~6.0V。5. More preferably, based on metal lithium, between the above lithium supply source and the positive electrode The charge and discharge is set to 5.0V to 6.0V.
6.更佳為以金屬鋰為基準,將鋰供給源與負極之間的電化學接觸所造成的負極的電位設為0.01V~0.1V。6. More preferably, the potential of the negative electrode caused by electrochemical contact between the lithium supply source and the negative electrode is set to 0.01 V to 0.1 V based on metallic lithium.
7.一種非水電解液二次電池,其藉由將電池的操作電壓範圍的上限電壓設為5.0V~6.0V的上述非水電解液二次電池的製造方法來製造。A nonaqueous electrolyte secondary battery produced by the method for producing a nonaqueous electrolyte secondary battery in which an upper limit voltage of an operating voltage range of a battery is 5.0 V to 6.0 V.
本發明並未限定於以上所教示的各構成,在說明書所記載的範圍內可進行各種變更,將不同的實施方式分別揭露的技術手段適當地組合而得的實施方式亦包括在本發明的技術範圍內。另外,引用本說明書中所記載的文獻全部來作為參考。The present invention is not limited to the respective configurations described above, and various modifications can be made within the scope of the specification, and embodiments in which the technical means disclosed in the different embodiments are appropriately combined are also included in the technology of the present invention. Within the scope. In addition, the documents described in the present specification are all incorporated by reference.
[實施例][Examples]
以下藉由實施例來對本發明更詳細地進行說明,但並非僅限定於本發明的實施例。Hereinafter, the present invention will be described in more detail by way of examples, but not limited to the examples of the invention.
[實施例1][Example 1]
製作圖1所示的構成的蓄電元件10。亦即,藉由下述製造方法來製作本實施例的蓄電元件。The electric storage device 10 having the configuration shown in Fig. 1 is produced. That is, the electric storage device of the present embodiment is produced by the following manufacturing method.
<正極1的製作><Production of positive electrode 1>
將作為黏合劑的聚偏二氟乙烯溶解於作為溶劑的N-甲基-2-吡咯啶酮後,在所得的溶液中分散作為正極活性物質的石墨(KS6:Timcal公司製作),從而製成漿料(分散液)。使用刮刀將該漿料塗布於作為正極集電體的多孔鋁箔(市售品;厚度20μm;開口率30%)的表面、背面,使其乾燥而製作正極1。所塗布的漿 料的乾燥後的厚度,亦即正極1的厚度(單面)為80μm。另外,石墨與聚偏二氟乙烯的重量比(石墨:聚偏二氟乙烯)為90:10。After dissolving polyvinylidene fluoride as a binder in N-methyl-2-pyrrolidone as a solvent, graphite (KS6: manufactured by Timcal Co., Ltd.) as a positive electrode active material was dispersed in the obtained solution to prepare Slurry (dispersion). This slurry was applied onto a surface and a back surface of a porous aluminum foil (commercial product; thickness: 20 μm; opening ratio: 30%) as a positive electrode current collector using a doctor blade, and dried to prepare a positive electrode 1. Coated slurry The thickness of the material after drying, that is, the thickness of the positive electrode 1 (single side) was 80 μm. Further, the weight ratio of graphite to polyvinylidene fluoride (graphite: polyvinylidene fluoride) was 90:10.
<負極2的製作><Production of Negative Electrode 2>
將作為黏合劑的聚偏二氟乙烯溶解於作為溶劑的N-甲基-2-吡咯啶酮後,在所得的溶液中分散作為負極活性物質的人造石墨(市售品;石墨),從而製成漿料(分散液)。使用刮刀將該漿料塗布於作為負極集電體的多孔銅箔(市售品;厚度15μm;開口率20%)的表面、背面或單面,使其乾燥而製作負極2。所塗布的漿料的乾燥後的厚度,亦即負極2的厚度(單面)為90μm。另外,人造石墨與聚偏二氟乙烯的重量比(人造石墨:聚偏二氟乙烯)為90:10。After dissolving polyvinylidene fluoride as a binder in N-methyl-2-pyrrolidone as a solvent, artificial graphite (commercial product; graphite) as a negative electrode active material is dispersed in the obtained solution to prepare Slurry (dispersion). This slurry was applied to the surface, the back surface, or the single surface of a porous copper foil (commercial product; thickness: 15 μm; opening ratio: 20%) as a negative electrode current collector by a doctor blade, and dried to prepare a negative electrode 2. The thickness of the applied slurry after drying, that is, the thickness of the negative electrode 2 (single side) was 90 μm. Further, the weight ratio of artificial graphite to polyvinylidene fluoride (artificial graphite: polyvinylidene fluoride) was 90:10.
<蓄電元件10的製作><Production of Power Storage Element 10>
在碳酸伸乙酯與碳酸二甲酯以重量比1:1混合而成的混合溶液中,將作為電解質(鋰鹽)的六氟磷酸鋰(LiPF6 )以其濃度(電解質濃度)成為1.5mol/L(1.5M)的方式進行溶解,藉此製作非水電解液9。Lithium hexafluorophosphate (LiPF 6 ) as an electrolyte (lithium salt) was made to have a concentration (electrolyte concentration) of 1.5 mol/L in a mixed solution of ethylene carbonate and dimethyl carbonate in a weight ratio of 1:1. The non-aqueous electrolyte 9 was produced by dissolving in a manner of 1.5 M).
並且,在乾燥環境下製作蓄電元件10。亦即,以最外層成為負極2的方式隔著間隔物3積層五層所製作的上述正極1及負極2,藉此製作積層體6。進而,在積層體6隔著間隔物3而積層了鋰離子供給源(市售品)5,上述鋰離子供給源(市售品)5包括具備金屬鋰4的銅箔。相對於負極2可吸附的鋰離子的最大重量(理論重量),金屬鋰的重量設定為成為70wt%的量。並且,將電 極部分別安裝於正極1、負極2以及鋰離子供給源5。Further, the storage element 10 is fabricated in a dry environment. In other words, the positive electrode 1 and the negative electrode 2 which are produced by laminating five layers via the spacer 3 so that the outermost layer becomes the negative electrode 2, thereby producing the laminated body 6. Further, a lithium ion supply source (commercial product) 5 is laminated in the laminated body 6 with the spacer 3 interposed therebetween, and the lithium ion supply source (commercial product) 5 includes a copper foil including metal lithium 4. The weight of the metal lithium is set to be 70% by weight with respect to the maximum weight (theoretical weight) of the lithium ions which can be adsorbed to the negative electrode 2. And, electricity The pole portions are attached to the positive electrode 1, the negative electrode 2, and the lithium ion supply source 5, respectively.
將包括積層體6與鋰離子供給源5的上述積層體隔著間隔物3而收容(組裝)於組裝構件(包括鋁的積層膜)7內,並且將上述非水電解液9注入該組裝構件7內。接著,藉由密閉組裝構件7而密封蓄電元件用單元8,藉此製作蓄電元件(藉由蓄電元件用單元製作步驟而製作的蓄電元件)10。The laminated body including the laminated body 6 and the lithium ion supply source 5 is housed (assembled) in the assembly member (including the laminated film of aluminum) 7 via the spacer 3, and the nonaqueous electrolyte 9 is injected into the assembled member. Within 7. Then, the storage element unit 8 is sealed by sealing the assembly member 7, thereby producing an electric storage element (an electric storage element produced by the unit for manufacturing the electric storage element) 10 .
在所製作的蓄電元件10的正極1及鋰離子供給源5之間進行一次充放電循環,上述充放電循環是以金屬鋰為基準,使正極電位成為5.3V來流通一定電流而進行充電,之後進行放電。A charge/discharge cycle is performed between the positive electrode 1 and the lithium ion supply source 5 of the produced storage element 10, and the charge/discharge cycle is performed by charging a constant current with a positive electrode potential of 5.3 V based on metal lithium, and then charging. Discharge.
之後,通過外部電路而使蓄電元件10的負極2及鋰離子供給源5之間短路,藉此使鋰離子吸附於負極2。Thereafter, the negative electrode 2 of the electric storage device 10 and the lithium ion supply source 5 are short-circuited by an external circuit, whereby lithium ions are adsorbed to the negative electrode 2.
藉此製作實施例1的蓄電元件。Thereby, the electric storage device of Example 1 was produced.
[實施例2][Embodiment 2]
與實施例1同樣進行而製作蓄電元件(藉由蓄電元件用單元製作步驟而製作的蓄電元件)10。In the same manner as in the first embodiment, an electric storage device (an electric storage device produced by the unit for manufacturing the electric storage device) 10 was produced.
通過外部電路而使所製作的蓄電元件10的負極2及鋰離子供給源5之間短路,藉此使鋰離子吸附於負極2。The negative electrode 2 of the produced electric storage device 10 and the lithium ion supply source 5 are short-circuited by an external circuit, whereby lithium ions are adsorbed to the negative electrode 2.
之後,在蓄電元件10的正極1及鋰離子供給源5之間進行一次充放電循環,上述充放電循環是以金屬鋰為基準,使正極電位成為5.3V來流通一定電流而進行充電,之後進行放電。After that, a charge/discharge cycle is performed between the positive electrode 1 of the energy storage device 10 and the lithium ion supply source 5, and the charge and discharge cycle is performed by charging a constant current with a positive electrode potential of 5.3 V based on metal lithium, and then performing charging. Discharge.
藉此製作實施例2的蓄電元件。Thereby, the electric storage device of Example 2 was produced.
[實施例3][Example 3]
與實施例1同樣進行而製作蓄電元件(藉由蓄電元件用單元製作步驟而製作的蓄電元件)10。In the same manner as in the first embodiment, an electric storage device (an electric storage device produced by the unit for manufacturing the electric storage device) 10 was produced.
之後,在蓄電元件10的正極1以及藉由吸附步驟來吸附鋰離子而藉此作為鋰離子供給源5發揮作用的負極2之間進行一次充放電循環,上述充放電循環是以金屬鋰為基準,使正極電位成為5.3V來流通一定電流而進行充電,之後進行放電。Thereafter, a charge/discharge cycle is performed between the positive electrode 1 of the electric storage device 10 and the negative electrode 2 that functions as a lithium ion supply source 5 by adsorbing lithium ions by an adsorption step, and the charge and discharge cycle is based on metallic lithium. The positive electrode potential was set to 5.3 V, and a constant current was passed to charge, and then discharged.
藉此製作實施例3的蓄電元件。Thereby, the electric storage device of Example 3 was produced.
[比較例1][Comparative Example 1]
<正極的製作><Production of positive electrode>
與實施例1的<正極1的製作>同樣進行而製作正極。接著,進行所製作的正極的事前處理(充放電)。亦即,將石油焦炭藉由水蒸氣活化所得的比表面積為2000m2 /g的活性碳、導電性碳黑以及作為黏合劑的聚四氟乙烯以活性碳80wt%、導電性碳黑10wt%、以及聚四氟乙烯10wt%的比例進行混合,使用乙醇進行混練而壓延,藉此成形為片狀的成形物。成形物的厚度為400μm。使用導電性黏著劑而將該成形物黏著於鋁箔,藉此製作正極處理用負極。The positive electrode was produced in the same manner as in <Preparation of the positive electrode 1 of Example 1>. Next, the pretreatment (charge and discharge) of the produced positive electrode was performed. That is, the activated carbon, the conductive carbon black having a specific surface area of 2000 m 2 /g, and the polytetrafluoroethylene as a binder of the petroleum coke activated by steam activation are 80 wt% of activated carbon and 10 wt% of conductive carbon black. Further, the mixture was mixed at a ratio of 10% by weight of polytetrafluoroethylene, and kneaded with ethanol and calendered to form a sheet-shaped molded product. The thickness of the molded product was 400 μm. The molded article was adhered to an aluminum foil by using a conductive adhesive to prepare a negative electrode for positive electrode treatment.
另外,在將4-三氟甲基-1,3-二氧雜環戊烷-2-酮與1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚「H(CF2 )2 CH2 O(CF2 )2 H」以重量比1:1混合而成的混合溶劑100重量份中,溶解電解質鹽(SBP-PF6;日本Carlit(股)製)100重量份,藉此製作非水電解液。In addition, 4-trifluoromethyl-1,3-dioxol-2-one and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropene The ethyl ether "H(CF 2 ) 2 CH 2 O(CF 2 ) 2 H" was dissolved in 100 parts by weight of a mixed solvent in a weight ratio of 1:1, and dissolved in an electrolyte salt (SBP-PF6; manufactured by Japan Carlit Co., Ltd.) 100 parts by weight, thereby producing a non-aqueous electrolyte.
隔著纖維素系的多孔質間隔物而使所製作的正極及正極處理 用負極對向,並且將電極部安裝於正極及正極處理用負極,從而收容(組裝)於組裝構件(包括鋁的積層膜)內。接著,將上述非水電解液注入該組裝構件內。接著,藉由密閉組裝構件而密封充放電單元,藉此製作充放電用元件。The positive electrode and the positive electrode are processed through a porous separator of cellulose type The electrode portion is opposed to the positive electrode and the negative electrode for positive electrode processing, and is housed (assembled) in an assembly member (including a laminated film of aluminum). Next, the nonaqueous electrolyte solution is injected into the assembly member. Next, the charge and discharge unit is sealed by sealing the assembly member, thereby producing a charge and discharge element.
在所製作的充放電用元件的正極以及正極處理用負極之間流通直流電流,藉此從0V充電至3.5V為止,之後立即以成為0V的方式進行放電。放電後,分解充放電用元件而僅取出正極。A direct current was passed between the positive electrode of the charge and discharge element to be produced and the negative electrode for positive electrode treatment, thereby charging from 0 V to 3.5 V, and immediately thereafter discharging was performed at 0 V. After the discharge, the charge and discharge elements were decomposed and only the positive electrode was taken out.
<負極的製作><Production of Negative Electrode>
與實施例1的<負極2的製作>同樣進行而製作負極。接著,與實施例1的<蓄電元件10的製作>同樣進行使鋰離子吸附於負極的事前處理(鋰的預摻雜)。亦即,在乾燥環境下,隔著纖維素系的多孔質間隔物而使所製作的負極以及包括具備金屬鋰的銅箔的鋰離子供給源(市售品)對向,並且將電極部安裝於負極以及鋰離子供給源,從而收容(組裝)於組裝構件(包括鋁的積層膜)內。接著,將與實施例1所製作的非水電解液相同的非水電解液注入該組裝構件內。接著,藉由密閉組裝構件而密封吸附處理用單元,藉此製作吸附處理用元件。之後,通過外部電路使所製作的吸附處理用元件的負極以及鋰離子供給源之間短路,藉此使鋰離子吸附於負極。吸附處理後,分解吸附處理用元件而僅取出負極。The negative electrode was produced in the same manner as in <Preparation of the negative electrode 2 of Example 1>. Next, in the same manner as in the preparation of <the storage element 10 of the first embodiment>, the lithium ion is adsorbed to the negative electrode in advance (pre-doping of lithium). In other words, in the dry environment, the produced negative electrode and the lithium ion supply source (commercial product) including the copper foil containing metal lithium are opposed to each other via the porous separator of the cellulose type, and the electrode portion is mounted. The negative electrode and the lithium ion supply source are housed (assembled) in an assembly member (including a laminated film of aluminum). Next, the same nonaqueous electrolyte as the nonaqueous electrolytic solution produced in Example 1 was injected into the assembly member. Next, the adsorption processing unit is sealed by sealing the assembly member, thereby producing an adsorption processing element. Thereafter, the negative electrode between the produced adsorption processing element and the lithium ion supply source are short-circuited by an external circuit, whereby lithium ions are adsorbed to the negative electrode. After the adsorption treatment, the element for the adsorption treatment is decomposed and only the negative electrode is taken out.
<蓄電元件的製作><Production of storage element>
使用進行了事前處理的上述正極及負極,與實施例1的<蓄 電元件10的製作>同樣進行而製作蓄電元件。亦即,在乾燥環境下,以最外層成為負極的方式隔著間隔物積層五層所製作的上述正極及負極,藉此製作積層體。並且,將電極部分別安裝於正極以及負極。將上述積層體隔著間隔物而收容(組裝)於組裝構件(包括鋁的積層膜)內,並且將與實施例1所製作的非水電解液相同的非水電解液注入該組裝構件內。接著,藉由密閉組裝構件而密封蓄電元件用單元,藉此製作蓄電元件。因此,製作蓄電元件時不進行充放電處理以及吸附處理。藉此製作比較例1的(現有的)蓄電元件。The above-mentioned positive electrode and negative electrode which have been subjected to the prior treatment are used, and the <Example of the first embodiment Preparation of Electrical Element 10 > The same was performed to produce an electrical storage element. In other words, in the dry environment, the above-mentioned positive electrode and negative electrode which are formed by laminating five layers with a separator in the outermost layer are formed to form a laminate. Further, the electrode portions are attached to the positive electrode and the negative electrode, respectively. The laminated body was housed (assembled) in an assembly member (including a laminated film of aluminum) via a spacer, and a non-aqueous electrolyte solution similar to the non-aqueous electrolyte solution produced in Example 1 was injected into the assembly member. Next, the electric storage element unit is sealed by sealing the assembly member, thereby producing an electric storage element. Therefore, the charge/discharge process and the adsorption process are not performed when the storage element is produced. Thus, the (conventional) electric storage device of Comparative Example 1 was produced.
<結果><Result>
<i.生產性><i.Productivity>
在將比較例1的蓄電元件的製造時間設為100(基準)的情況下,在製作蓄電元件前,亦可不進行正極以及負極的事前處理(充放電處理以及吸附處理)的實施例1、實施例2以及實施例3的蓄電元件10的製造時間為30。亦即,製造實施例1、實施例2以及實施例3的蓄電元件10時所需要的時間為製造比較例1的蓄電元件時所需要的時間的3成。When the production time of the electric storage device of the comparative example 1 is 100 (reference), the first embodiment of the positive electrode and the negative electrode (charge and discharge treatment and adsorption treatment) may be performed before the storage of the electric storage device. The manufacturing time of the electric storage device 10 of Example 2 and Example 3 was 30. That is, the time required to manufacture the electric storage device 10 of the first embodiment, the second embodiment, and the third embodiment is 30% of the time required to manufacture the electric storage device of the comparative example 1.
因此,可知藉由製造步驟經簡略化的本發明的蓄電元件的製造方法,可大幅地縮短蓄電元件的製造時間(週期時間)。亦即,可知本發明的蓄電元件的製造方法的生產性優異。Therefore, it is understood that the manufacturing time (cycle time) of the electric storage device can be greatly shortened by the method for manufacturing the electric storage device of the present invention which is simplified in the manufacturing steps. In other words, it is understood that the method for producing an electric storage device of the present invention is excellent in productivity.
另外,藉由本發明的蓄電元件的製造方法,在製作蓄電元件前亦可不進行正極以及負極的事前處理(充放電處理以及吸 附處理)。亦即,並不需要製作用以進行正極的事前處理(充放電)的充放電用元件以及用以進行負極的事前處理(吸附處理)的吸附處理用元件。因此,並不需要製作(或準備)用以製作該充放電用元件以及吸附處理用元件的正極處理用負極或非水電解液、多孔質間隔物、電極部、組裝構件等。因此,可知藉由製造步驟經簡略化的本發明的蓄電元件的製造方法,可大幅地減少蓄電元件的製造成本(材料所耗費的成本)。亦即,能夠以低成本製造蓄電元件。Further, according to the method for producing an electric storage device of the present invention, the positive electrode and the negative electrode may not be subjected to the prior treatment (charge and discharge treatment and suction) before the storage of the electric storage device. Attached to the process). In other words, it is not necessary to produce a charge/discharge element for performing the preliminary treatment (charge and discharge) of the positive electrode and an adsorption treatment element for performing the preliminary treatment (adsorption treatment) of the negative electrode. Therefore, it is not necessary to prepare (or prepare) a negative electrode for positive electrode treatment, a nonaqueous electrolytic solution, a porous separator, an electrode portion, an assembly member, and the like for producing the charge/discharge element and the adsorption treatment element. Therefore, it is understood that the manufacturing method of the electric storage device of the present invention, which is simplified in the manufacturing steps, can significantly reduce the manufacturing cost of the electric storage device (the cost of the material). That is, the storage element can be manufactured at low cost.
另外,在將比較例1的蓄電元件的製造成本設為100(基準)的情況下,在製作蓄電元件前,亦可不進行正極以及負極的事前處理(充放電處理以及吸附處理)的實施例1、實施例2以及實施例3的蓄電元件10的製造成本為40。In addition, in the case where the manufacturing cost of the electric storage device of the comparative example 1 is 100 (reference), the first embodiment (charge-discharge treatment and adsorption treatment) of the positive electrode and the negative electrode may not be performed before the storage of the electric storage device. The manufacturing cost of the electric storage device 10 of the second embodiment and the third embodiment is 40.
<ii.性能><ii. Performance>
對上述實施例1、實施例2以及實施例3的蓄電元件10以及比較例1的蓄電元件進行充放電循環試驗。充放電循環試驗的條件是在25℃的恆溫槽內,將操作電壓範圍設為3.0V~5.3V,且設定為2C-CC充電速率以及0.5C-CC放電速率。The charge storage cycle test was performed on the electric storage device 10 of the above-described first, second and third embodiments and the electric storage device of the comparative example 1. The charge and discharge cycle test was carried out under the conditions of a 25 ° C constant temperature bath, and the operating voltage range was set to 3.0 V to 5.3 V, and was set to a 2 C-CC charge rate and a 0.5 C-CC discharge rate.
並且,對上述實施例1的蓄電元件10以及比較例1的蓄電元件進行100循環的充放電循環試驗,測定試驗前以及試驗後(100循環後)的容量而測定容量變化。亦即,測定將試驗前的容量(初期容量)設為100(基準)時的試驗後的容量變化(降低),從而評價兩蓄電元件的性能。將結果示於表1。另外,上述實施例1 的蓄電元件10以及比較例1的蓄電元件的初期容量彼此相同。Further, the electric storage device 10 of the first embodiment and the electric storage device of the comparative example 1 were subjected to a charge and discharge cycle test for 100 cycles, and the capacity before and after the test (after 100 cycles) was measured to measure the change in capacity. In other words, the capacity change (decrease) after the test when the capacity (initial capacity) before the test was set to 100 (reference) was measured, and the performance of the two storage elements was evaluated. The results are shown in Table 1. In addition, the above embodiment 1 The initial capacities of the storage element 10 and the storage element of Comparative Example 1 are the same as each other.
同樣地,對上述實施例1、實施例2以及實施例3的蓄電元件10以及比較例1的蓄電元件進行500循環的充放電循環試驗,測定試驗前以及試驗後(500循環後)的容量而測定容量變化。亦即,測定將試驗前的容量(初期容量)設為100(基準)時的試驗後的容量變化(降低),從而評價各蓄電元件的性能。將結果示於表2。另外,上述實施例1、實施例2以及實施例3的蓄電元件10以及比較例1的蓄電元件的初期容量彼此相同。Similarly, the charge storage/discharge cycle test of the electric storage device 10 of the first embodiment, the second embodiment, and the third embodiment and the electric storage device of the comparative example 1 was performed for 500 cycles, and the capacities before and after the test (after 500 cycles) were measured. The capacity change was measured. In other words, the capacity change (decrease) after the test when the capacity (initial capacity) before the test was set to 100 (reference) was measured, and the performance of each of the electric storage devices was evaluated. The results are shown in Table 2. In addition, the initial capacities of the electric storage device 10 of the first embodiment, the second embodiment, the third embodiment, and the electric storage device of the first embodiment are the same as each other.
從表1、表2的記載明確可知,與比較例1的蓄電元件 相較下,實施例1、實施例2以及實施例3的蓄電元件10的試驗後的容量變化(降低)較少,且具有長期特性優異的性能。亦即,可知藉由本發明的蓄電元件的製造方法所製造的蓄電元件的長期穩定性優異。另外,比較例1的蓄電元件中,作為試驗後的容量變化(降低)較多的主因,認為是進行電極的事前處理後,從充放電用元件以及吸附處理用元件取出正極以及負極而製作蓄電元件時,與乾燥環境中殘留的氧接觸所造成的電極或非水電解液的性能降低,以及由於充放電用元件以及吸附處理用元件的分解所產生的異物(例如組裝構件的破片等)混入蓄電元件等。As is clear from the descriptions of Tables 1 and 2, the storage element of Comparative Example 1 is known. In contrast, in the electric storage device 10 of the first embodiment, the second embodiment, and the third embodiment, the capacity change (decrease) after the test is small, and the long-term characteristics are excellent. In other words, the electric storage device manufactured by the method for producing an electric storage device of the present invention is excellent in long-term stability. In addition, in the electric storage device of the first comparative example, the main cause of the change (decrease) in the capacity after the test is that the positive electrode and the negative electrode are taken out from the charge and discharge element and the adsorption processing element to prepare the electric storage. In the case of the element, the performance of the electrode or the non-aqueous electrolyte caused by contact with the oxygen remaining in the dry environment is lowered, and the foreign matter (for example, a fragment of the assembly member) generated by the decomposition of the charge/discharge element and the adsorption processing element is mixed. Power storage components, etc.
[產業上的可利用性][Industrial availability]
藉由本發明的蓄電元件的製造方法,可製造製作步驟經簡略化、低成本(生產性優異)且長期穩定性優異的蓄電元件。因此,藉由該製造方法所製造的蓄電元件或具備該蓄電元件的蓄電裝置可廣泛地用於筆記型電腦或行動電話等的各種便攜型機器等的一般電氣機器、電動車或混合動力車所搭載的汽車用的蓄電裝置、或組合有太陽電池或風力發電等新能量系統而成的電力儲藏用蓄電池等各種領域。According to the method for producing an electric storage device of the present invention, it is possible to manufacture an electric storage device having a simplified production process, low cost (excellent productivity), and excellent long-term stability. Therefore, the electric storage device manufactured by the manufacturing method or the electric storage device including the electric storage device can be widely used in general electric equipment, electric vehicles, or hybrid vehicles such as various portable devices such as notebook computers and mobile phones. Various types of fields such as a power storage device for automobiles and a battery for power storage in which a new energy system such as a solar battery or wind power generation is combined.
1‧‧‧正極1‧‧‧ positive
2‧‧‧負極2‧‧‧negative
3‧‧‧間隔物3‧‧‧ spacers
4‧‧‧金屬鋰4‧‧‧metal lithium
5‧‧‧鋰離子供給源5‧‧‧Lithium ion supply source
6‧‧‧積層體6‧‧‧Layer
7‧‧‧組裝構件7‧‧‧Assembled components
8‧‧‧蓄電元件用單元8‧‧‧Units for electrical storage components
9‧‧‧非水電解液9‧‧‧ Non-aqueous electrolyte
10‧‧‧蓄電元件10‧‧‧Power storage components
Claims (8)
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JP2013055600A JP5429678B1 (en) | 2012-12-27 | 2013-03-18 | Method for manufacturing power storage device |
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JP5429678B1 (en) * | 2012-12-27 | 2014-02-26 | 日新電機株式会社 | Method for manufacturing power storage device |
JP6498423B2 (en) * | 2014-11-28 | 2019-04-10 | イビデン株式会社 | Method for manufacturing power storage device |
JP2016201295A (en) * | 2015-04-13 | 2016-12-01 | 日新電機株式会社 | Power storage device |
JP2017152139A (en) * | 2016-02-23 | 2017-08-31 | 積水化学工業株式会社 | Lithium ion secondary battery |
CN110098377B (en) * | 2019-04-25 | 2022-04-05 | 浙江锋锂新能源科技有限公司 | Lithium ion battery with high capacity retention rate, preparation method and charge-discharge mode thereof |
JP2021061113A (en) * | 2019-10-03 | 2021-04-15 | イビデン株式会社 | Electrode for power storage device, power storage device, secondary battery, lithium ion capacitor, air battery and all-solid battery |
KR20210093528A (en) * | 2020-01-20 | 2021-07-28 | 주식회사 엘지에너지솔루션 | New method for preparing secondary battery |
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JP2007305522A (en) * | 2006-05-15 | 2007-11-22 | Fdk Corp | Storage element |
JP2011077156A (en) * | 2009-09-29 | 2011-04-14 | Nissin Electric Co Ltd | Storage device |
CN102301439A (en) * | 2008-12-26 | 2011-12-28 | Jm能源股份有限公司 | Wound-type accumulator |
JP2012004491A (en) * | 2010-06-21 | 2012-01-05 | Nec Tokin Corp | Power storage device |
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JP2008041489A (en) * | 2006-08-08 | 2008-02-21 | Fdk Corp | Lithium ion electricity storage element |
JP5317688B2 (en) * | 2008-12-26 | 2013-10-16 | Jmエナジー株式会社 | Winding type accumulator and method for manufacturing the same |
JP5686076B2 (en) * | 2011-09-08 | 2015-03-18 | 株式会社豊田自動織機 | Method for producing lithium ion secondary battery |
JP5429678B1 (en) * | 2012-12-27 | 2014-02-26 | 日新電機株式会社 | Method for manufacturing power storage device |
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JP2007305522A (en) * | 2006-05-15 | 2007-11-22 | Fdk Corp | Storage element |
CN102301439A (en) * | 2008-12-26 | 2011-12-28 | Jm能源股份有限公司 | Wound-type accumulator |
JP2011077156A (en) * | 2009-09-29 | 2011-04-14 | Nissin Electric Co Ltd | Storage device |
JP2012004491A (en) * | 2010-06-21 | 2012-01-05 | Nec Tokin Corp | Power storage device |
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WO2014104127A1 (en) | 2014-07-03 |
JP6284198B2 (en) | 2018-02-28 |
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JPWO2014104127A1 (en) | 2017-01-12 |
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