JP2000012026A - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary batteryInfo
- Publication number
- JP2000012026A JP2000012026A JP10177502A JP17750298A JP2000012026A JP 2000012026 A JP2000012026 A JP 2000012026A JP 10177502 A JP10177502 A JP 10177502A JP 17750298 A JP17750298 A JP 17750298A JP 2000012026 A JP2000012026 A JP 2000012026A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- secondary battery
- electrolyte secondary
- aqueous electrolyte
- active material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 5
- 239000010439 graphite Substances 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 10
- 239000007773 negative electrode material Substances 0.000 claims description 10
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 16
- 229910052748 manganese Inorganic materials 0.000 description 16
- 239000011572 manganese Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- UUAMLBIYJDPGFU-UHFFFAOYSA-N 1,3-dimethoxypropane Chemical compound COCCCOC UUAMLBIYJDPGFU-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FKQOMXQAEKRXDM-UHFFFAOYSA-N [Li].[As] Chemical compound [Li].[As] FKQOMXQAEKRXDM-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Carbon And Carbon Compounds (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
(57)【要約】
【課題】負極に炭素材量を用いた非水電解液を用いる二
次電池において、保存特性及びサイクル寿命特性を向上
させる。
【解決手段】負極の炭素材料の表面に金属酸化物をコー
ティングして使用する。負極の炭素材料として黒鉛系炭
素材を用いる。(57) [Problem] To improve storage characteristics and cycle life characteristics of a secondary battery using a nonaqueous electrolyte using a carbon material amount for a negative electrode. A surface of a carbon material of a negative electrode is coated with a metal oxide for use. A graphite-based carbon material is used as the carbon material for the negative electrode.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は非水電解液二次電池
に関し、保存特性及びサイクル寿命特性の改善を目的と
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery, and an object thereof is to improve storage characteristics and cycle life characteristics.
【０００２】[0002]
【従来の技術】携帯用電話機、コードレス電話器、ビデ
オカメラなどの映像機器、パソコンなどの事務用機器、
家電機器、電気自動車などの主電源あるいはバックアッ
プ用電源として、長時間使用できるリチウムイオン二次
電池が強く要求されている。なお、これらのリチウムイ
オン二次電池に使用されている正極活物質としては、リ
チウムコバルト複合酸化物、リチウムニッケル複合酸化
物、リチウムマンガン複合酸化物などが用いられてお
り、その中でも資源的に豊富で安価なマンガンを主原料
としたリチウムマンガン複合酸化物が注目をされてい
る。2. Description of the Related Art Mobile phones, cordless phones, video equipment such as video cameras, office equipment such as personal computers,
There is a strong demand for a lithium ion secondary battery that can be used for a long time as a main power supply or a backup power supply for home appliances and electric vehicles. As the positive electrode active material used in these lithium ion secondary batteries, lithium cobalt composite oxide, lithium nickel composite oxide, lithium manganese composite oxide and the like are used, and among them, resources are abundant in resources. Attention has been paid to lithium-manganese composite oxides using manganese as a main raw material, which is inexpensive.
【０００３】このリチウムマンガン複合酸化物は、リチ
ウムが出入りしやすいスピネル構造をとっている。そし
て、リチウムマンガン複合酸化物を正極活物質に用いた
場合には、初期のサイクル特性や放置特性はある程度満
足できるものの、充放電サイクルの進行や放置期間の長
期化に伴い、正極活物質中のマンガンがイオンとなって
電解液中に溶出し、溶出したマンガンイオンが負極の活
物質表面で析出して不導体皮膜を生成し、充放電に関与
する反応場を減少させるため放電容量が劣化することが
明らかになっている。[0003] The lithium manganese composite oxide has a spinel structure in which lithium can easily enter and exit. When the lithium manganese composite oxide is used for the positive electrode active material, although the initial cycle characteristics and the leaving characteristics can be satisfied to some extent, with the progress of the charge / discharge cycle and the prolonged leaving period, Manganese elutes into the electrolyte as ions, and the eluted manganese ions precipitate on the active material surface of the negative electrode to form a nonconductive film, which reduces the reaction field involved in charging and discharging, resulting in deterioration of discharge capacity. It is clear that
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、充放
電サイクルによる容量劣化が少なく、放置後の放電特性
が良好な非水電解液二次電池を提供することを目的する
ものである。SUMMARY OF THE INVENTION An object of the present invention is to provide a non-aqueous electrolyte secondary battery which has a small capacity deterioration due to charge / discharge cycles and good discharge characteristics after being left.
【０００５】[0005]
【発明が解決しようとする手段】上記した課題を解決す
るために、第一の発明ではリチウムの吸蔵・放出が可能
な正極及び負極を用いる非水電解液二次電池において、
前記負極用活物質の表面に金属酸化物をコーティングす
ることを特徴とし、第二の発明では前記負極活物質の表
面にコーティングする金属元素としてニッケル、コバル
ト、銅、金、モリブデン、タングステンから選ばれた少
なくとも１種類以上の金属元素を使用することを特徴と
し、第三の発明では前記負極用活物質として黒鉛系炭素
材を使用することを特徴とし、第四の発明ではリチウム
を吸蔵・放出が可能な正極及び負極を用いる非水電解液
二次電池において、前記正極の活物質がスピネル構造を
有したリチウムマンガン複合酸化物であることを特徴と
している。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, a first invention relates to a non-aqueous electrolyte secondary battery using a positive electrode and a negative electrode capable of inserting and extracting lithium.
The surface of the negative electrode active material is coated with a metal oxide, and in the second invention, the metal element coated on the surface of the negative electrode active material is selected from nickel, cobalt, copper, gold, molybdenum, and tungsten. The third invention is characterized in that a graphite-based carbon material is used as the negative electrode active material, and the fourth invention is characterized in that lithium is occluded / released. In a nonaqueous electrolyte secondary battery using a possible positive electrode and negative electrode, the active material of the positive electrode is a lithium manganese composite oxide having a spinel structure.
【０００６】[0006]
【発明の実施の形態】上記した課題を解決するために種
々努力した結果、負極の改良が有効であることがわかっ
た。以下において、発明の実施の形態を詳細に述べる。DESCRIPTION OF THE PREFERRED EMBODIMENTS As a result of various efforts to solve the above-mentioned problems, it has been found that improvement of a negative electrode is effective. Hereinafter, embodiments of the invention will be described in detail.
【０００７】１．正極 正極活物質としては、平均粒径１０μmのリチウムマン
ガン複合酸化物と導電助剤としては平均粒径３μmの炭
素粉末と結着剤として、ポリフッ化ビニリデン（以下、
ＰＶｄＦと略す）とを８２：１０：８の重量％で混合す
る。そこに、Ｎ−メチル−２−ピロリドンを投入混合し
て、スラリー状の溶液を作製する。厚みが２０μmのア
ルミニウム箔の両面に作製したスラリー状の溶液を塗布
し、溶剤を乾燥した後、ローラプレス機にて圧延して、
正極合剤電極を作製し、５４ｍｍ幅で長さが４５０ｍｍ
に切断して短細状の正極を作製した。[0007] 1. Positive electrode As a positive electrode active material, a lithium manganese composite oxide having an average particle diameter of 10 μm, a carbon powder having an average particle diameter of 3 μm as a conductive additive, and polyvinylidene fluoride (hereinafter, referred to as a binder)
PVdF) at 82: 10: 8% by weight. There, N-methyl-2-pyrrolidone is charged and mixed to prepare a slurry-like solution. A slurry-like solution prepared on both surfaces of an aluminum foil having a thickness of 20 μm was applied, and after the solvent was dried, it was rolled with a roller press.
Prepare a positive electrode mixture electrode, 54mm width and 450mm length
Into a short positive electrode.
【０００８】２．負極 負極は負極活物質としては平均粒径２０μmの炭素材料
（商品名：カーボトロンＰ、呉羽化学工業（株）製）を
無電解メッキ法にて酸化コバルトの皮膜をコーティング
した。この粉末の皮膜は粉末Ｘ線回折（ＸＲＤ）ではリ
チウムマンガン複合酸化物によるピークが測定され、Ｘ
線光電子分析（以下、ＸＰＳと略す）で酸化コバルトに
よるＣｏ（１ｓ）ピークが測定された。この粉末をエッ
チングしたところ、ＸＰＳでは酸化コバルトのピークは
測定されないことから極表面にのみ存在し、活物質内部
には認められないことが明らかになった。この炭素材と
フッ化ビニリデン（ＰＶｄＦ）の結着剤を９２：８の重
量％で混合し、Ｎ−メチル−２−ピロリドンを投入混合
して、スラリー状の溶液を作製する。厚み１０μmの銅
箔の両面にこの混合溶液を塗布し、溶剤を乾燥した後、
ローラプレス機にて圧延して、負極合剤電極を作製し、
その後５６ｍｍ幅で、長さが４９０ｍｍに切断して短冊
状の負極を作製した。[0008] 2. Negative Electrode The negative electrode was coated with a cobalt oxide film by an electroless plating method using a carbon material (trade name: CARBOTRON P, manufactured by Kureha Chemical Industry Co., Ltd.) having an average particle size of 20 μm as a negative electrode active material. In the powder coating, a peak due to a lithium manganese composite oxide was measured by powder X-ray diffraction (XRD).
A Co (1s) peak due to cobalt oxide was measured by linear photoelectron analysis (hereinafter abbreviated as XPS). When this powder was etched, it was clarified that the peak of cobalt oxide was not measured by XPS, so that it was present only on the very surface and was not recognized inside the active material. This carbon material and a binder of vinylidene fluoride (PVdF) are mixed at a weight ratio of 92: 8, and N-methyl-2-pyrrolidone is added and mixed to prepare a slurry-like solution. This mixed solution was applied to both sides of a copper foil having a thickness of 10 μm, and after the solvent was dried,
Rolled with a roller press to produce a negative electrode mixture electrode,
Thereafter, the strip was cut into a width of 56 mm and a length of 490 mm to prepare a strip-shaped negative electrode.
【０００９】３．電池 上記した方法で作製した正極と負極とを厚さ４０μm、
幅５８ｍｍのポリエチレン微多孔膜からなるセパレータ
を介して捲回し、スパイラル状の捲回群を作製する。こ
の捲回群を電池缶に挿入し、予め負極集電体の銅箔に溶
接しておいたニッケルタブ端子を電池缶底に溶接する。
次にエチレンカーボネートとジメチルカーボネートを
１：２の体積比で混合した溶液にＬｉＰＦ6を１ｍｏｌ
／ｌの濃度で溶解した電解液を電池容器に５ｍｌ注入し
た。次に、予め正極集電体のアルミニウム箔に溶接した
アルミニウムタブ端子を蓋に溶接して、蓋を絶縁性のガ
スケットを介して電池缶の上部に配置させ、この部分を
かしめて密閉し、直径１８ｍｍ、高さ６５ｍｍの円筒型
電池を作製した。3. Battery The positive electrode and the negative electrode produced by the above-described method are 40 μm thick,
It is wound through a separator made of a microporous polyethylene film having a width of 58 mm to form a spiral wound group. The wound group is inserted into a battery can, and a nickel tab terminal previously welded to the copper foil of the negative electrode current collector is welded to the bottom of the battery can.
Next, 1 mol of LiPF 6 was added to a solution in which ethylene carbonate and dimethyl carbonate were mixed at a volume ratio of 1: 2.
5 ml of the electrolytic solution dissolved at a concentration of / l was injected into the battery container. Next, an aluminum tab terminal previously welded to the aluminum foil of the positive electrode current collector was welded to the lid, and the lid was placed on the top of the battery can via an insulating gasket. A cylindrical battery having a size of 18 mm and a height of 65 mm was produced.
【００１０】なお、非水溶媒としては、上記した以外に
エチレンカーボネイト、プロピレンカーボネイト、ブチ
レンカーボネイト、ジメチルカーボネイト、γ―ブチロ
ラクトン、アセトニトリル、スルホラン、１，２−ヂメ
トキシエタン、１，３−ジメトキシプロパン、ジメチル
エーテル、テトラヒドロプラン、２−メチルテトラヒド
ロプラン、炭酸ジメチル、炭酸ジエチル、及びエチルメ
チルカーボネイトから選べられる単独もしくは二種類以
上の混合溶媒が使用できる。電解質としては、たとえ
ば、過塩素酸リチウム（ＬｉＣｌＯ4）、六フッ化燐酸
リチウム（ＬｉＰＦ6）、ホウフッ化リチウム（ＬｉＢ
Ｆ4）六フッ化ヒ素リチウム（ＬｉＡｓＦ6）、トリフル
オロメタンスルホン酸リチウム（ＬｉＣＦ3ＳＯ3）など
のリチウム塩が使用できる。Examples of the non-aqueous solvent include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, γ-butyrolactone, acetonitrile, sulfolane, 1,2-dimethoxyethane, 1,3-dimethoxypropane, and the like. A single solvent or a mixed solvent of two or more selected from dimethyl ether, tetrahydroplan, 2-methyltetrahydroplan, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate can be used. Examples of the electrolyte include lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), and lithium borofluoride (LiB
F 4 ) Lithium salts such as lithium arsenic hexafluoride (LiAsF 6 ) and lithium trifluoromethanesulfonate (LiCF 3 SO 3 ) can be used.
【００１１】４．初期充放電試験 作製した電池を２５℃にて２４時間放置後、初期の充放
電試験をした。すなわち、充放電条件として、充電電圧
４．２Ｖ（ただし、制限電流９００ｍＡ）で４時間充電
した後、放電電流３００ｍＡで放電終止電圧２．７Ｖの
条件下で１０サイクル行った。4. Initial charge / discharge test After the produced battery was left at 25 ° C. for 24 hours, an initial charge / discharge test was performed. That is, as charging and discharging conditions, after charging for 4 hours at a charging voltage of 4.2 V (however, a limiting current of 900 mA), 10 cycles were performed under the conditions of a discharging current of 300 mA and a discharging end voltage of 2.7 V.
【００１２】５．サイクル試験及びマンガン溶出量の測
定 初期充放電試験をした電池の一部は、５０℃にて充電電
流９００ｍＡで充電終止電圧４．２Ｖ、放電電流３００
ｍＡにて放電終止電圧２．７Ｖの条件下で充放電サイク
ル試験を行った。１００サイクル充放電後の電池を分解
し、電解液中へのマンガンの溶出量、負極合剤中のマン
ガン量をＩＣＰで測定した。5. Cycle test and measurement of manganese elution amount A part of the battery subjected to the initial charge / discharge test was charged at 900 mA at 50 ° C. with a charge end voltage of 4.2 V and a discharge current of 300 mA.
A charge / discharge cycle test was performed under the condition of a discharge end voltage of 2.7 V at mA. The battery after 100 cycles of charge / discharge was disassembled, and the amount of manganese eluted into the electrolytic solution and the amount of manganese in the negative electrode mixture were measured by ICP.
【００１３】６．放置試験及びマンガン溶出量の測定 初期充放電試験をした電池の一部は、充電状態で５０
℃、１４日間放置し、その後電池を分解し、電解液中へ
のマンガンの溶出量、負極合剤中のマンガン量をＩＣＰ
で測定した。6. Leaving test and measurement of manganese elution amount Some of the batteries that were subjected to the initial charge / discharge test were charged 50%.
At 14 ° C for 14 days, then disassemble the battery and measure the amount of manganese eluted in the electrolyte and the amount of manganese in the negative electrode mixture by ICP.
Was measured.
【００１４】[0014]
【実施例】本発明を実施例及び比較例により、詳細に説
明する。但し、本発明はこれらに限定されるものではな
い。The present invention will be described in detail with reference to examples and comparative examples. However, the present invention is not limited to these.
【００１５】（実施例１）実施例１としては、前記した
負極活物質の表面にコバルト化合物をコーティングした
材料を用いた。それ以外の電極や電池の作製条件等は前
記したものである。Example 1 In Example 1, a material in which the surface of the above-described negative electrode active material was coated with a cobalt compound was used. The other conditions for producing electrodes and batteries are as described above.
【００１６】（比較例１）比較例１としては、負極に用
いる負極活物質として金属酸化物など何も表面にコーテ
ィングしていない材料を用いた。それ以外の電極や電池
の作製条件等は前記したものである。Comparative Example 1 In Comparative Example 1, a material having no surface coated such as a metal oxide was used as a negative electrode active material used for a negative electrode. The other conditions for producing electrodes and batteries are as described above.
【００１７】上記した、サイクル試験後の容量維持率
（１００サイクル時の放電容量と初期の放電容量の比
率）及び電解液中へのマンガン溶出量と負極合剤中のマ
ンガン量を表１に示す。また放置後における、電解液中
へのマンガン溶出量と負極合剤中のマンガン量を表２に
示す。これらの結果から、本発明を用いると電解液中及
び負極合剤中に溶出するマンガン量を抑えることがで
き、充放電サイクル時の放電容量の劣化も改善された。Table 1 shows the above-mentioned capacity retention rate after the cycle test (the ratio of the discharge capacity at 100 cycles to the initial discharge capacity), the amount of manganese eluted into the electrolyte and the amount of manganese in the negative electrode mixture. . Table 2 shows the amount of manganese eluted into the electrolyte and the amount of manganese in the negative electrode mixture after standing. From these results, when the present invention was used, the amount of manganese eluted in the electrolytic solution and the negative electrode mixture was able to be suppressed, and the deterioration of the discharge capacity during the charge / discharge cycle was also improved.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【表２】 [Table 2]
【００２０】（実施例２）黒鉛系炭素材（商品名：ＭＡ
Ｇ、日立化成工業（株）製）の表面にコバルト化合物を
コーティングした負極活物質を用いて円筒型電池を作製
してサイクル試験をし、試験後のマンガン溶出量及び充
放電サイクル時の放電容量の劣化を測定した結果を表３
に示す。黒鉛系炭素材を用いることにより、サイクル試
験特性が良好であり、電解液中へのマンガンの溶出量、
負極合剤中のマンガン量ともに実施例１よりも減少して
いることが確認された。Example 2 Graphite-based carbon material (trade name: MA)
G, manufactured by Hitachi Chemical Co., Ltd.), using a negative electrode active material coated with a cobalt compound on the surface of a negative electrode active material, producing a cylindrical battery, performing a cycle test, and eluted manganese after the test and the discharge capacity during a charge / discharge cycle. Table 3 shows the results of measuring the deterioration of
Shown in By using a graphite-based carbon material, the cycle test characteristics are good, the amount of manganese eluted into the electrolyte,
It was confirmed that both the amounts of manganese in the negative electrode mixture were lower than in Example 1.
【００２１】[0021]
【表３】 [Table 3]
【００２２】[0022]
【発明の効果】上記したように、本発明を用いると保存
特性及び充放電サイクルに優れた非水電解液二次電池を
提供することができる。なお、本実施例では円筒型電池
を例に記載しているが角型、コイン型等、種々の形状の
電池に適用できる。As described above, by using the present invention, a non-aqueous electrolyte secondary battery having excellent storage characteristics and charge / discharge cycles can be provided. In this embodiment, a cylindrical battery is described as an example, but the present invention can be applied to batteries having various shapes such as a square battery and a coin battery.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田中 伸和 東京都中央区日本橋本町２丁目８番７号 新神戸電機株式会社内 Ｆターム(参考） 5H003 AA03 AA04 BA00 BB02 BB04 BB05 BC05 5H014 AA02 BB08 CC01 EE08 EE10 5H029 AJ04 AJ05 AK03 AL07 AM03 AM07 BJ02 BJ14 ────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shinkazu Tanaka 2-8-7 Nihonbashi Honcho, Chuo-ku, Tokyo F-term in Shin-Kobe Electric Co., Ltd. 5H003 AA03 AA04 BA00 BB02 BB04 BB05 BC05 5H014 AA02 BB08 CC01 EE08 EE10 5H029 AJ04 AJ05 AK03 AL07 AM03 AM07 BJ02 BJ14
Claims (4)
極を用いる非水電解液二次電池において、前記負極用活
物質の表面に金属酸化物をコーティングすることを特徴
とする非水電解液二次電池。1. A non-aqueous electrolyte secondary battery using a positive electrode and a negative electrode capable of inserting and extracting lithium, wherein a metal oxide is coated on the surface of the active material for the negative electrode. Rechargeable battery.
金属元素としてニッケル、コバルト、銅、金、モリブデ
ン、タングステンから選ばれた少なくとも１種類以上の
金属元素を使用することを特徴とする請求項１記載の非
水電解液二次電池。2. The method according to claim 1, wherein at least one metal element selected from nickel, cobalt, copper, gold, molybdenum and tungsten is used as the metal element coated on the surface of the negative electrode active material. The non-aqueous electrolyte secondary battery according to the above.
用することを特徴とする請求項１又は２記載の非水電解
液二次電池。3. The non-aqueous electrolyte secondary battery according to claim 1, wherein a graphite-based carbon material is used as the negative electrode active material.
極を用いる非水電解液二次電池において、前記正極の活
物質がスピネル構造を有したリチウムマンガン複合酸化
物であることを特徴とする請求項１、２又は３記載の非
水電解液二次電池。4. A non-aqueous electrolyte secondary battery using a positive electrode and a negative electrode capable of inserting and extracting lithium, wherein the active material of the positive electrode is a lithium manganese composite oxide having a spinel structure. The non-aqueous electrolyte secondary battery according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10177502A JP2000012026A (en) | 1998-06-24 | 1998-06-24 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10177502A JP2000012026A (en) | 1998-06-24 | 1998-06-24 | Non-aqueous electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000012026A true JP2000012026A (en) | 2000-01-14 |
Family
ID=16032036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10177502A Pending JP2000012026A (en) | 1998-06-24 | 1998-06-24 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000012026A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002352801A (en) * | 2001-05-25 | 2002-12-06 | Rikogaku Shinkokai | Lithium secondary cell, negative electrode material for it, and improving method therefor |
| KR100433822B1 (en) * | 2002-01-17 | 2004-06-04 | 한국과학기술연구원 | Metal-coated carbon, preparation method thereof, and composite electrode and lithium secondary batteries comprising the same |
| WO2014081269A1 (en) | 2012-11-26 | 2014-05-30 | 주식회사 엘지화학 | Precursor of electrode active material coated with metal, and method for preparing same |
| WO2018135929A1 (en) * | 2017-01-23 | 2018-07-26 | 주식회사 엘지화학 | Negative electrode for lithium secondary battery, lithium secondary battery comprising same, and method for manufacturing same |
| US10062901B2 (en) | 2013-12-10 | 2018-08-28 | Samsung Sdi Co., Ltd. | Negative active material, lithium battery including the material, and method of manufacturing the material |
| US11539039B2 (en) | 2017-01-23 | 2022-12-27 | Lg Energy Solution, Ltd. | Negative electrode for lithium secondary battery, lithium secondary battery comprising the same, and preparation method thereof |
-
1998
- 1998-06-24 JP JP10177502A patent/JP2000012026A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002352801A (en) * | 2001-05-25 | 2002-12-06 | Rikogaku Shinkokai | Lithium secondary cell, negative electrode material for it, and improving method therefor |
| KR100433822B1 (en) * | 2002-01-17 | 2004-06-04 | 한국과학기술연구원 | Metal-coated carbon, preparation method thereof, and composite electrode and lithium secondary batteries comprising the same |
| WO2014081269A1 (en) | 2012-11-26 | 2014-05-30 | 주식회사 엘지화학 | Precursor of electrode active material coated with metal, and method for preparing same |
| US10243208B2 (en) | 2012-11-26 | 2019-03-26 | Lg Chem, Ltd. | Precursor of electrode active material coated with metal and method of preparing the same |
| US10062901B2 (en) | 2013-12-10 | 2018-08-28 | Samsung Sdi Co., Ltd. | Negative active material, lithium battery including the material, and method of manufacturing the material |
| WO2018135929A1 (en) * | 2017-01-23 | 2018-07-26 | 주식회사 엘지화학 | Negative electrode for lithium secondary battery, lithium secondary battery comprising same, and method for manufacturing same |
| US11539039B2 (en) | 2017-01-23 | 2022-12-27 | Lg Energy Solution, Ltd. | Negative electrode for lithium secondary battery, lithium secondary battery comprising the same, and preparation method thereof |
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