TWI835939B - Electrolytes and electrochemical devices - Google Patents
Electrolytes and electrochemical devices Download PDFInfo
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- TWI835939B TWI835939B TW108144541A TW108144541A TWI835939B TW I835939 B TWI835939 B TW I835939B TW 108144541 A TW108144541 A TW 108144541A TW 108144541 A TW108144541 A TW 108144541A TW I835939 B TWI835939 B TW I835939B
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- electrolyte
- negative electrode
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Abstract
本發明的一態樣提供一種電解液，其含有：由下述式(1)表示的化合物；及，具有碳-碳雙鍵之環狀碳酸酯； 式(1)中，R1 ～R3 各自獨立地表示烷基或氟原子，R4 表示伸烷基，R5 表示包含氮原子或硫原子之有機基團。One aspect of the present invention provides an electrolyte solution containing: a compound represented by the following formula (1); and a cyclic carbonate having a carbon-carbon double bond; In the formula (1), R 1 to R 3 each independently represent an alkyl group or a fluorine atom, R 4 represents an alkylene group, and R 5 represents an organic group containing a nitrogen atom or a sulfur atom.
Description
本發明有關一種電解液及電化學裝置。The present invention relates to an electrolyte and an electrochemical device.
近年來，因可攜型電子機器、電動汽車等的普及，而正需要下述高性能的電化學裝置：以鋰離子二次電池為代表的非水電解液二次電池、電容器等。作為用以提高電化學裝置的性能的手段，正在研究例如下述方法：在電解液中添加規定的添加劑。專利文獻1中揭示一種非水電解液電池用電解液，其是為了改善循環特性及內部電阻特性而含有特定矽氧烷化合物而成。 [先前技術文獻] (專利文獻)In recent years, due to the spread of portable electronic devices, electric vehicles, etc., high-performance electrochemical devices such as non-aqueous electrolyte secondary batteries represented by lithium ion secondary batteries, capacitors, and the like are in demand. As a means for improving the performance of an electrochemical device, a method of adding a predetermined additive to an electrolytic solution is being studied, for example. Patent Document 1 discloses an electrolyte for a nonaqueous electrolyte battery that contains a specific siloxane compound in order to improve cycle characteristics and internal resistance characteristics. [Prior technical literature] (patent document)
專利文獻1：日本特開2015-005329號公報Patent Document 1: Japanese Patent Application Publication No. 2015-005329
[發明所欲解決的問題] 本發明的目的在於提供一種電解液，其能夠提高電化學裝置的性能。 [解決問題的技術手段][Problem to be solved by the invention] The object of the present invention is to provide an electrolyte that can improve the performance of an electrochemical device. [Technical means to solve the problem]
本發明的一態樣是一種電解液，其含有：由下述式(1)表示的化合物；及，具有碳-碳雙鍵之環狀碳酸酯； 式(1)中，R1 ～R3 各自獨立地表示烷基或氟原子，R4 表示伸烷基，R5 表示包含氮原子或硫原子之有機基團。One aspect of the present invention is an electrolyte solution containing: a compound represented by the following formula (1); and a cyclic carbonate having a carbon-carbon double bond; In the formula (1), R 1 to R 3 each independently represent an alkyl group or a fluorine atom, R 4 represents an alkylene group, and R 5 represents an organic group containing a nitrogen atom or a sulfur atom.
若藉由此電解液，則在一態樣中，作為電化學裝置的性能，能夠提高循環特性。此外，若藉由此電解液，則在另一態樣中，能夠降低電化學裝置放電時的直流電阻(放電DCR)。此外，若藉由此電解液，則在另一態樣中，能夠提高在高溫將電化學裝置保存後的容量維持率。此外，若藉由此電解液，則在另一態樣中，能夠抑制在高溫將電化學裝置保存後的體積增加。If this electrolyte is used, in one embodiment, as the performance of the electrochemical device, the cycle characteristics can be improved. In addition, if this electrolyte is used, in another embodiment, the DC resistance (discharge DCR) of the electrochemical device during discharge can be reduced. In addition, if this electrolyte is used, in another embodiment, the capacity retention rate after the electrochemical device is stored at a high temperature can be improved. In addition, if this electrolyte is used, in another embodiment, the volume increase after the electrochemical device is stored at a high temperature can be suppressed.
R1 ～R3 中的至少1個可為氟原子。At least one of R 1 to R 3 may be a fluorine atom.
由式(1)表示的化合物一分子中的矽原子數可為1個。The number of silicon atoms in one molecule of the compound represented by formula (1) may be one.
R5 可為包含氮原子之有機基團。R5 可為由下述式(2)表示的基團： 式(2)中，R6 和R7 各自獨立地表示氫原子或烷基，＊表示鍵結鍵(bond)。R 5 may be an organic group containing a nitrogen atom. R 5 may be a group represented by the following formula (2): In formula (2), R 6 and R 7 each independently represent a hydrogen atom or an alkyl group, and * represents a bond.
R5 可為包含硫原子之有機基團。R5 可以是由下述式(3)、式(4)及式(5)中的任一者表示的基團： 式(3)中，R8 表示烷基，＊表示鍵結鍵； 式(4)中，R9 表示烷基，＊表示鍵結鍵； 式(5)中，R10 表示烷基，＊表示鍵結鍵。R 5 may be an organic group containing a sulfur atom. R 5 may be a group represented by any one of the following formulas (3), (4) and (5): In formula (3), R 8 represents an alkyl group, and * represents a bond; In formula (4), R 9 represents an alkyl group, and * represents a bond; In formula (5), R 10 represents an alkyl group, and * represents a bond.
環狀碳酸酯可為碳酸伸乙烯酯。The cyclic carbonate may be vinyl carbonate.
由式(1)表示的化合物的含量和環狀碳酸酯的含量的合計量，以電解液總量作為基準計，可為10質量％以下。The total amount of the content of the compound represented by formula (1) and the content of the cyclic carbonate may be 10% by mass or less based on the total amount of the electrolyte solution.
本發明的另一態樣是一種電化學裝置，其具備：正極、負極、及上述電解液。Another aspect of the present invention is an electrochemical device, which comprises: a positive electrode, a negative electrode, and the above-mentioned electrolyte.
負極可含有碳材料。碳材料可含有石墨。負極可進一步含有下述材料，該材料包含選自由矽及錫所組成之群組中的至少1種元素。The negative electrode may contain a carbon material. The carbon material may contain graphite. The negative electrode may further contain a material containing at least one element selected from the group consisting of silicon and tin.
電化學裝置，可為非水電解液二次電池或電容器。 [功效]The electrochemical device may be a non-aqueous electrolyte secondary battery or a capacitor. [effect]
根據本發明，能夠提供一種電解液，其能夠提高電化學裝置的性能。According to the present invention, an electrolyte solution capable of improving the performance of an electrochemical device can be provided.
以下，一邊適當地參照圖式，一邊說明本發明的實施形態。但是，本發明並不受下述實施形態所限定。Hereinafter, embodiments of the present invention will be described with reference to the drawings as appropriate. However, the present invention is not limited to the embodiments described below.
第1圖是顯示一實施形態的電化學裝置的斜視圖。在本實施形態中，電化學裝置是非水電解液二次電池。如第1圖所示，非水電解液二次電池1，具備：電極群2，其由正極、負極及間隔件所構成；及，袋狀的電池外殼體3，其用以容置電極群2。於正極及負極分別設置有正極集電端子(tab)4及負極集電端子5。正極集電端子4及負極集電端子5分別以使正極及負極能夠與非水電解液二次電池1的外部電性連接的方式從電池外殼體3的內部突出至外部。電池外殼體3內填充有電解液(未圖示)。非水電解液二次電池1可為像上述這樣的亦即所謂的「疊層型」以外之形狀的電池(硬幣型、圓筒型、積層型等)。Fig. 1 is a perspective view showing an electrochemical device according to an embodiment. In this embodiment, the electrochemical device is a non-aqueous electrolyte secondary battery. As shown in Figure 1, the non-aqueous electrolyte secondary battery 1 includes: an electrode group 2, which is composed of a positive electrode, a negative electrode, and a separator; and a bag-shaped battery outer case 3 for accommodating the electrode group. 2. A positive current collection terminal (tab) 4 and a negative current collection terminal 5 are provided on the positive electrode and the negative electrode respectively. The positive electrode current collecting terminal 4 and the negative electrode current collecting terminal 5 respectively protrude from the inside of the battery outer case 3 to the outside in such a manner that the positive electrode and the negative electrode can be electrically connected to the outside of the non-aqueous electrolyte secondary battery 1 . The battery outer case 3 is filled with electrolyte (not shown). The non-aqueous electrolyte secondary battery 1 may be a battery (coin type, cylindrical type, laminated type, etc.) other than the so-called "laminated type" as described above.
電池外殼體3可為例如：由疊層薄膜所形成的容器。疊層薄膜可為例如一種積層薄膜，其是將下述依序積層而成：聚對苯二甲酸乙二酯(PET)薄膜等樹脂薄膜；鋁、銅、不鏽鋼等的金屬箔；及，聚丙烯等的密封劑層。The battery outer case 3 may be, for example, a container formed of laminated films. The laminated film may be, for example, a laminated film in which the following are laminated in this order: resin films such as polyethylene terephthalate (PET) films; metal foils such as aluminum, copper, stainless steel, etc.; and polyethylene terephthalate (PET) films. A layer of sealant such as acrylic.
第2圖是顯示第1圖所示的非水電解液二次電池1的電極群2的一實施形態的分解斜視圖。如第2圖所示，電極群2依序具備：正極6、間隔件7、及負極8。正極6及負極8是以使正極合劑層10側及負極合劑層12側的面分別與間隔件7相對向的方式配置。FIG. 2 is an exploded perspective view showing an embodiment of the electrode group 2 of the non-aqueous electrolyte secondary battery 1 shown in FIG. 1 . As shown in FIG. 2 , the electrode group 2 includes a positive electrode 6 , a separator 7 , and a negative electrode 8 in this order. The positive electrode 6 and the negative electrode 8 are arranged so that the surfaces on the positive electrode mixture layer 10 side and the negative electrode mixture layer 12 side face the separator 7 , respectively.
正極6具備正極集電體9及正極合劑層10，該正極合劑層10設置於正極集電體9上。於正極集電體9設置有正極集電端子4。The positive electrode 6 includes a positive electrode collector 9 and a positive electrode mixture layer 10, and the positive electrode mixture layer 10 is provided on the positive electrode collector 9. The positive electrode collector terminal 4 is provided on the positive electrode collector 9.
正極集電體9是由例如下述所形成：鋁、鈦、不鏽鋼、鎳、碳極(baked carbon)、導電性高分子、導電性玻璃等。正極集電體9可為了提高黏著性、導電性及耐氧化性的目的而經以碳、鎳、鈦、銀等來對鋁、銅等的表面實施處理。從電極強度及能量密度的觀點來看，正極集電體9的厚度為例如1～50 μm。The positive electrode collector 9 is formed of, for example, aluminum, titanium, stainless steel, nickel, baked carbon, conductive polymer, conductive glass, etc. The positive electrode collector 9 may be formed by treating the surface of aluminum, copper, etc. with carbon, nickel, titanium, silver, etc. in order to improve adhesion, conductivity, and oxidation resistance. From the perspective of electrode strength and energy density, the thickness of the positive electrode collector 9 is, for example, 1 to 50 μm.
一實施形態中，正極合劑層10含有：正極活性物質、導電劑、及黏合劑。正極合劑層10的厚度為例如20～200 μm。In one embodiment, the positive electrode mixture layer 10 contains: a positive electrode active material, a conductive agent, and a binder. The thickness of the positive electrode mixture layer 10 is, for example, 20 to 200 μm.
正極活性物質可為例如鋰氧化物。作為鋰氧化物，可舉例如：Lix CoO2 、Lix NiO2 、Lix MnO2 、Lix Coy Ni1 － y O2 、Lix Coy M1 － y Oz 、Lix Ni1 － y My Oz 、Lix Mn2 O4 、及Lix Mn2 － y My O4 (各式中，M表示選自由Na、Mg、Sc、Y、Mn、Fe、Co、Cu、Zn、Al、Cr、Pb、Sb、V及B所組成之群組中的至少1種元素(其中，M為與各式中的其它元素不同之元素)；x＝0～1.2，y＝0～0.9，z＝2.0～2.3)。Lix Ni1 － y My Oz 表示的鋰氧化物可為Lix Ni1 － (y1 ＋ y2) Coy1 Mny2 Oz (其中，x及z與上述相同，y1＝0～0.9，y2＝0～0.9，且y1＋y2＝0～0.9)，可為例如：LiNi1/3 Co1/3 Mn1/3 O2 、LiNi0.5 Co0.2 Mn0.3 O2 、LiNi0.6 Co0.2 Mn0.2 O2 、LiNi0.8 Co0.1 Mn0.1 O2 。Lix Ni1 － y My Oz 表示的鋰氧化物可為Lix Ni1 － (y3 ＋ y4) Coy3 Aly4 Oz (其中，x及z與上述相同，y3＝0～0.9，y4＝0～0.9，且y3＋y4＝0～0.9)，可為例如：LiNi0.8 Co0.15 Al0.05 O2 。The positive active material may be, for example, lithium oxide. Examples of the lithium oxide include Li x CoO 2 , Li x NiO 2 , Li x MnO 2 , Li x Co y Ni 1 - y O 2 , Li x Co y M 1 - y O z , and Li x Ni 1 - y M y O z , Li x Mn 2 O 4 , and Li x Mn 2 - y M y O 4 (in each formula, M means selected from Na, Mg, Sc, Y, Mn, Fe, Co, Cu, At least one element from the group consisting of Zn, Al, Cr, Pb, Sb, V and B (where M is an element different from other elements in each formula); x=0~1.2, y=0 ~0.9, z=2.0~2.3). The lithium oxide represented by Li x Ni 1 - y M y O z can be Li x Ni 1 - (y1 + y2) Co y1 Mn y2 O z (where x and z are the same as above, y1=0~0.9, y2 =0~0.9, and y1+y2=0~0.9), which can be, for example: LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 . The lithium oxide represented by Li x Ni 1 - y M y O z can be Li x Ni 1 - (y3 + y4) Co y3 Al y4 O z (where x and z are the same as above, y3=0~0.9, y4 =0~0.9, and y3+y4=0~0.9), for example: LiNi 0.8 Co 0.15 Al 0.05 O 2 .
正極活性物質可為例如鋰的磷酸鹽。作為鋰的磷酸鹽，可舉例如：磷酸錳鋰(LiMnPO4 )、磷酸鐵鋰(LiFePO4 )、磷酸鈷鋰(LiCoPO4 )、及磷酸釩鋰(Li3 V2 (PO4 )3 )。The positive electrode active material may be, for example, lithium phosphate, such as lithium manganese phosphate (LiMnPO 4 ), lithium iron phosphate (LiFePO 4 ), lithium cobalt phosphate (LiCoPO 4 ), and lithium vanadium phosphate (Li 3 V 2 (PO 4 ) 3 ).
以正極合劑層總量作為基準計，正極活性物質的含量可為80質量％以上、或85質量％以上，並且可為99質量％以下。The content of the positive electrode active material may be 80% by mass or more, or 85% by mass or more, and may be 99% by mass or less, based on the total amount of the positive electrode agent layer.
導電劑可為：乙炔黑、科琴黑(Ketjen black)等碳黑；石墨、石墨烯、奈米碳管等碳材料。以正極合劑層總量作為基準計，導電劑的含量可為例如：0.01質量％以上、0.1質量％以上、或1質量％以上，並且可為50質量％以下、30質量％以下、或15質量％以下。The conductive agent can be: carbon black such as acetylene black and Ketjen black; carbon materials such as graphite, graphene, and carbon nanotubes. Based on the total amount of the positive electrode mixture layer, the content of the conductive agent may be, for example, 0.01 mass% or more, 0.1 mass% or more, or 1 mass% or more, and may be 50 mass% or less, 30 mass% or less, or 15 mass%. %the following.
黏合劑可舉例如：聚乙烯、聚丙烯、聚對苯二甲酸乙二酯、聚甲基丙烯酸甲酯、聚醯亞胺、芳香族聚醯胺、纖維素、硝基纖維素等樹脂；SBR(苯乙烯-丁二烯橡膠)、NBR(丙烯腈-丁二烯橡膠)、氟橡膠、異戊二烯橡膠、丁二烯橡膠、乙烯-丙烯橡膠等橡膠；苯乙烯-丁二烯-苯乙烯嵌段共聚物或其氫化物、EPDM(乙烯-丙烯-二烯三元共聚物)、苯乙烯-乙烯-丁二烯-乙烯共聚物、苯乙烯-異戊二烯-苯乙烯嵌段共聚物或其氫化物等熱塑性彈性體；間規1,2-聚丁二烯(syndiotactic 1,2-polybutadiene)、聚乙酸乙烯酯、乙烯-乙酸乙烯酯共聚物、丙烯-α-烯烴共聚物等軟質樹脂；聚偏二氟乙烯(PVDF)、聚四氟乙烯、氟化聚偏二氟乙烯、聚四氟乙烯-乙烯共聚物、聚四氟乙烯-偏二氟乙烯共聚物等含氟樹脂；具有含腈基單體來作為單體單元的樹脂；具有鹼金屬離子(例如鋰離子)的離子傳導性的高分子組成物等。Examples of the adhesive include: resins such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polyimide, aromatic polyamide, cellulose, nitrocellulose, etc.; rubbers such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), fluororubber, isoprene rubber, butadiene rubber, ethylene-propylene rubber, etc.; thermoplastic elastomers such as styrene-butadiene-styrene block copolymer or its hydrogenated product, EPDM (ethylene-propylene-diene terpolymer), styrene-ethylene-butadiene-ethylene copolymer, styrene-isoprene-styrene block copolymer or its hydrogenated product; syndiotactic 1,2-polybutadiene (syndiotactic 1,2-polybutadiene), polyvinyl acetate, ethylene-vinyl acetate copolymer, propylene-α-olefin copolymer and other soft resins; polyvinylidene fluoride (PVDF), polytetrafluoroethylene, fluorinated polyvinylidene fluoride, polytetrafluoroethylene-ethylene copolymer, polytetrafluoroethylene-vinylidene fluoride copolymer and other fluorine-containing resins; resins having nitrile-containing monomers as monomer units; polymer compositions having ion conductivity of alkaline metal ions (such as lithium ions), etc.
以正極合劑層總量作為基準計，黏合劑的含量例如可為0.1質量％以上、1質量％以上、或1.5質量％以上，並且可為30質量％以下、20質量％以下、或10質量％以下。Based on the total amount of the positive electrode mixture layer, the content of the binder may be, for example, 0.1 mass% or more, 1 mass% or more, or 1.5 mass% or more, and may be 30 mass% or less, 20 mass% or less, or 10 mass%. the following.
間隔件7只要將正極6及負極8之間電性絕緣另一方面使離子穿透，且具備對正極6側的氧化性及負極8側的還原性的耐性，則無特別限制。作為這樣的間隔件7的材料(材質)，可舉例如：樹脂、無機物等。The separator 7 is not particularly limited as long as it electrically insulates the positive electrode 6 and the negative electrode 8 while allowing ions to penetrate it, and has resistance to oxidation on the positive electrode 6 side and reduction on the negative electrode 8 side. Examples of the material (material) of the spacer 7 include resin, inorganic substances, and the like.
作為樹脂，可舉例如：烯烴系聚合物、氟系聚合物、纖維素系聚合物、聚醯亞胺、耐綸等。從對電解液為穩定且保液性優異的觀點來看，間隔件7較佳為：由聚乙烯、聚丙烯等聚烯烴所形成的多孔質薄片或不織布。Examples of the resin include olefin polymers, fluorine polymers, cellulose polymers, polyimide, and polyester. From the perspective of stability and excellent liquid retention for the electrolyte, the spacer 7 is preferably a porous sheet or nonwoven fabric made of polyolefins such as polyethylene and polypropylene.
作為無機物，可舉例如：氧化鋁、二氧化矽等氧化物；氮化鋁、氮化矽等氮化物；硫酸鋇、硫酸鈣等硫酸鹽。間隔件7可為例如：使纖維狀或粒子狀的無機物附著在薄膜狀基材而成的間隔件，該薄膜狀基材為不織布、織布、微多孔性薄膜等。Examples of inorganic substances include oxides such as aluminum oxide and silicon dioxide; nitrides such as aluminum nitride and silicon nitride; and sulfates such as barium sulfate and calcium sulfate. The spacer 7 may be, for example, a spacer in which a fibrous or particulate inorganic substance is adhered to a film-like base material, and the film-like base material may be a nonwoven fabric, a woven fabric, a microporous film, or the like.
負極8具備負極集電體11及負極合劑層12，該負極合劑層12設置於負極集電體11上。於負極集電體11設置有負極集電端子5。The negative electrode 8 includes a negative electrode current collector 11 and a negative electrode mixture layer 12. The negative electrode mixture layer 12 is provided on the negative electrode current collector 11. The negative electrode current collector 11 is provided with a negative electrode current collecting terminal 5.
負極集電體11是由下述所形成：銅、不鏽鋼、鎳、鋁、鈦、碳極(baked carbon)、導電性高分子、導電性玻璃、鋁-鎘合金等。負極集電體11可為了提高黏著性、導電性、耐還原性的目的而經以碳、鎳、鈦、銀等來對鋁、銅等的表面實施處理。從電極強度及能量密度的觀點來看，負極集電體11的厚度為例如1～50 μm。The negative electrode current collector 11 is made of copper, stainless steel, nickel, aluminum, titanium, baked carbon, conductive polymer, conductive glass, aluminum-cadmium alloy, etc. The negative electrode current collector 11 may have the surface of aluminum, copper, etc. treated with carbon, nickel, titanium, silver, etc. for the purpose of improving adhesion, conductivity, and reduction resistance. From the viewpoint of electrode strength and energy density, the thickness of the negative electrode current collector 11 is, for example, 1 to 50 μm.
負極合劑層12含有例如：負極活性物質、及黏合劑。The negative electrode binder layer 12 contains, for example, a negative electrode active material and a binder.
負極活性物質只要為能夠吸附及放出鋰離子的物質，則無特別限制。作為負極活性物質，可舉例如：碳材料；金屬複合氧化物；錫、鍺、矽等的第四族元素的氧化物或氮化物；鋰的單體；鋰鋁合金等鋰合金；Sn、Si等能夠與鋰形成合金的金屬等。從安全性的觀點來看，負極活性物質較佳是選自由碳材料及金屬複合氧化物所組成之群組中的至少1種。負極活性物質可為此等之中的單獨1種或2種以上的混合物。負極活性物質的形狀可為例如粒子狀。There are no particular restrictions on the negative electrode active material as long as it is a material that can adsorb and release lithium ions. Examples of the negative electrode active material include: carbon materials; metal composite oxides; oxides or nitrides of Group IV elements such as tin, germanium, and silicon; lithium monomers; lithium alloys such as lithium aluminum alloys; metals such as Sn and Si that can form alloys with lithium, etc. From the perspective of safety, the negative electrode active material is preferably at least one selected from the group consisting of carbon materials and metal composite oxides. The negative electrode active material may be a single type or a mixture of two or more of these. The shape of the negative electrode active material may be, for example, particulate.
作為碳材料，可舉例如：非晶型碳材料、天然石墨、於天然石墨形成非晶型碳材料而成的複合碳材料、人造石墨(將環氧樹脂、酚樹脂等樹脂原料、或由石油、煤等所獲得的瀝青系原料煅燒而得的石墨)等。從高電流密度充放電特性的觀點來看，金屬複合氧化物較佳是含有鈦及鋰之中的任一種或兩種，更佳是含有鋰。Examples of the carbon material include amorphous carbon materials, natural graphite, composite carbon materials in which natural graphite is made into an amorphous carbon material, artificial graphite (resin raw materials such as epoxy resin and phenol resin, or petroleum). Graphite obtained by calcining pitch-based raw materials obtained from coal, etc.), etc. From the viewpoint of high current density charge and discharge characteristics, the metal composite oxide preferably contains one or both of titanium and lithium, and more preferably contains lithium.
負極活性物質中，碳材料的導電性高且低溫特性及循環穩定性特別優異。從高容量化的觀點來看，碳材料中，以石墨為佳。石墨中，較佳是X射線廣角繞射法的碳網面層間(d002)未達0.34 nm，更佳為0.3354 nm以上且0.337 nm以下。有時將滿足這樣的條件的碳材料稱為準異向性碳(quasi-anisotropic carbon)。Among negative electrode active materials, carbon materials have high electrical conductivity and are particularly excellent in low-temperature characteristics and cycle stability. From the viewpoint of increasing the capacity, graphite is preferred among carbon materials. Among graphite, it is preferable that the interlayer (d002) of the carbon mesh surface measured by X-ray wide-angle diffraction method is less than 0.34 nm, and more preferably it is 0.3354 nm or more and 0.337 nm or less. A carbon material that satisfies such conditions is sometimes called quasi-anisotropic carbon.
負極活性物質中，可進一步含有下述材料，該材料包含選自由矽及錫所組成之群組中的至少1種元素。包含選自由矽及錫所組成之群組中的至少1種元素之材料，可為：矽或錫的單體、包含選自由矽及錫所組成之群組中的至少1種元素之化合物。該化合物可為包含選自由矽及錫所組成之群組中的至少1種元素之合金，例如為一種合金，其除了矽及錫以外還包含選自由鎳、銅、鐵、鈷、錳、鋅、銦、銀、鈦、鍺、鉍、銻及鉻所組成之群組中的至少1種。包含選自由矽及錫所組成之群組中的至少1種元素之化合物，可為氧化物、氮化物、或碳化物，具體而言可為例如：SiO、SiO2 、LiSiO等矽氧化物；Si3 N4 、Si2 N2 O等矽氮化物；SiC等矽碳化物；SnO、SnO2 、LiSnO等錫氧化物等。The negative electrode active material may further contain a material containing at least one element selected from the group consisting of silicon and tin. The material containing at least one element selected from the group consisting of silicon and tin may be a monomer of silicon or tin, or a compound containing at least one element selected from the group consisting of silicon and tin. The compound may be an alloy containing at least one element selected from the group consisting of silicon and tin. For example, it may be an alloy containing, in addition to silicon and tin, an alloy selected from the group consisting of nickel, copper, iron, cobalt, manganese, and zinc. , at least one of the group consisting of indium, silver, titanium, germanium, bismuth, antimony and chromium. The compound containing at least one element selected from the group consisting of silicon and tin can be an oxide, a nitride, or a carbide. Specifically, it can be a silicon oxide such as SiO, SiO 2 , LiSiO, etc.; Silicon nitrides such as Si 3 N 4 and Si 2 N 2 O; silicon carbides such as SiC; tin oxides such as SnO, SnO 2 and LiSnO.
從更加提高低溫輸入特性等電化學裝置的性能的觀點來看，負極8較佳是包含碳材料，更佳是包含石墨，進一步更佳是包含碳材料與選自由矽及錫所組成之群組中的至少1種元素之材料之混合物，特佳是包含石墨與矽氧化物的混合物，來作為負極活性物質。該混合物中，以該混合物總量作為基準計，碳材料(石墨)相對於選自由矽及錫所組成之群組中的至少1種元素之材料(矽氧化物)的含量可為1質量％以上、或3質量％以上，並且可為30質量％以下。From the viewpoint of further improving the performance of the electrochemical device such as low-temperature input characteristics, the negative electrode 8 preferably comprises a carbon material, more preferably graphite, and further preferably a mixture of a carbon material and a material of at least one element selected from the group consisting of silicon and tin, and particularly preferably a mixture of graphite and silicon oxide, as a negative electrode active material. In the mixture, the content of the carbon material (graphite) relative to the material of at least one element selected from the group consisting of silicon and tin (silicon oxide) can be 1% by mass or more, or 3% by mass or more, and can be 30% by mass or less, based on the total amount of the mixture.
以負極合劑總量作為基準計，負極活性物質的含量可為80質量％以上、或85質量％以上，並且可為99質量％以下。The content of the negative electrode active substance may be 80% by mass or more, or 85% by mass or more, and may be 99% by mass or less, based on the total amount of the negative electrode compound.
黏合劑及其含量，可與上述正極合劑層中的黏合劑及其含量相同。The binder and its content may be the same as the binder and its content in the above-mentioned positive electrode binder layer.
負極合劑層12可為了調節黏度而含有增黏劑。增黏劑無特別限制，可為：羧甲基纖維素、甲基纖維素、羥甲基纖維素、乙基纖維素、聚乙烯醇、氧化澱粉、磷酸化澱粉、酪蛋白、此等的鹽等。增黏劑可為此等之中的單獨1種或2種以上的混合物。The negative electrode agent layer 12 may contain a thickener for adjusting the viscosity. The thickener is not particularly limited and may be carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphated starch, casein, salts thereof, etc. The thickener may be a single one or a mixture of two or more of these.
當負極合劑層12包含增黏劑時，其含量無特別限制，從負極合劑層的塗佈性的觀點來看，以負極合劑層總量作為基準計，增黏劑的含量可為0.1質量％以上，以0.2質量％以上為佳，以0.5質量％以上較佳。從抑制電池容量降低或負極活性物質間的電阻上升的觀點來看，以負極合劑層總量作為基準計，增黏劑的含量可為5質量％以下，以3質量％以下為佳，以2質量％以下較佳。When the negative electrode compound layer 12 contains a thickener, its content is not particularly limited. From the perspective of the coating properties of the negative electrode compound layer, the content of the thickener can be 0.1% by mass or more, preferably 0.2% by mass or more, and more preferably 0.5% by mass or more, based on the total amount of the negative electrode compound layer. From the perspective of suppressing the reduction of battery capacity or the increase of resistance between negative electrode active materials, the content of the thickener can be 5% by mass or less, preferably 3% by mass or less, and more preferably 2% by mass or less, based on the total amount of the negative electrode compound layer.
一實施形態中，電解液含有：由下述式(1)表示的化合物、具有碳-碳雙鍵之環狀碳酸酯(以下，亦僅稱為「環狀碳酸酯」)、電解質鹽、及非水溶劑。 式(1)中，R1 ～R3 各自獨立地表示烷基或氟原子，R4 表示伸烷基，R5 表示包含氮原子或硫原子之有機基團。In one embodiment, the electrolyte solution contains: a compound represented by the following formula (1), a cyclic carbonate having a carbon-carbon double bond (hereinafter, also simply referred to as "cyclic carbonate"), an electrolyte salt, and a non-aqueous solvent. In formula (1), R 1 to R 3 each independently represent an alkyl group or a fluorine atom, R 4 represents an alkylene group, and R 5 represents an organic group containing a nitrogen atom or a sulfur atom.
由R1 ～R3 表示的烷基的碳數可為1以上，並且可為3以下。R1 ～R3 可為甲基、乙基、或丙基，並且可為直鏈狀或分枝狀。R1 ～R3 中的至少1個以氟原子為佳。R1 ～R3 之中的任1個可為氟原子，R1 ～R3 之中的任2個可為氟原子，R1 ～R3 全部可皆為氟原子。The number of carbon atoms in the alkyl group represented by R 1 to R 3 may be 1 or more and may be 3 or less. R 1 to R 3 may be methyl, ethyl, or propyl, and may be linear or branched. At least one of R 1 to R 3 is preferably a fluorine atom. Any one of R 1 to R 3 may be a fluorine atom, any two of R 1 to R 3 may be a fluorine atom, and all of R 1 to R 3 may be a fluorine atom.
由R4 表示的伸烷基的碳數可為1以上或2以上，並且可為5以下或4以下。由R4 表示的伸烷基可為亞甲基、伸乙基、伸丙基、伸丁基、或伸戊基，並且可為直鏈狀或分枝狀。The carbon number of the alkylene group represented by R4 may be 1 or more or 2 or more, and may be 5 or less or 4 or less. The alkylene group represented by R4 may be a methylene group, an ethylene group, a propylene group, a butylene group, or a pentylene group, and may be linear or branched.
一實施形態中，由式(1)表示的化合物一分子中的矽原子數為1個。換言之，一實施形態中，由R5 表示的有機基團不含矽原子。In one embodiment, the number of silicon atoms in one molecule of the compound represented by formula (1) is 1. In other words, in one embodiment, the organic group represented by R 5 does not contain a silicon atom.
一實施形態中，R5 是包含氮原子之有機基團，從能夠更加提高電化學裝置的性能的觀點來看，R5 較佳為由下述式(2)表示的基團： 式(2)中，R6 和R7 各自獨立地表示氫原子或烷基，由R6 或R7 表示的烷基可與上述的由R1 ～R3 表示的烷基相同，＊表示鍵結鍵。In one embodiment, R 5 is an organic group containing a nitrogen atom. From the viewpoint of further improving the performance of the electrochemical device, R 5 is preferably a group represented by the following formula (2): In the formula (2), R 6 and R 7 each independently represent a hydrogen atom or an alkyl group. The alkyl group represented by R 6 or R 7 may be the same as the above-mentioned alkyl group represented by R 1 to R 3 . * represents a bond. Knot.
另一實施形態中，R5 是包含硫原子之有機基團，從能夠更加提高電化學裝置的性能的觀點來看，較佳是由下述式(3)、式(4)及式(5)中的任一者表示的基團： 式(3)中，R8 表示烷基，烷基可與上述的由R1 ～R3 表示的烷基相同，＊表示鍵結鍵； 式(4)中，R9 表示烷基，烷基可與上述的由R1 ～R3 表示的烷基相同，＊表示鍵結鍵； 式(5)中，R10 表示烷基，烷基可與上述的由R1 ～R3 表示的烷基相同，＊表示鍵結鍵。In another embodiment, R 5 is an organic group containing a sulfur atom. From the viewpoint of further improving the performance of the electrochemical device, R 5 is preferably represented by the following formula (3), formula (4) and formula (5). ) represents a group represented by any one of: In formula (3), R 8 represents an alkyl group, and the alkyl group can be the same as the alkyl group represented by R 1 to R 3 mentioned above, and * represents a bond; In formula (4), R 9 represents an alkyl group, and the alkyl group can be the same as the above-mentioned alkyl group represented by R 1 to R 3 , and * represents a bond; In formula (5), R 10 represents an alkyl group, and the alkyl group may be the same as the alkyl group represented by R 1 to R 3 described above, and * represents a bond.
從能夠更加提高電化學裝置的性能的觀點來看，以電解液總量作為基準計，由式(1)表示的化合物的含量較佳為：0.001質量％以上、0.005質量％以上、0.01質量％以上、0.05質量％以上、或0.1質量％以上，且8質量％以下、5質量％以下、3質量％以下、2質量％以下、或1質量％以下。From the viewpoint of further improving the performance of the electrochemical device, the content of the compound represented by formula (1) is preferably: 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% based on the total amount of the electrolyte solution. or more, 0.05 mass% or more, or 0.1 mass% or more, and 8 mass% or less, 5 mass% or less, 3 mass% or less, 2 mass% or less, or 1 mass% or less.
具有碳-碳雙鍵之環狀碳酸酯(cyclic carbonate)為一種具有碳-碳雙鍵之環狀碳酸酯(cyclic carbonic ester)。一實施形態中，環狀碳酸酯中，用以構成環的兩個碳可形成雙鍵。環狀碳酸酯可為例如：碳酸伸乙烯酯、碳酸甲基伸乙烯酯、碳酸二甲基伸乙烯酯(碳酸4,5-二甲基伸乙烯酯)、碳酸乙基伸乙烯酯、碳酸二乙基伸乙烯酯(碳酸4,5-二乙基伸乙烯酯)等，從能夠更加提高電化學裝置的性能的觀點來看，以碳酸伸乙烯酯為佳。A cyclic carbonate having a carbon-carbon double bond is a cyclic carbonic ester having a carbon-carbon double bond. In one embodiment, in the cyclic carbonate, the two carbons constituting the ring may form a double bond. The cyclic carbonate may be, for example: vinyl carbonate, methyl vinyl carbonate, dimethyl vinyl carbonate (4,5-dimethyl vinyl carbonate), ethyl vinyl carbonate, diethyl carbonate Vinyl carbonate (4,5-diethyl vinyl carbonate) and the like, vinyl carbonate is preferred from the viewpoint that the performance of the electrochemical device can be further improved.
從能夠更加提高電化學裝置的性能的觀點來看，以電解液總量作為基準計，環狀碳酸酯的含量較佳是0.001質量％以上、0.005質量％以上、0.01質量％以上、0.05質量％以上、或0.1質量％以上，且較佳是5質量％以下、3質量％以下、或2質量％以下。From the viewpoint of further improving the performance of the electrochemical device, the content of the cyclic carbonate is preferably 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, or 0.05 mass% based on the total amount of the electrolyte solution. or more, or 0.1 mass% or more, and preferably 5 mass% or less, 3 mass% or less, or 2 mass% or less.
從能夠更加提高電化學裝置的性能的觀點來看，以電解液總量作為基準計，由式(1)表示的化合物的含量和環狀碳酸酯的含量的合計量，較佳是0.001質量％以上、0.005質量％以上、0.01質量％以上、0.1質量％以上、0.5質量％以上、或1質量％以上，且較佳是10質量％以下、7質量％以下、5質量％以下、3質量％以下、或2質量％以下。From the viewpoint of further improving the performance of the electrochemical device, the total amount of the content of the compound represented by formula (1) and the content of the cyclic carbonate is preferably 0.001% by mass based on the total amount of the electrolyte solution. or more, 0.005 mass% or more, 0.01 mass% or more, 0.1 mass% or more, 0.5 mass% or more, or 1 mass% or more, and preferably 10 mass% or less, 7 mass% or less, 5 mass% or less, 3 mass% or less, or 2 mass% or less.
從能夠更加提高電化學裝置的性能的觀點來看，由式(1)表示的化合物的含量相對於環狀碳酸酯的含量的質量比(由式(1)表示的化合物的含量/環狀碳酸酯的含量)，較佳是0.01以上、0.05以上、0.1以上、0.2以上、或0.25以上，並且，較佳是500以下、100以下、50以下、20以下、10以下、5以下、3以下、或1以下。From the viewpoint of being able to further improve the performance of the electrochemical device, the mass ratio of the content of the compound represented by formula (1) to the content of the cyclic carbonate (content of the compound represented by formula (1)/content of the cyclic carbonate) is preferably greater than 0.01, greater than 0.05, greater than 0.1, greater than 0.2, or greater than 0.25, and is preferably less than 500, less than 100, less than 50, less than 20, less than 10, less than 5, less than 3, or less than 1.
電解質鹽可為例如鋰鹽。鋰鹽可為例如選自由下述所組成之群組中的至少1種：LiPF6 、LiBF4 、LiClO4 、LiB(C6 H5 )4 、LiCH3 SO3 、CF3 SO2 OLi、LiN(SO2 F)2 (Li[FSI]、雙(氟磺醯)亞胺鋰)、LiN(SO2 CF3 )2 (Li[TFSI]、雙(三氟甲磺醯)亞胺鋰)、及LiN(SO2 CF2 CF3 )2 。從對溶劑的溶解性、二次電池的充放電特性、輸出特性、循環特性等更優異的觀點來看，鋰鹽較佳是包含LiPF6 。The electrolyte salt may be, for example, a lithium salt. The lithium salt may be, for example, at least one selected from the group consisting of: LiPF 6 , LiBF 4 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiCH 3 SO 3 , CF 3 SO 2 OLi, LiN (SO 2 F) 2 (Li[FSI], lithium bis(fluoromethanesulfonyl)imide), LiN(SO 2 CF 3 ) 2 (Li[TFSI], lithium bis(trifluoromethanesulfonyl)imide), and LiN(SO 2 CF 2 CF 3 ) 2 . The lithium salt preferably contains LiPF 6 from the viewpoint of superior solubility in solvents, charge and discharge characteristics, output characteristics, and cycle characteristics of the secondary battery.
從充放電特性優異的觀點來看，以非水溶劑總量作為基準計，電解質鹽的濃度以0.5 mol/L以上為佳，以0.7 mol/L以上較佳，以0.8 mol/L以上更佳，並且，以1.5 mol/L以下為佳，以1.3 mol/L以下較佳，以1.2 mol/L以下更佳。From the viewpoint of excellent charge and discharge characteristics, the concentration of the electrolyte salt is preferably 0.5 mol/L or more, more preferably 0.7 mol/L or more, and more preferably 0.8 mol/L or more based on the total amount of non-aqueous solvent. , and it is preferably 1.5 mol/L or less, more preferably 1.3 mol/L or less, and more preferably 1.2 mol/L or less.
非水溶劑可為例如：碳酸伸乙酯、碳酸伸丙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、γ-丁內酯、乙腈、1,2-二甲氧基乙烷、二甲氧基甲烷、四氫呋喃、二氧雜環戊烷(dioxolane)、二氯甲烷、乙酸甲酯等。非水溶劑可為此等之中的單獨1種或2種以上的混合物，以2種以上的混合物為佳。Non-aqueous solvents may be, for example: ethyl carbonate, propyl carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, γ-butyrolactone, acetonitrile, 1,2-dimethoxyethane , dimethoxymethane, tetrahydrofuran, dioxolane, methylene chloride, methyl acetate, etc. The non-aqueous solvent may be a single type of these or a mixture of two or more types, preferably a mixture of two or more types.
電解液可進一步含有由式(1)表示的化合物、具有碳-碳雙鍵之環狀碳酸酯、電解質鹽及非水溶劑以外的其它材料。其它材料可為例如：含氟環狀碳酸酯；由式(1)表示的化合物以外的含有氮原子、硫原子、或是氮原子及硫原子之化合物；環狀羧酸酯等。The electrolyte solution may further contain materials other than the compound represented by formula (1), a cyclic carbonate having a carbon-carbon double bond, an electrolyte salt, and a non-aqueous solvent. Other materials may be, for example: fluorine-containing cyclic carbonate; compounds other than the compound represented by formula (1) containing nitrogen atoms, sulfur atoms, or nitrogen atoms and sulfur atoms; cyclic carboxylic acid esters, etc.
含氟環狀碳酸酯可為例如：4-氟-1,3-二氧雜環戊烷-2-酮(碳酸氟伸乙酯；FEC)、碳酸1,2-二氟伸乙酯、碳酸1,1-二氟伸乙酯、碳酸1,1,2-三氟伸乙酯、碳酸1,1,2,2-四氟伸乙酯等，以4-氟-1,3-二氧雜環戊烷-2-酮(碳酸氟伸乙酯；FEC)為佳。由式(1)表示的化合物以外的含有氮原子的化合物可為例如：琥珀腈等腈類化合物。由式(1)表示的化合物以外的含有硫原子之化合物，可為例如：1,3-丙烷磺內酯、1-丙烯基-1,3-磺內酯等環狀磺酸酯化合物。The fluorine-containing cyclic carbonate may be, for example, 4-fluoro-1,3-dioxacyclopentane-2-one (fluoroethyl carbonate; FEC), 1,2-difluoroethyl carbonate, 1,1-difluoroethyl carbonate, 1,1,2-trifluoroethyl carbonate, 1,1,2,2-tetrafluoroethyl carbonate, etc., preferably 4-fluoro-1,3-dioxacyclopentane-2-one (fluoroethyl carbonate; FEC). The nitrogen-containing compound other than the compound represented by formula (1) may be, for example, a nitrile compound such as succinonitrile. The sulfur-containing compound other than the compound represented by formula (1) may be, for example, a cyclic sulfonate compound such as 1,3-propane sultone and 1-propenyl-1,3-sultone.
本發明人對具有各種結構及官能基之化合物進行研究後，結果明確得知下述事實：藉由將由上述式(1)表示的化合物及具有碳-碳雙鍵之環狀碳酸酯應用於電解液，即能夠提高電化學裝置的性能。本發明人推測藉由將由式(1)表示的化合物及具有碳-碳雙鍵之環狀碳酸酯用於電解液來產生的作用效果是如下所述。換言之，我們認為：由式(1)表示的化合物及具有碳-碳雙鍵之環狀碳酸酯，會分別對在鋰離子二次電池內最容易顯現效果的位置產生作用，而例如有助於在正極或負極形成穩定的被膜、或使電解液穩定化。結果會提高像非水電解液二次電池1這樣的電化學裝置的性能。例如：在一態樣中，藉由使用此電解液，即能夠提高電化學裝置的循環特性。在另一態樣中，藉由使用此電解液，即能夠降低電化學裝置的放電DCR。在另一態樣中，藉由使用此電解液，即能夠提高在高溫將電化學裝置保存後的容量維持率。在另一態樣中，能夠抑制在高溫將電化學裝置保存後的體積增加。As a result of research on compounds having various structures and functional groups, the present inventors clearly found out that by applying the compound represented by the above formula (1) and the cyclic carbonate having a carbon-carbon double bond to electrolysis liquid, which can improve the performance of electrochemical devices. The present inventors speculate that the effects produced by using the compound represented by formula (1) and the cyclic carbonate having a carbon-carbon double bond in the electrolyte are as follows. In other words, we believe that the compound represented by formula (1) and the cyclic carbonate having a carbon-carbon double bond will respectively act on the positions where the effect is most likely to appear in the lithium ion secondary battery, and, for example, contribute to Form a stable coating on the positive electrode or negative electrode, or stabilize the electrolyte. As a result, the performance of electrochemical devices such as the non-aqueous electrolyte secondary battery 1 will be improved. For example, in one aspect, by using the electrolyte, the cycle characteristics of the electrochemical device can be improved. In another aspect, by using the electrolyte, the discharge DCR of the electrochemical device can be reduced. In another aspect, by using the electrolyte, the capacity retention rate of the electrochemical device after being stored at high temperature can be improved. In another aspect, an increase in the volume of the electrochemical device after being stored at high temperature can be suppressed.
然後，說明非水電解液二次電池1的製造方法。非水電解液二次電池1的製造方法具備：第1步驟，其獲得正極6；第2步驟，其獲得負極8；第3步驟，其將電極群2容置於電池外殼體3中；及，第4步驟，其將電解液注入電池外殼體3中。第1～第4步驟的順序為任意順序。Next, the manufacturing method of the non-aqueous electrolyte secondary battery 1 is described. The manufacturing method of the non-aqueous electrolyte secondary battery 1 comprises: a first step of obtaining a positive electrode 6; a second step of obtaining a negative electrode 8; a third step of placing an electrode group 2 in a battery casing 3; and a fourth step of injecting an electrolyte into the battery casing 3. The order of the first to fourth steps is arbitrary.
第1步驟中，使用揉合機、分散機等來使正極合劑層10中所使用的材料分散在分散介質中而獲得漿液狀的正極合劑後，藉由刮刀(doctor blade)法、浸漬法、噴霧法等來將此正極合劑塗佈於正極集電體9上，然後使分散介質揮發，藉此獲得正極6。使分散介質揮發後，可因應需要來設置藉由輥壓來進行的壓縮成型步驟。正極合劑層10可藉由進行複數次從上述正極合劑的塗佈至分散介質揮發為止的步驟，來形成為多層結構的正極合劑層。分散介質可為水、1-甲基-2-吡咯啶酮(以下亦稱為NMP)等。In the first step, a kneader, a disperser, etc. are used to disperse the materials used in the positive electrode agent layer 10 in a dispersion medium to obtain a slurry positive electrode agent, and then the positive electrode agent is applied to the positive electrode collector 9 by a doctor blade method, an immersion method, a spray method, etc., and then the dispersion medium is volatilized to obtain a positive electrode 6. After the dispersion medium is volatilized, a compression molding step by roller pressing can be set as needed. The cathode agent layer 10 can be formed into a multi-layered cathode agent layer by performing the steps of coating the cathode agent and volatilizing the dispersion medium a plurality of times. The dispersion medium can be water, 1-methyl-2-pyrrolidone (hereinafter also referred to as NMP), etc.
第2步驟可與上述第1步驟相同，於負極集電體11形成負極合劑層12的方法可為與上述第1步驟相同的方法。The second step may be the same as the first step, and the method for forming the negative electrode mixture layer 12 on the negative electrode current collector 11 may be the same as the first step.
第3步驟中，將間隔件7夾在所製得的正極6與負極8之間而形成電極群2。然後，將此電極群2容置於電池外殼體3中。In the third step, the separator 7 is sandwiched between the prepared positive electrode 6 and negative electrode 8 to form the electrode group 2 . Then, this electrode group 2 is accommodated in the battery outer case 3 .
第4步驟中，將電解液注入電池外殼體3中。電解液能夠藉由例如下述方式來調製：一開始使電解質鹽溶於溶劑中後，再使其它材料溶解。In the fourth step, the electrolyte is injected into the battery outer case 3 . The electrolyte solution can be prepared, for example, by first dissolving an electrolyte salt in a solvent and then dissolving other materials.
作為其它實施形態，電化學裝置可為電容器。電容器可與上述非水電解液二次電池1同樣具備：電極群，其由正極、負極及間隔件所構成；及，袋狀的電池外殼體，其用以容置電極群。電容器中的各構成要素的詳細內容與非水電解液二次電池1相同。 [實施例]As another embodiment, the electrochemical device may be a capacitor. Like the non-aqueous electrolyte secondary battery 1 described above, the capacitor may include: an electrode group composed of a positive electrode, a negative electrode, and a separator; and a bag-shaped battery outer case for accommodating the electrode group. The details of each component in the capacitor are the same as those of the non-aqueous electrolyte secondary battery 1 . [Example]
以下，藉由實施例來具體說明本發明，但本發明並不受此等實施例所限定。The present invention will be specifically described below through examples, but the present invention is not limited by these examples.
(實施例1) [正極的製作] 在作為正極活性物質的鎳鈷錳酸鋰(92質量％)中，依序添加作為導電劑的乙炔黑(AB)(4質量％)及黏合劑(4質量％)並混合。藉由對所獲得的混合物添加作為分散介質的NMP並揉合，來調製漿液狀的正極合劑。將規定量的此正極合劑均等且均質地塗佈於作為正極集電體的厚度20 μm的鋁箔。然後，使分散介質揮發後，藉由加壓來壓緊至密度2.8 g/cm3 為止，而獲得正極。(Example 1) [Preparation of positive electrode] Acetylene black (AB) (4 mass%) and a binder (4 mass%) as a conductive agent are added to lithium nickel cobalt manganate (92 mass%) as a positive electrode active material in sequence and mixed. A slurry positive electrode compound is prepared by adding NMP as a dispersion medium to the obtained mixture and kneading. A specified amount of this positive electrode compound is evenly and uniformly applied to an aluminum foil with a thickness of 20 μm as a positive electrode collector. Then, after the dispersion medium is volatilized, it is pressed by applying pressure to a density of 2.8 g/ cm3 to obtain a positive electrode.
[負極的製作] 在作為負極活性物質的石墨中添加黏合劑及作為增黏劑的羧甲基纖維素。此等的質量比是設為石墨：黏合劑：增黏劑＝98：1：1。藉由對所獲得的混合物添加作為分散介質的水並揉合，來調製漿液狀的負極合劑。將規定量的此負極合劑均等且均質地塗佈於作為負極集電體的厚度10 μm的壓延銅箔。然後，使分散介質揮發後，藉由加壓來壓緊至密度1.6 g/cm3 為止，而獲得負極。[Preparation of negative electrode] Add a binder and carboxymethyl cellulose as a thickener to graphite as the negative electrode active material. The mass ratio is set to graphite: binder: thickener = 98:1:1. Add water as a dispersion medium to the obtained mixture and knead it to prepare a slurry of negative electrode compound. Apply a specified amount of this negative electrode compound evenly and uniformly to a 10 μm thick rolled copper foil as a negative electrode collector. Then, after the dispersion medium is volatilized, pressurize it to a density of 1.6 g/ cm3 to obtain a negative electrode.
[鋰離子二次電池的製作] 以間隔件亦即聚乙烯製多孔質薄片(商品名：HIPORE(註冊商標)，旭化成股份有限公司製，厚度30 μm)來將切割成13.5 cm2 的四方形的正極電極夾住，並進一步將切割成14.3 cm2 的四方形的負極疊合，而製作電極群。將此電極群容置於由鋁製的疊層薄膜(商品名：鋁疊層薄膜，大日本印刷股份有限公司製)所形成的容器(電池外殼體)。然後，在容器中添加電解液1 mL，並使容器熱熔接，而製作評估用的鋰離子二次電池。作為電解液，是使用一電解液，其是在1 mol/L的包含LiPF6 之碳酸伸乙酯、碳酸二甲酯及碳酸二乙酯的混合溶液中，添加1質量％的由下述式(6)表示的化合物A、及1質量％的碳酸伸乙烯酯(VC)(任一種皆以電解液總量作為基準計)而成。 [Preparation of lithium ion secondary battery] A polyethylene porous sheet (trade name: HIPORE (registered trademark), manufactured by Asahi Kasei Co., Ltd., thickness 30 μm), which is a spacer, is cut into a square shape of 13.5 cm 2 The positive electrode is clamped, and the negative electrode cut into a square shape of 14.3 cm 2 is further laminated to make an electrode group. This electrode group was housed in a container (battery outer case) made of an aluminum laminated film (trade name: aluminum laminated film, manufactured by Dainippon Printing Co., Ltd.). Then, 1 mL of the electrolyte solution was added to the container, and the container was heat-welded to produce a lithium ion secondary battery for evaluation. As the electrolyte, an electrolyte was used in which 1 mol/L of a mixed solution of ethyl carbonate, dimethyl carbonate, and diethyl carbonate containing LiPF 6 was added with 1 mass % of the following formula: It is composed of the compound A represented by (6) and 1% by mass of vinyl carbonate (VC) (either based on the total amount of the electrolyte solution).
(實施例2) 針對實施例1，除了添加以電解液總量作為基準計為0.3質量％的由下述式(7)表示的化合物B來取代化合物A以外，其餘與實施例1同樣地進行，而製作鋰離子二次電池。 (Example 2) The same procedure as Example 1 was performed except that 0.3% by mass of compound B represented by the following formula (7) based on the total amount of the electrolyte solution was added instead of compound A. , and make lithium-ion secondary batteries.
(實施例3) 針對實施例1，除了添加以電解液總量作為基準計為0.1質量％的由下述式(8)表示的化合物C來取代化合物A以外，其餘與實施例1同樣地進行，而製作鋰離子二次電池。 (Example 3) The same procedure as in Example 1 was performed except that 0.1% by mass of compound C represented by the following formula (8) was added based on the total amount of the electrolyte instead of compound A. , and make lithium-ion secondary batteries.
(比較例1) 針對實施例1，除了不使用化合物A及碳酸伸乙烯酯以外，其餘與實施例1同樣地進行，而製作鋰離子二次電池。(Comparative example 1) In Example 1, a lithium ion secondary battery was produced in the same manner as in Example 1, except that compound A and vinyl carbonate were not used.
(比較例2) 針對實施例1，除了不使用化合物A以外，其餘與實施例1同樣地進行，而製作鋰離子二次電池。(Comparative Example 2) A lithium ion secondary battery was prepared in the same manner as in Example 1 except that compound A was not used.
[初次充放電] 對所製得的二次電池，以如下所示的方法來實施初次充放電。首先，在25℃的環境中以0.1 C的電流值來進行定電流充電至上限電壓4.2 V為止，然後以4.2 V來進行定電壓充電。充電截止條件是設為電流值0.01 C。然後，以0.1 C的電流值來進行截止電壓2.7 V的定電流放電。反覆進行3次此充放電循環(所謂作為電流值的單位使用的「C」，是意指「電流值(A)/電池容量(Ah)」)。將第3次循環的放電容量設為此電流的容量Q1。[Initial charge and discharge] The secondary battery was charged and discharged for the first time as shown below. First, constant current charging was performed at a current value of 0.1 C in an environment of 25°C until the upper limit voltage reached 4.2 V, and then constant voltage charging was performed at 4.2 V. The charge cut-off condition was set to a current value of 0.01 C. Then, constant current discharge was performed at a current value of 0.1 C with a cut-off voltage of 2.7 V. This charge and discharge cycle was repeated three times (the so-called "C" used as a unit of current value means "current value (A)/battery capacity (Ah)"). The discharge capacity of the third cycle was set to the capacity Q1 of this current.
[循環特性的評估] 在初次充放電後，藉由反覆進行充放電的循環測試，來評估各二次電池的循環特性。充電模式是對實施例1～3及比較例1～2的二次電池，在45℃的環境中以0.5 C的電流值來進行定電流充電至上限電壓4.2 V為止，然後以4.2 V來進行定電壓充電。充電截止條件是設為電流0.05 C。放電是以0.5 C來進行定電流放電至2.7 V為止，而求出放電容量。反覆進行此一連串的充放電300次循環，並在每次充放電皆測定放電容量。在各循環的放電容量相對於第1次循環的充放電後的放電容量的相對值(放電容量維持率(％))。循環測試的結果是如第3圖所示。第3圖(a)、第3圖(b)、第3圖(c)中分別顯示實施例1、實施例2、及實施例3的結果，為了進行比較，而在第3圖(a)～第3圖(c)的全部圖表中顯示比較例1及比較例2的結果。[Evaluation of cycle characteristics] After the initial charge and discharge, the cycle characteristics of each secondary battery are evaluated by repeatedly performing charge and discharge cycle tests. The charging mode is to perform constant current charging on the secondary batteries of Examples 1 to 3 and Comparative Examples 1 to 2 in an environment of 45°C with a current value of 0.5 C until the upper limit voltage is 4.2 V, and then continue charging at 4.2 V. Constant voltage charging. The charging cut-off condition is set to a current of 0.05 C. The discharge was carried out at a constant current of 0.5 C until it reached 2.7 V, and the discharge capacity was obtained. Repeat this series of charge and discharge cycles for 300 times, and measure the discharge capacity at each charge and discharge. The relative value of the discharge capacity in each cycle to the discharge capacity after charge and discharge in the first cycle (discharge capacity retention rate (%)). The results of the loop test are shown in Figure 3. Figure 3(a), Figure 3(b), and Figure 3(c) show the results of Example 1, Example 2, and Example 3 respectively. For comparison, Figure 3(a) ～The results of Comparative Example 1 and Comparative Example 2 are shown in all graphs in Figure 3 (c).
結果明顯可知，實施例1～3中的第300次循環的放電容量維持率分別為90％、89％、89％，而較比較例1及比較例2中的第300次循環的放電容量維持率(分別為67％、86％)更加提高。我們認為其理由為：由於化合物A、化合物B或化合物C與碳酸伸乙烯酯於正極或負極上形成穩定的被膜，且電解液的分解受到此被膜所抑制，故能夠達成二次電池的長壽命化。The results clearly show that the discharge capacity maintenance rates at the 300th cycle in Examples 1 to 3 were 90%, 89%, and 89% respectively, and compared with the discharge capacity maintenance rates at the 300th cycle in Comparative Examples 1 and 2, The rates (67% and 86% respectively) were further improved. We believe that the reason is: Compound A, Compound B or Compound C and vinyl carbonate form a stable coating on the positive electrode or negative electrode, and the decomposition of the electrolyte is inhibited by this coating, so the secondary battery can have a long life. change.
(放電DCR的測定) 對循環測試後的各二次電池，以下述方式測定放電時的直流電阻(放電DCR)。 首先，進行0.2 C的定電流充電至上限電壓4.2 V為止，然後以4.2 V來進行定電壓充電。充電截止條件是設為電流值0.02 C。然後，以0.2 C的電流值來進行截止電壓2.7 V的定電流放電後，將此時的電流值設為I0.2C 、將放電開始10秒後的電壓變化設為ΔV0.2C 。然後，進行0.2 C的定電流充電至上限電壓4.2 V為止，然後以4.2 V來進行定電壓充電後(充電截止條件是設為電流值0.02 C)，以0.5 C的電流值來進行截止電壓2.7 V的定電流放電後，將此時的電流值設為I0.5C 、將放電開始10秒後的電壓變化設為ΔV0.5C 。從相同的充放電來評估1 C的電流值I1C 、放電開始10秒後的電壓變化ΔV1C 。使用最小平方法來在該電流值-電壓變化的3個描繪點(I0.2C ,ΔV0.2C )、(I0.5C ,ΔV0.5C )、(I1C ,ΔV1C )畫出線性近似直線，並將其斜率設為放電DCR的值。300次循環後的放電DCR的測定結果是如第4圖所示。(Measurement of Discharge DCR) For each secondary battery after the cycle test, the DC resistance during discharge (discharge DCR) was measured in the following manner. First, constant current charging of 0.2 C is performed until the upper limit voltage is 4.2 V, and then constant voltage charging is performed at 4.2 V. The charging cutoff condition is set to a current value of 0.02 C. Then, after performing constant current discharge with a cut-off voltage of 2.7 V at a current value of 0.2 C, the current value at this time is set to I 0.2C , and the voltage change 10 seconds after the start of discharge is set to ΔV 0.2C . Then, charge with a constant current of 0.2 C until the upper limit voltage is 4.2 V, and then charge with a constant voltage of 4.2 V (charge cutoff condition is set to a current value of 0.02 C), then charge with a current value of 0.5 C to a cutoff voltage of 2.7 After discharge with a constant current of V, let the current value at this time be I 0.5C , and let the voltage change 10 seconds after the start of discharge be ΔV 0.5C . From the same charge and discharge, the current value I 1C of 1 C and the voltage change ΔV 1C 10 seconds after the start of discharge were evaluated. Use the least squares method to draw a linear approximation straight line at the three plot points of the current value-voltage change (I 0.2C , ΔV 0.2C ), (I 0.5C , ΔV 0.5C ), (I 1C , ΔV 1C ), And set its slope to the value of discharge DCR. The measurement results of discharge DCR after 300 cycles are shown in Figure 4.
結果明顯可知，實施例1～3的放電DCR分別為2.6 Ω、2.5 Ω、2.5 Ω，而電阻較比較例1及比較例2的放電DCR(分別為4.9 Ω、4.0 Ω)更加降低。我們認為其理由為：由於化合物A、化合物B或化合物C與碳酸伸乙烯酯於正極或負極上形成穩定的被膜，且電解液的過剩分解受到此被膜所抑制，故能夠抑制二次電池的電阻增加。The results clearly show that the discharge DCR of Examples 1 to 3 are 2.6 Ω, 2.5 Ω, and 2.5 Ω respectively, and the resistance is lower than the discharge DCR of Comparative Example 1 and Comparative Example 2 (respectively 4.9 Ω and 4.0 Ω). We believe that the reason is: Compound A, Compound B or Compound C and vinyl carbonate form a stable coating on the positive electrode or negative electrode, and excessive decomposition of the electrolyte is suppressed by this coating, so the resistance of the secondary battery can be suppressed. Increase.
[高溫保存測試] 對實施例1、比較例1～2的各二次電池，進行上述初回充放電後，在25℃的環境中以0.1 C的電流值來進行定電流充電至上限電壓4.2 V為止，然後以4.2 V來進行定電壓充電。充電截止條件是設為電流值0.01 C。然後，在60℃的恆溫槽中將該等二次電池保管4週。[High-temperature storage test] After the initial charge and discharge, the secondary batteries of Example 1 and Comparative Examples 1-2 were charged at a current value of 0.1 C in a 25°C environment until the upper limit voltage reached 4.2 V, and then charged at a constant voltage of 4.2 V. The charging cut-off condition was set to a current value of 0.01 C. The secondary batteries were then stored in a 60°C constant temperature chamber for 4 weeks.
[體積增加率的測定] 使用依照阿基米德(Archimedes)法的比重計(電子比重計MDS-300，Alfa Mirage公司製)，來測定實施例1、比較例1～2的各二次電池的體積。從高溫保存測試前的體積(V1)、及在高溫保存測試後在25℃的環境中保持30分鐘後的二次電池的體積(V2)，藉由下述式來算出體積增加率。 體積增加率(％)＝V2/V1×100[Measurement of volume increase rate] The volume of each secondary battery in Example 1 and Comparative Examples 1 to 2 was measured using a densimeter based on the Archimedes method (electronic densimeter MDS-300, manufactured by Alfa Mirage). The volume increase rate was calculated from the volume before the high-temperature storage test (V1) and the volume of the secondary battery after being kept in an environment of 25°C for 30 minutes after the high-temperature storage test (V2) by the following formula. Volume increase rate (%) = V2/V1×100
結果，實施例1的體積增加率為105.5％，比較例1的體積增加率為107.1％，比較例2的體積增加率為108.9％。比較例2的鋰離子二次電池應用了僅包含碳酸伸乙烯酯之電解液，比較例1的鋰離子二次電池應用了不含化合物A及碳酸伸乙烯酯之中的任一方之電解液，而與比較例1的鋰離子二次電池相比，比較例2的鋰離子二次電池的體積增加率更增加。我們認為其原因為：在高溫(60℃)的環境中，碳酸伸乙烯酯分解而產生氣體。另一方面，實施例1的鋰離子二次電池應用了包含化合物A及碳酸伸乙烯酯雙方之電解液，而與比較例1及比較例2的鋰離子二次電池相比，實施例1的鋰離子二次電池的體積增加率更加降低。我們認為其原因為：化合物A有助於包含碳酸伸乙烯酯之電解液穩定化而能夠抑制氣體產生。As a result, the volume increase rate of Example 1 was 105.5%, the volume increase rate of Comparative Example 1 was 107.1%, and the volume increase rate of Comparative Example 2 was 108.9%. The lithium ion secondary battery of Comparative Example 2 used an electrolyte containing only vinyl carbonate, while the lithium ion secondary battery of Comparative Example 1 used an electrolyte containing neither compound A nor vinyl carbonate, and the volume increase rate of the lithium ion secondary battery of Comparative Example 2 was greater than that of the lithium ion secondary battery of Comparative Example 1. We believe that the reason is that vinyl carbonate decomposes and generates gas in a high temperature (60°C) environment. On the other hand, the lithium ion secondary battery of Example 1 uses an electrolyte containing both Compound A and vinyl carbonate, and the volume increase rate of the lithium ion secondary battery of Example 1 is further reduced compared with the lithium ion secondary batteries of Comparative Examples 1 and 2. We believe that the reason is that Compound A helps stabilize the electrolyte containing vinyl carbonate and can suppress gas generation.
[容量維持率的測定] 將在60℃的恆溫槽中保管4週後的實施例1、比較例1～2的各二次電池從恆溫槽取出，並在25℃的環境中保持30分鐘後，以0.1 C的電流值來進行截止電壓2.7 V的定電流放電。將此時的放電容量設為Q2。使用上述Q1、Q2，並使用下述式來算出容量維持率。 容量維持率(％)＝Q2/Q1×100[Measurement of capacity maintenance rate] Each secondary battery of Example 1 and Comparative Examples 1 to 2, which had been stored in a constant temperature bath at 60°C for 4 weeks, was taken out of the constant temperature bath and kept in an environment of 25°C for 30 minutes. to perform constant current discharge with a cut-off voltage of 2.7 V. Let the discharge capacity at this time be Q2. The capacity maintenance rate is calculated using the following equation using the above Q1 and Q2. Capacity maintenance rate (%)=Q2/Q1×100
結果，實施例1的容量維持率為92.9％，比較例1的容量維持率為90.7％，比較例2的容量維持率為92.3％。比較例2的鋰離子二次電池應用了僅包含碳酸伸乙烯酯之電解液，比較例1的鋰離子二次電池應用了不含化合物A及碳酸伸乙烯酯之中的任一方之電解液，而與比較例1的鋰離子二次電池相比，比較例2的鋰離子二次電池的容量維持率更良好。我們認為其原因為：碳酸伸乙烯酯在負極上形成穩定的被膜，而抑制由於在高溫(60℃)環境中電解液分解所造成的容量維持率降低。此外，實施例1的鋰離子二次電池應用了包含化合物A及碳酸伸乙烯酯雙方之電解液，比較例2的鋰離子二次電池應用了僅包含碳酸伸乙烯酯之電解液，而與比較例2的鋰離子二次電池相比，實施例1的鋰離子二次電池的容量維持率更加提高。我們認為其原因為：因除了碳酸伸乙烯酯在負極上形成穩定的被膜以外，化合物A使電解液穩定化，而更加抑制電解液分解。As a result, the capacity retention rate of Example 1 was 92.9%, the capacity retention rate of Comparative Example 1 was 90.7%, and the capacity retention rate of Comparative Example 2 was 92.3%. The lithium ion secondary battery of Comparative Example 2 used an electrolyte containing only vinyl carbonate, while the lithium ion secondary battery of Comparative Example 1 used an electrolyte containing neither compound A nor vinyl carbonate, and the capacity retention rate of the lithium ion secondary battery of Comparative Example 2 was better than that of the lithium ion secondary battery of Comparative Example 1. We believe that the reason is that vinyl carbonate forms a stable film on the negative electrode, which inhibits the decrease in capacity retention rate caused by the decomposition of the electrolyte in a high temperature (60°C) environment. In addition, the lithium ion secondary battery of Example 1 used an electrolyte containing both Compound A and vinyl carbonate, and the lithium ion secondary battery of Comparative Example 2 used an electrolyte containing only vinyl carbonate, and the capacity retention rate of the lithium ion secondary battery of Example 1 was further improved compared with the lithium ion secondary battery of Comparative Example 2. We believe that the reason is that in addition to vinyl carbonate forming a stable film on the negative electrode, Compound A stabilizes the electrolyte and further suppresses the decomposition of the electrolyte.
如上所述，實施例1～3的鋰離子二次電池應用了包含化合物A及具有碳-碳雙鍵之環狀碳酸酯雙方之電解液，比較例1的鋰離子二次電池應用了不含具有碳-碳雙鍵之環狀碳酸酯及化合物A之電解液，比較例2的鋰離子二次電池應用了包含具有碳-碳雙鍵之環狀碳酸酯且不含化合物A之電解液，而相較於比較例1的鋰離子二次電池及比較例2的鋰離子二次電池，實施例1～3的鋰離子二次電池顯示更優異的性能。As described above, the lithium ion secondary batteries of Examples 1 to 3 used an electrolyte solution containing both Compound A and the cyclic carbonate having a carbon-carbon double bond, and the lithium ion secondary battery of Comparative Example 1 used an electrolyte solution that did not contain An electrolyte solution containing a cyclic carbonate having a carbon-carbon double bond and compound A. The lithium ion secondary battery of Comparative Example 2 uses an electrolyte solution containing a cyclic carbonate having a carbon-carbon double bond and not containing compound A. Compared with the lithium ion secondary battery of Comparative Example 1 and the lithium ion secondary battery of Comparative Example 2, the lithium ion secondary batteries of Examples 1 to 3 show more excellent performance.
1:非水電解液二次電池(電化學裝置) 2:電極群 3:電池外殼體 4:正極集電端子 5:負極集電端子 6:正極 7:間隔件 8:負極 9:正極集電體 10:正極合劑層 11:負極集電體 12:負極合劑層1: Non-aqueous electrolyte secondary battery (electrochemical device) 2: Electrode group 3: Battery casing 4: Positive electrode collector terminal 5: Negative electrode collector terminal 6: Positive electrode 7: Spacer 8: Negative electrode 9: Positive electrode collector 10: Positive electrode compound layer 11: Negative electrode collector 12: Negative electrode compound layer
第1圖是顯示作為一實施形態的電化學裝置的非水電解液二次電池的斜視圖。 第2圖是顯示第1圖所示的二次電池的電極群的分解斜視圖。 第3圖是實施例及比較例中的循環測試的結果的圖表。 第4圖是實施例及比較例中的放電DCR的測定結果的圖表。FIG. 1 is a perspective view showing a non-aqueous electrolyte secondary battery as an electrochemical device according to an embodiment. Fig. 2 is an exploded perspective view showing the electrode group of the secondary battery shown in Fig. 1 . Fig. 3 is a graph showing the results of the cycle test in the Examples and Comparative Examples. Fig. 4 is a graph showing the measurement results of discharge DCR in Examples and Comparative Examples.
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