JPH04355056A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPH04355056A JPH04355056A JP3127320A JP12732091A JPH04355056A JP H04355056 A JPH04355056 A JP H04355056A JP 3127320 A JP3127320 A JP 3127320A JP 12732091 A JP12732091 A JP 12732091A JP H04355056 A JPH04355056 A JP H04355056A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- positive electrode
- secondary battery
- aqueous electrolyte
- electrolyte secondary
- 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.)
- Granted
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 28
- 239000011973 solid acid Substances 0.000 claims abstract description 15
- 229910032387 LiCoO2 Inorganic materials 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 239000011149 active material Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 4
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 3
- 238000009831 deintercalation Methods 0.000 claims description 2
- 238000009830 intercalation Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 230000007423 decrease Effects 0.000 abstract description 10
- -1 is used Inorganic materials 0.000 abstract description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 abstract description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 abstract description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 abstract description 3
- 239000007774 positive electrode material Substances 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000006243 chemical reaction Methods 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
- 239000004743 Polypropylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 150000002642 lithium compounds 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、非水電解液二次電池に
関し、特に正極を改良した非水電解液二次電池に関する
。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly to a non-aqueous electrolyte secondary battery with an improved positive electrode.
【０００２】0002
【従来の技術】リチウム，リチウム合金またはリチウム
化合物を負極とする非水電解液二次電池は高電圧で高エ
ネルギー密度となることが期待され、多くの研究が行わ
れている。BACKGROUND OF THE INVENTION Nonaqueous electrolyte secondary batteries using lithium, lithium alloys, or lithium compounds as negative electrodes are expected to have high voltage and high energy density, and many studies are being conducted.
【０００３】特に、これら電池の正極活物質としてＭｎ
Ｏ２やＴｉＳ２がよく検討されている。これらの正極活
物質はＬｉに対する電位が３Ｖ程度であるが、最近、Ｌ
ｉＭｎ２Ｏ４およびＬｉＣｏＯ２がＬｉに対して４Ｖ以
上の電位を示す正極活物質として注目されている。In particular, Mn is used as the positive electrode active material of these batteries.
O2 and TiS2 are often considered. These positive electrode active materials have a potential of about 3V with respect to Li, but recently, L
iMn2O4 and LiCoO2 are attracting attention as positive electrode active materials exhibiting a potential of 4 V or more with respect to Li.
【０００４】すなわち、電池の高エネルギー密度を得る
手段として容量の拡大とともに電池電圧を高める努力が
なされている。That is, efforts are being made to increase the battery voltage as well as expand the capacity as a means of obtaining a high energy density of the battery.
【０００５】このうち、ＬｉＣｏＯ２は、その放電容量
が大きく、優れた充放電サイクル特性を有する可能性が
あることから正極活物質として有望と考えられている。Among these, LiCoO2 is considered to be promising as a positive electrode active material because it has a large discharge capacity and may have excellent charge-discharge cycle characteristics.
【０００６】さらに、二次電池として重要な必要特性の
１つである充放電サイクル特性を向上するため、ＬｉＣ
ｏＯ２へのＭｎ，Ｎｉ，Ｃｒ，Ｆｅなどの添加も試みら
れ、充放電サイクル特性の一層の向上が図られている。Furthermore, in order to improve the charge/discharge cycle characteristics, which is one of the important characteristics required for a secondary battery, LiC
Attempts have also been made to add Mn, Ni, Cr, Fe, etc. to oO2, with the aim of further improving the charge/discharge cycle characteristics.
【０００７】[0007]
【発明が解決しようとする課題】上記の正極活物質を用
いることにより放電容量が大きく充放電サイクル特性に
優れた非水電解液二次電池を実現できるが、充電電圧が
４Ｖを越えるため、充電後の電池の高温保存特性が不充
分であるという問題があった。非水電解液二次電池の高
温保存については電池内部の正極活物質ＬｉＣｏＯ２に
混在する可能性のあるＬｉＯＨなどのアルカリ、電解液
中の微量水分や電解液溶媒の分解が原因となり、電池内
部抵抗の増大や充放電容量の低下という問題を引き起こ
す。特に電池電圧が高くなるほどこれらの現象は顕著に
なり、また、高温保存時においてより著しいものとなる
。[Problems to be Solved by the Invention] By using the above positive electrode active material, a non-aqueous electrolyte secondary battery with a large discharge capacity and excellent charge/discharge cycle characteristics can be realized, but since the charging voltage exceeds 4V, There was a problem that the high temperature storage characteristics of the later batteries were insufficient. When storing nonaqueous electrolyte secondary batteries at high temperatures, the internal resistance of the battery increases due to alkali such as LiOH that may be mixed in the positive electrode active material LiCoO2 inside the battery, trace water in the electrolyte, and decomposition of the electrolyte solvent. This causes problems such as an increase in energy consumption and a decrease in charge/discharge capacity. In particular, these phenomena become more pronounced as the battery voltage increases, and become more pronounced during high-temperature storage.
【０００８】電池内部へ持ち込まれる水分については、
電解液の蒸留処理を始めとする精製および正極活物質の
乾燥処理などにより電池内部への水分の持込みを抑える
努力がなされている。しかし、充放電を繰り返し行う必
要のある二次電池の場合、特に、充電電圧が４Ｖを越え
る場合にはこれら水分の除去などの前処理だけでは良好
な高温保存特性を得ることができない。Regarding moisture brought into the battery,
Efforts are being made to suppress the introduction of moisture into the battery through purification such as distillation of the electrolyte and drying of the positive electrode active material. However, in the case of a secondary battery that requires repeated charging and discharging, particularly when the charging voltage exceeds 4 V, it is not possible to obtain good high-temperature storage characteristics only by pretreatment such as removing moisture.
【０００９】正極活物質と電解液溶媒との反応やこの反
応により生成した物質と負極活物質との反応が起こりや
すくなり、電池の性能低下が生じると考えられる。[0009] It is thought that the reaction between the positive electrode active material and the electrolyte solvent and the reaction between the substance produced by this reaction and the negative electrode active material tend to occur, resulting in a decrease in battery performance.
【００１０】本発明はこのような課題を解決するもので
、高温保存特性を向上した非水電解液二次電池を提供す
ることを目的とする。[0010] The present invention solves these problems, and aims to provide a non-aqueous electrolyte secondary battery with improved high-temperature storage characteristics.
【００１１】[0011]
【課題を解決するための手段】この課題を解決するため
本発明の非水電解液二次電電池は、ＬｉＣｏＯ２で表わ
される複合酸化物を活物質とする正極、リチウムを吸蔵
放出することのできる負極および非水電解液を有し、前
記正極中に固体酸を添加したものを用いる。[Means for Solving the Problem] In order to solve this problem, the non-aqueous electrolyte secondary battery of the present invention has a positive electrode that uses a composite oxide represented by LiCoO2 as an active material, and a positive electrode that can occlude and release lithium. A negative electrode and a non-aqueous electrolyte are used, and a solid acid is added to the positive electrode.
【００１２】また、固体酸が無水ＳｉＯ２，ＩｒＯ２，
Ａｌ２Ｏ３，Ｖ２Ｏ５から選ばれる少なくとも１つであ
ることが望ましい。[0012] In addition, the solid acid may be anhydrous SiO2, IrO2,
It is desirable that the material be at least one selected from Al2O3 and V2O5.
【００１３】また、固体酸の添加量が１モルのＬｉＣｏ
Ｏ２に対して０．００２モルから０．２モルであること
が好ましい。[0013] Furthermore, when the amount of solid acid added is 1 mol of LiCo
Preferably, the amount is from 0.002 mol to 0.2 mol relative to O2.
【００１４】[0014]
【作用】この構成により、本発明の非水電解液二次電池
は、非水電解液二次電池内部における固体酸の働きはア
ルカリとの高い反応性を挙げることができる。[Function] With this structure, in the non-aqueous electrolyte secondary battery of the present invention, the solid acid inside the non-aqueous electrolyte secondary battery has high reactivity with alkali.
【００１５】本発明における正極活物質ＬｉＣｏＯ２に
混在する可能性のあるＬｉＯＨなどのアルカリへの作用
を考えることができる。正極中に固体酸を添加すること
により、残留アルカリを減少させることが可能で、残留
アルカリが原因と考えられる高温保存による電池性能の
低下を軽減できる。[0015] In the present invention, the effect on alkali such as LiOH that may be mixed in the positive electrode active material LiCoO2 can be considered. By adding a solid acid to the positive electrode, it is possible to reduce residual alkali, and it is possible to reduce the decrease in battery performance due to high temperature storage, which is thought to be caused by residual alkali.
【００１６】[0016]
【実施例】以下、本発明の実施例の非水電解液二次電池
について図面を基にして説明する。[Embodiments] Hereinafter, non-aqueous electrolyte secondary batteries according to embodiments of the present invention will be described with reference to the drawings.
【００１７】（実施例１）電池の製造は次のようにして
行う。正極活物質としてＬｉＣｏＯ２ １００ｇに導
電剤としてアセチレンブラック ３．０ｇを混合し、
さらに、無水ＳｉＯ２３．０８ｇ（ＬｉＣｏＯ２ １
モルに対して０．０５モル）を添加、混合し、さらに、
結着剤としてのポリ４弗化エチレン樹脂４．０ｇを混合
して正極合剤とした。正極合剤０．１グラムを直径１７
．５ｍｍに１トン／ｃｍ２でプレス成型して、正極とし
た。図１において、成型した正極１をケース２に置く。
正極１の上にセパレータ３としての多孔性ポリプロピレ
ンフィルムを置いた。負極４として直径１７．５ｍｍ厚
さ０．３ｍｍのリチウム板を、ポリプロピレン製ガスケ
ット６を付けた封口板５に圧着した。(Example 1) A battery was manufactured as follows. 100 g of LiCoO2 as a positive electrode active material and 3.0 g of acetylene black as a conductive agent were mixed,
Furthermore, anhydrous SiO23.08g (LiCoO2 1
0.05 mol to mol) is added and mixed, and further,
A positive electrode mixture was prepared by mixing 4.0 g of polytetrafluoroethylene resin as a binder. 0.1 gram of positive electrode mixture in diameter 17
．． The positive electrode was press-molded to 5 mm at 1 ton/cm2. In FIG. 1, a molded positive electrode 1 is placed in a case 2. A porous polypropylene film as a separator 3 was placed on the positive electrode 1 . A lithium plate having a diameter of 17.5 mm and a thickness of 0.3 mm was press-bonded to a sealing plate 5 equipped with a polypropylene gasket 6 as the negative electrode 4.
【００１８】非水電解液として、プロピレンカーボネー
ト溶液に１モル／ｌの過塩素酸リチウムを溶解したもの
を用いた。このようにして得た非水電解液をセパレータ
３上および負極４上に加えた。その後ケース２の上縁部
をかしめて電池を封口した。The non-aqueous electrolyte used was a propylene carbonate solution in which 1 mol/l of lithium perchlorate was dissolved. The non-aqueous electrolyte thus obtained was added onto the separator 3 and the negative electrode 4. Thereafter, the upper edge of the case 2 was caulked to seal the battery.
【００１９】さらに、無水ＳｉＯ２の正極活物質に対す
る添加濃度（正極活物質に対するモル比）についても検
討を行い、その添加濃度範囲は（表１）に示した。Furthermore, the concentration of anhydrous SiO2 added to the positive electrode active material (molar ratio to the positive electrode active material) was also investigated, and the range of the added concentration is shown in (Table 1).
【００２０】比較のため、無水ＳｉＯ２を添加しない正
極について上記と同様な方法で電池を製造した。For comparison, a battery was manufactured in the same manner as above using a positive electrode to which anhydrous SiO2 was not added.
【００２１】電池の高温保存試験を次の方法で行う。す
なわち、上記の方法で得られた電池について、２０℃に
おいて１ｍＡの定電流で４．２ボルトまで充電し、次い
でこれを３ボルトまで放電した。この充電放電を１０サ
イクル行った後、１１サイクル目の充電が終わった後、
６０℃で４週間保存した。保存後２０℃に戻し、同じ条
件で放電した。ここで、容量維持率は次のように定義し
た。[0021] A high temperature storage test of the battery is carried out in the following manner. That is, the battery obtained by the above method was charged to 4.2 volts at a constant current of 1 mA at 20° C., and then discharged to 3 volts. After performing this charging and discharging for 10 cycles, after the 11th cycle of charging is completed,
It was stored at 60°C for 4 weeks. After storage, it was returned to 20°C and discharged under the same conditions. Here, the capacity maintenance rate was defined as follows.
【００２２】
容量維持率＝１００×１１サイクル目の放電電気量／１
０サイクル目の放電電気量
また、保存終了後に充電を行い、その後の放電容量を評
価した。[0022] Capacity maintenance rate = 100 x amount of discharged electricity at 11th cycle/1
The amount of electricity discharged at the 0th cycle was also charged after storage, and the subsequent discharge capacity was evaluated.
【００２３】ここで、容量回復率を次のように定義した
。
容量回復率＝１００×１２サイクル目の放電電気量／１
０サイクル目の放電電気量
上記各電池の６０℃４週間保存にともなう電池内部抵抗
の変化を示す図２において、内部抵抗は電池電圧をバイ
アス電圧とし、１．０ｋＨｚにおいて振幅１００ｍＶの
条件で２０℃において測定した。[0023] Here, the capacity recovery rate is defined as follows. Capacity recovery rate = 100 x amount of discharged electricity at 12th cycle/1
Discharge amount of electricity at 0th cycle In Figure 2, which shows the change in battery internal resistance of each of the above batteries as they were stored at 60°C for 4 weeks, the internal resistance was measured at 20°C with the battery voltage as the bias voltage and an amplitude of 100 mV at 1.0 kHz. Measured at.
【００２４】無水ＳｉＯ２を添加しない電池では、保存
直後から急激な電池内部抵抗の増加が認められ、４週間
後には３０Ω以上になる。一方、実施例の電池において
は、電池内部抵抗の増加は小さいものである。[0024] In a battery to which anhydrous SiO2 is not added, a rapid increase in battery internal resistance is observed immediately after storage, and after 4 weeks it reaches 30Ω or more. On the other hand, in the battery of the example, the increase in battery internal resistance is small.
【００２５】また、（表１）には、各電池の正極合剤１
ｇ当りの初期放電容量および４週間後の容量維持率，容
量回復率を示す。In addition, (Table 1) shows the positive electrode mixture 1 of each battery.
The initial discharge capacity per gram, the capacity retention rate after 4 weeks, and the capacity recovery rate are shown.
【００２６】[0026]
【表１】[Table 1]
【００２７】無水ＳｉＯ２を添加しない電池では、６０
℃４週間保存にともない非常に大きな容量低下を示す。
一方、無水ＳｉＯ２を添加した電池では容量維持率およ
び容量回復率が高い。しかし、電池の初期容量は無水Ｓ
ｉＯ２の添加量が０．２モルを越えると急激に減少して
いる。したがって、特に容量維持率が８０％以上で、容
量回復率が８５％以上であった無水ＳｉＯ２の添加濃度
０．００２〜０．２モルの範囲が望ましいことがわかっ
た。このように正極への無水ＳｉＯ２の添加は高温保存
にともなう容量低下を抑制する効果がある。[0027] In a battery without adding anhydrous SiO2, 60
After storage for 4 weeks at ℃, there is a very large decrease in capacity. On the other hand, a battery containing anhydrous SiO2 has a high capacity retention rate and a high capacity recovery rate. However, the initial capacity of the battery is anhydrous S
When the amount of iO2 added exceeds 0.2 mol, it decreases rapidly. Therefore, it has been found that it is particularly desirable that the concentration of anhydrous SiO2 added is in the range of 0.002 to 0.2 mol, so that the capacity retention rate is 80% or more and the capacity recovery rate is 85% or more. As described above, the addition of anhydrous SiO2 to the positive electrode has the effect of suppressing the capacity decrease due to high temperature storage.
【００２８】（実施例２）つぎに、Ａｌ２Ｏ３について
の検討を行った。(Example 2) Next, a study was conducted on Al2O3.
【００２９】電池の製造および高温保存試験は実施例１
と同様に行った。上記各電池の６０℃４週間保存にとも
なう電池内部抵抗の変化を示す図３において、Ａｌ２Ｏ
３を添加しない電池では、保存直後から急激な電池内部
抵抗の増加が認められ、４週間後には３０Ω以上になる
。
一方、実施例の電池においては、電池内部抵抗の増加は
小さいものである。[0029] Battery manufacturing and high temperature storage test were carried out in Example 1.
I did the same thing. In Figure 3, which shows the change in battery internal resistance as each of the above batteries was stored at 60°C for 4 weeks, Al2O
In the battery to which No. 3 was not added, a rapid increase in battery internal resistance was observed immediately after storage, and it reached 30Ω or more after 4 weeks. On the other hand, in the battery of the example, the increase in battery internal resistance is small.
【００３０】また、（表２）には、各電池の正極合剤１
ｇ当りの初期放電容量および４週間後の容量維持率，容
量回復率を示す。In addition, (Table 2) shows the positive electrode mixture 1 of each battery.
The initial discharge capacity per gram, the capacity retention rate after 4 weeks, and the capacity recovery rate are shown.
【００３１】[0031]
【表２】[Table 2]
【００３２】Ａｌ２Ｏ３を添加しない電池では、６０℃
４週間保存にともない非常に大きな容量低下を示すが、
Ａｌ２Ｏ３を添加した電池では容量維持率および容量回
復率が高い。しかし、電池の初期容量はＡｌ２Ｏ３の添
加量が０．２モルを越えると急激に減少している。した
がって、特に容量維持率が７５％以上で、容量回復率が
８０％以上であったＡｌ２Ｏ３の添加濃度０．００２〜
０．２モルの範囲が望ましいことがわかった。このよう
に正極へのＡｌ２Ｏ３の添加は高温保存にともなう容量
低下を抑制する効果がある。[0032] In the battery without adding Al2O3, the temperature is 60°C.
After storage for 4 weeks, the capacity decreases significantly.
Batteries containing Al2O3 have high capacity retention and capacity recovery rates. However, the initial capacity of the battery decreases rapidly when the amount of Al2O3 added exceeds 0.2 mol. Therefore, in particular, the concentration of Al2O3 added was 0.002 to 0.002 with a capacity retention rate of 75% or more and a capacity recovery rate of 80% or more.
A range of 0.2 moles has been found to be desirable. As described above, the addition of Al2O3 to the positive electrode has the effect of suppressing the capacity decrease due to high temperature storage.
【００３３】また、固体酸として、Ｖ２Ｏ５，ＩｒＯ２
を用いた場合にも同様の効果が認められた。[0033] Also, as solid acids, V2O5, IrO2
A similar effect was observed when using .
【００３４】検討した固体酸の中では高温保存特性への
効果は無水ＳｉＯ２の場合に最も顕著であった。Among the solid acids examined, the effect on high-temperature storage properties was most remarkable in the case of anhydrous SiO2.
【００３５】以上のように、ＬｉＣｏＯ２で表わされる
複合酸化物を正極活物質とする非水電解液電池において
、正極中に固体酸を添加することにより、高温保存特性
に優れた非水電解液二次電池を得ることができる。As described above, in a non-aqueous electrolyte battery using a composite oxide represented by LiCoO2 as a positive electrode active material, by adding a solid acid to the positive electrode, a non-aqueous electrolyte battery with excellent high-temperature storage characteristics can be obtained. You can get the next battery.
【００３６】さらに、これらの固体酸を混合して添加し
た場合にも同様の効果が認められた。Furthermore, similar effects were observed when a mixture of these solid acids was added.
【００３７】以上の実施例では、電解液として１モル／
ｌの過塩素酸リチウムを溶解したプロピレンカーボネー
ト溶液を用いた場合の結果であるが、電解液としてこれ
以外に、溶質として６フッ化燐酸リチウムやトリフロロ
メタンスルフォン酸リチウム，ホウフッ化リチウム、溶
媒としてプロピレンカーボネート，エチレンカーボネー
トなどのカーボネート類、ガンマーブチロラクトン，酢
酸メチルなどのエステル類を用いた電解液が良好であっ
た。しかしながら、ジメトキシエタンやテトラヒドロフ
ランなどのエーテル類を使用した場合には、高温保存特
性は悪く、電解液中にルイス酸を添加することにより高
温保存特性の向上は認められなかった。実施例では正極
は４Ｖ以上の電圧となるため、エーテル類は酸化される
ためと考えている。[0037] In the above examples, the electrolyte was 1 mol/
These are the results when using a propylene carbonate solution in which 1 liter of lithium perchlorate was dissolved, but in addition to this as an electrolyte, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium borofluoride were used as a solute, and as a solvent. Electrolytes using carbonates such as propylene carbonate and ethylene carbonate, and esters such as gamma butyrolactone and methyl acetate were good. However, when ethers such as dimethoxyethane and tetrahydrofuran were used, the high-temperature storage properties were poor, and no improvement in the high-temperature storage properties was observed by adding a Lewis acid to the electrolyte. It is thought that this is because in the example, the positive electrode has a voltage of 4V or more, so the ethers are oxidized.
【００３８】[0038]
【発明の効果】以上の実施例の説明で明らかなように本
発明の非水電解液二次電池によれば、リチウムを吸蔵放
出できる負極、ＬｉＣｏＯ２で表わされる複合酸化物を
活物質とする正極および非水電解液を有し、前記正極中
に固体酸を添加したものを用いることにより高温保存特
性が良好な非水電解液二次電池を得ることができ、産業
上の意義は大きい。Effects of the Invention As is clear from the description of the embodiments above, the non-aqueous electrolyte secondary battery of the present invention has a negative electrode capable of intercalating and deintercalating lithium, and a positive electrode having a composite oxide represented by LiCoO2 as an active material. By using a positive electrode having a non-aqueous electrolyte and a solid acid added to the positive electrode, a non-aqueous electrolyte secondary battery with good high-temperature storage characteristics can be obtained, which is of great industrial significance.
【図１】本発明の実施例の非水電解液二次電池の縦断面
図[Fig. 1] A vertical cross-sectional view of a non-aqueous electrolyte secondary battery according to an embodiment of the present invention.
【図２】同実施例１の電池の６０℃保存にともなう電池
内部抵抗の変化を示したグラフ[Figure 2] Graph showing changes in battery internal resistance as the battery of Example 1 is stored at 60°C
【図３】同実施例２の電池の６０℃保存にともなう電池
内部抵抗の変化を示したグラフ[Figure 3] Graph showing changes in battery internal resistance as the battery of Example 2 is stored at 60°C
１ 正極 ２ ケース ３ セパレータ ４ 負極 ５ 封口板 ６ ガスケット 1 Positive electrode 2 Case 3 Separator 4 Negative electrode 5 Sealing plate 6 Gasket
Claims (3)
物質とする正極と、リチウムを吸蔵放出することのでき
る負極および非水電解液を有し、前記正極中に固体酸を
添加した非水電解液二次電池。1. A non-aqueous electrolyte comprising a positive electrode using a composite oxide represented by LiCoO2 as an active material, a negative electrode capable of intercalating and deintercalating lithium, and a non-aqueous electrolyte, with a solid acid added to the positive electrode. Liquid secondary battery.
Ｏ５，ＩｒＯ２から選ばれる少なくとも１つである請求
項１記載の非水電解液二次電池。Claim 2: The solid acid is anhydrous SiO2, Al2O3, V2
The non-aqueous electrolyte secondary battery according to claim 1, wherein the non-aqueous electrolyte is at least one selected from O5 and IrO2.
対して０．００２モルから０．２モルである請求項１記
載の非水電解液二次電池。3. The non-aqueous electrolyte secondary battery according to claim 1, wherein the amount of the solid acid added is from 0.002 mol to 0.2 mol per 1 mol of LiCoO2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12732091A JP3245886B2 (en) | 1991-05-30 | 1991-05-30 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12732091A JP3245886B2 (en) | 1991-05-30 | 1991-05-30 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04355056A true JPH04355056A (en) | 1992-12-09 |
| JP3245886B2 JP3245886B2 (en) | 2002-01-15 |
Family
ID=14957019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12732091A Expired - Fee Related JP3245886B2 (en) | 1991-05-30 | 1991-05-30 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3245886B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6753112B2 (en) | 2000-12-27 | 2004-06-22 | Kabushiki Kaisha Toshiba | Positive electrode active material and non-aqueous secondary battery using the same |
| JP2005093371A (en) * | 2003-09-19 | 2005-04-07 | Toshiba Corp | Nonaqueous electrolyte secondary battery |
| JP2006261132A (en) * | 2006-05-17 | 2006-09-28 | Nichia Chem Ind Ltd | Positive electrode active material for lithium secondary battery and its manufacturing method |
| JP2010003642A (en) * | 2008-06-23 | 2010-01-07 | Tdk Corp | Electrode, lithium-ion secondary battery, and method for manufacturing electrode |
| US7799462B2 (en) | 2005-10-26 | 2010-09-21 | Lg Chem, Ltd. | Mixture for anode of improved adhesive strength and lithium secondary battery containing the same |
| JP2014186837A (en) * | 2013-03-22 | 2014-10-02 | Toyota Industries Corp | Positive electrode for lithium ion secondary battery and lithium ion secondary battery |
| WO2018123671A1 (en) * | 2016-12-28 | 2018-07-05 | パナソニックＩｐマネジメント株式会社 | Nonaqueous electrolyte secondary battery positive electrode and nonaqueous electrolyte secondary battery |
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1991
- 1991-05-30 JP JP12732091A patent/JP3245886B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6753112B2 (en) | 2000-12-27 | 2004-06-22 | Kabushiki Kaisha Toshiba | Positive electrode active material and non-aqueous secondary battery using the same |
| JP2005093371A (en) * | 2003-09-19 | 2005-04-07 | Toshiba Corp | Nonaqueous electrolyte secondary battery |
| JP4503964B2 (en) * | 2003-09-19 | 2010-07-14 | 株式会社東芝 | Nonaqueous electrolyte secondary battery |
| US7799462B2 (en) | 2005-10-26 | 2010-09-21 | Lg Chem, Ltd. | Mixture for anode of improved adhesive strength and lithium secondary battery containing the same |
| JP2006261132A (en) * | 2006-05-17 | 2006-09-28 | Nichia Chem Ind Ltd | Positive electrode active material for lithium secondary battery and its manufacturing method |
| JP4736943B2 (en) * | 2006-05-17 | 2011-07-27 | 日亜化学工業株式会社 | Positive electrode active material for lithium secondary battery and method for producing the same |
| JP2010003642A (en) * | 2008-06-23 | 2010-01-07 | Tdk Corp | Electrode, lithium-ion secondary battery, and method for manufacturing electrode |
| JP2014186837A (en) * | 2013-03-22 | 2014-10-02 | Toyota Industries Corp | Positive electrode for lithium ion secondary battery and lithium ion secondary battery |
| WO2018123671A1 (en) * | 2016-12-28 | 2018-07-05 | パナソニックＩｐマネジメント株式会社 | Nonaqueous electrolyte secondary battery positive electrode and nonaqueous electrolyte secondary battery |
| JPWO2018123671A1 (en) * | 2016-12-28 | 2019-10-31 | パナソニックＩｐマネジメント株式会社 | Positive electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3245886B2 (en) | 2002-01-15 |
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