JPH01134863A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPH01134863A JPH01134863A JP62291105A JP29110587A JPH01134863A JP H01134863 A JPH01134863 A JP H01134863A JP 62291105 A JP62291105 A JP 62291105A JP 29110587 A JP29110587 A JP 29110587A JP H01134863 A JPH01134863 A JP H01134863A
- Authority
- JP
- Japan
- Prior art keywords
- chromium oxide
- particle size
- charging
- particle
- alkali metal
- 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 7
- 239000002245 particle Substances 0.000 claims abstract description 59
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 30
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 9
- 239000011651 chromium Substances 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 11
- 238000005336 cracking Methods 0.000 abstract description 5
- 230000006866 deterioration Effects 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 2
- 229910019923 CrOx Inorganic materials 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- -1 Cr30s*Cr20s Chemical class 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium dioxide Chemical compound O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001786 chalcogen compounds Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、非水電解質二次電池、特に、その正極の改良
に関する０
従来の技術
非水電解質二次電池の正極活物質については、これまで
、Ｔ ｉ 、’Ｖ 、Ｃｒ 、Ｍｏ等の層状もしくはト
ンネル構造を有する酸化物及びカルコゲン化合物が知ら
れている。これらの中で、特に、Ｃｒ３Ｏ８゜Ｃｒ２Ｏ
５等のクロム酸化物は、高エネルギー密度を有する活物
質として開示されている〔ヨツト・オー・ベーゼンハル
ト他、ジャーナル・エレクトロケミカル・ソサエテー、
１２４ 、９６８ 、（１９７７））。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to non-aqueous electrolyte secondary batteries, and in particular to improvements in positive electrodes. Oxides and chalcogen compounds having layered or tunnel structures such as Ti, 'V, Cr, Mo, etc. are known. Among these, especially Cr3O8゜Cr2O
Chromium oxides such as No. 5 have been disclosed as active materials with high energy density [Jord O. Bösenhard et al., Journal Electrochemical Society,
124, 968, (1977)).
Ｃｒ５ｏ８．Ｃｒ２Ｏ５等のクロム酸化物は、通常、Ｃ
ｒ Ｏ３の熱分解′によって製造される。たとえば、大
気圧下ではＣｒ５Ｑ８は約２６０〜３ｏＯｏＣ１Ｃｒ２
ｏ５は約３００〜３６０°Ｃの温度範囲で得ることがで
きる。この過程で、原料のＣｒＯ２は約２００ ’（：
、で融解し、融解状態のＣｒ Ｏ３が徐々に酸素を放出
することにより、Ｃｒ５ｏ８．Ｃｒ２０６等の酸化物が
生生ずる。この融解状態のＣｒ ＯａからＣｒ３Ｏ８，
Ｃｒ２０６等が形成される温度へ昇温する場合、昇温速
度が大きいとＣｒ Ｏ３の蒸気が飛散するため、公害性
という面から昇温速度は約２℃／ｍ ｉ ｎ以下に制御
される。以上のようにして得られたクロム酸化物はいず
れも緊密な塊状物となるため、Ｃｒ Ｏ３の熱分解過程
の後、生成したクロム酸化物は粉砕工程を経て電池の正
極活物質として使用される。ここで、粉砕後のクロム酸
化物の粉末の平均粒度は、通常、３〜６０μｍの範囲に
またがる。Cr5o8. Chromium oxides such as Cr2O5 usually contain C
Produced by pyrolysis of rO3. For example, under atmospheric pressure, Cr5Q8 is approximately 260~3oOoC1Cr2
o5 can be obtained at a temperature range of about 300-360°C. In this process, the raw material CrO2 is about 200' (:
, and the molten CrO3 gradually releases oxygen to form Cr5o8. Oxides such as Cr206 are generated. From this molten Cr Oa to Cr3O8,
When increasing the temperature to a temperature at which Cr206 and the like are formed, if the temperature increase rate is high, CrO3 vapor will scatter, so the temperature increase rate is controlled to about 2° C./min or less from the viewpoint of pollution. All of the chromium oxides obtained in the above manner form tight lumps, so after the thermal decomposition process of CrO3, the produced chromium oxides undergo a pulverization process and are used as positive electrode active materials for batteries. . Here, the average particle size of the chromium oxide powder after crushing usually ranges from 3 to 60 μm.
発明が解決しようとする問題点
しかし、このようにして得たクロム酸化物粉末を正極に
用い、Ｌｉ等のアルカリ金属を負極に用いた非水電解質
二次電池を構成し充放電をくり返した場合、充放電サイ
クルでの容量劣化が著しいという問題点があった。これ
は下記の理由による。Problems to be Solved by the Invention However, when a non-aqueous electrolyte secondary battery is constructed using the chromium oxide powder thus obtained as the positive electrode and an alkali metal such as Li as the negative electrode, and the battery is repeatedly charged and discharged. However, there was a problem in that the capacity deteriorated significantly during charge/discharge cycles. This is due to the following reasons.
Ｃｒ３０ｓ ＊ Ｃｒ ２０ ｓ等のクロム酸化物では
、放電・充電過程でＬｉ＋等のアルカリ金属イオンが酸
化物結晶格子内へ侵入又は格子内から放出される。In chromium oxides such as Cr30s*Cr20s, alkali metal ions such as Li+ enter or are released from the oxide crystal lattice during the discharging and charging processes.
このためクロム酸化物粒子は充放電過程で膨張。For this reason, chromium oxide particles expand during the charging and discharging process.
収縮をくり返す。この膨張、収縮の度合は約３０係もの
体積変化である。Ｃｒ ｓｏ ａ 、Ｃｒ２Ｏ５等のク
ロム酸化物結晶格子内でのＬｉ＋等のアルカリ金属イオ
ンの拡散係数は１ｏ−” ｃｒ！／ｓｅｃ と他の層状
又はトンネル化合物に比べ３桁小さい。このため、充放
電反応はクロム酸化物粒子の表面近傍でのみ起こること
になシ、Ｌｉ＋等が侵入した粒子の表面近傍では粒子の
著しい膨張があるのに対し、イオンが侵入していない粒
子内部では膨張が見られない〇したがって、充放電をく
り返すとクロム酸化物粒子は表面からひび割れを生じ分
離していく。Repeat contractions. The degree of expansion and contraction is a volume change of about 30 factors. The diffusion coefficient of alkali metal ions such as Li+ within the crystal lattice of chromium oxides such as Cr so a and Cr2O5 is 1o-" cr!/sec, which is three orders of magnitude smaller than that of other layered or tunnel compounds. The reaction occurs only near the surface of the chromium oxide particles, and while there is significant expansion of the particles near the surface where Li+ etc. have entered, no expansion is observed inside the particles where no ions have entered. No〇 Therefore, when charging and discharging are repeated, the chromium oxide particles crack and separate from the surface.
Ｃｒ３Ｏ８やＣｒ２Ｏ５等のクロム酸化物は電子伝導性
に乏しいため、正極板内に混合されている導電剤のカー
ボンブラック粒子等に接触しているクロム酸化物粒子以
外、充放電過程で分離したクロム酸化物は充放電に寄与
できなくなる。充放電をくり返すと分離し充放電に寄与
できなくなるクロム酸化物の量は増加するだめ、充放電
サイクルでの容量劣化が著しくなるのである。Since chromium oxides such as Cr3O8 and Cr2O5 have poor electronic conductivity, chromium oxide particles separated during the charging and discharging process, other than the chromium oxide particles that are in contact with the carbon black particles of the conductive agent mixed in the positive electrode plate, Objects can no longer contribute to charging and discharging. As charging and discharging are repeated, the amount of chromium oxide that separates and becomes unable to contribute to charging and discharging increases, resulting in significant capacity deterioration during charging and discharging cycles.
そこで本発明は、正極活物質にクロム酸化物（Ｃｒｙｘ
、２．７≧Ｘ≧２．６）を用いても、充放電サイクルに
ともなう容量劣化が小さい非水電解質二次電池を提供す
ることを目的とする。Therefore, the present invention uses chromium oxide (Cryx) as the positive electrode active material.
, 2.7 ≧
問題点を解決するための手段
以上のような問題点を解決するため、本発明は、平均粒
度が１．７μｍ以下であるクロム酸化物粉末を正極活物
質に用いることを特徴とするものである。Means for Solving the Problems In order to solve the above-mentioned problems, the present invention is characterized in that a chromium oxide powder having an average particle size of 1.7 μm or less is used as a positive electrode active material. .
作 用
クロム酸化物粒子の粒径が極めて小さい場合、充放電過
程では、Ｌｉ＋等のアルカリ金属イオンは粒子内奥部に
まで拡散することになり、粒子は表面から内部まで均一
に膨張、収縮する。したがって、クロム酸化物粒子の表
面からのひび割れ、分離を阻止することができる。Effect When the particle size of chromium oxide particles is extremely small, alkali metal ions such as Li+ will diffuse deep into the particles during the charging and discharging process, and the particles will expand and contract uniformly from the surface to the inside. . Therefore, cracking and separation of the chromium oxide particles from the surface can be prevented.
クロム酸化物粒子の粒径がやや大きくなり、充放電過程
でＬｉ＋等のアルカリ金属イオンの粒子内奥部までの拡
散が困難となり反応が粒子表面近傍のみで起こるように
なった場合でも、粒子表面層全体にアルカリ金属イオン
が拡散しうる程度の粒径であれば、表面層は均一に膨張
、収縮することができ、粒子の表面からのひび割れが抑
制される。Even if the particle size of the chromium oxide particles becomes slightly larger and it becomes difficult for alkali metal ions such as Li+ to diffuse deep inside the particles during the charging and discharging process, and the reaction occurs only near the particle surface, If the particle size is large enough to allow alkali metal ions to diffuse throughout the layer, the surface layer can expand and contract uniformly, and cracks from the surface of the particles can be suppressed.
しかし、クロム酸化物粒子の粒径が極めて大きい場合、
充放電過程でのＬｉ＋等のアルカリ金属イオンの拡散は
、正極板内に混合されている導電剤のカーボンブラック
粒子等がクロム酸化物粒子に接触している近傍のみにな
るため、クロム酸化物粒子の膨張、収縮は不均一になり
、充放電をくり返すと粒子のひび割れ、分離が著しくな
る。However, when the particle size of chromium oxide particles is extremely large,
During the charging and discharging process, alkali metal ions such as Li+ diffuse only in the vicinity where the carbon black particles, etc. of the conductive agent mixed in the positive electrode plate, are in contact with the chromium oxide particles. The expansion and contraction of the particles become uneven, and when charging and discharging are repeated, cracking and separation of particles becomes noticeable.
以上のようなりロム酸化物粒子の充放（過程でのひび割
れ、分離は、クロム酸化物の平均粒度が１．７μｍ以下
であれば抑制することができる。なお、ここでの平均粒
度は次式で定義される算術平均径である。As described above, the filling (cracking and separation during the process) of chromium oxide particles can be suppressed if the average particle size of chromium oxide is 1.7 μm or less.The average particle size here is calculated using the following formula: is the arithmetic mean diameter defined by
ｄａ・・・・・・平均粒度 ｄ、・・・・・・個々の粒子の粒子径 ｎ、・・・・・・粒子径ｄ、の粒子数 以下、本発明の実施例を示す。da・・・・・・Average particle size d, ...Particle diameter of individual particles n, ... Number of particles with particle diameter d, Examples of the present invention will be shown below.
実施例
種々の平均粒度を五するクロム阪化物は以下のようにし
て作製した。EXAMPLE Chromium peroxides having various average particle sizes were prepared as follows.
Ｃｒ Ｏ３を約２００’Ｃで融解した後、Ｃｒ３Ｏ８を
作製する場合には２ａｏ’ｃ、Ｃｒ２Ｏ５を作製する場
合には３２０°Ｃの温度まで約７’Ｃ／ｆｎｉｎで昇温
し、各温度で約８時間保った。昇温速度が約７°Ｃ／ｍ
ｉｎ以上では、融解しているＣ ｒ Ｏ３は沸騰状、１
πになると同時に、Ｃｒ Ｏｓの熱分解によシ酸素ガス
が急激に放出されるため、生成した塊状のクロム酸化物
は、空隙の多いスポンジ状であった。このようにして得
られたクロム酸化物は容易に平均粒度を１〜２μｍまで
粉砕することが可能であり、粉砕時間を調整することで
種々の平均粒度をもつクロム酸化物を作製した。After melting CrO3 at about 200'C, the temperature is raised at about 7'C/fnin to a temperature of 2ao'c when producing Cr3O8 and 320°C when producing Cr2O5, and at each temperature. It lasted about 8 hours. Temperature increase rate is approximately 7°C/m
Above in, the melted C r O3 is boiling, 1
At the same time as the temperature reaches π, oxygen gas is rapidly released by thermal decomposition of CrOs, so the resulting lumpy chromium oxide was sponge-like with many voids. The chromium oxide thus obtained can be easily ground to an average particle size of 1 to 2 μm, and by adjusting the grinding time, chromium oxides having various average particle sizes were produced.
充放電試験はすべて第４図に示すような扁平型電池で行
なった。All charging and discharging tests were conducted using flat batteries as shown in FIG.
扁平型電池の作製は次のように行なった。The flat battery was manufactured as follows.
上記のように作製したクロム酸化物粉末とカーボンブラ
ック、四沸化エチレン樹脂を重量比で７０対２０対１ｏ
の割合で混合し、混合物５０１１Ｑをとり、正極集電体
１をスポット溶接した電池ケース２内へ直接１７．５１
１に正極板３を成型した。The weight ratio of the chromium oxide powder prepared above, carbon black, and tetrafluoroethylene resin is 70:20:10.
Take the mixture 5011Q and directly put it into the battery case 2 to which the positive electrode current collector 1 was spot welded 17.51
A positive electrode plate 3 was molded on 1.
負極にはリチウムを用い、厚さ３８０μｍのリチウムシ
ートを直径１７１Ｂのディスクに打ち抜き、負極集電体
４をスポット溶接した封口板６に圧着した。Lithium was used as the negative electrode, and a lithium sheet with a thickness of 380 μm was punched out into a disk with a diameter of 171 B, and the negative electrode current collector 4 was pressure-bonded to a spot-welded sealing plate 6.
セパレータ６には、ポリプロピレン不織布を用い、電解
液には、プロピレンカーボネートとジメトキシエタンを
等体積で混合したものに、Ｌｉｃｋ○４を１Ｍ／ｌの割
合で溶解したものを用いた。The separator 6 was made of polypropylene nonwoven fabric, and the electrolytic solution was a mixture of propylene carbonate and dimethoxyethane in equal volumes, in which Lick○4 was dissolved at a ratio of 1 M/l.
−このように作製した扁平型電池を用いて、２ｍＡの定
電流、充電上限電圧３．９Ｖ、放電下限電圧１．６■の
条件で充放電試験を行なった。- Using the flat battery thus prepared, a charge/discharge test was conducted under the conditions of a constant current of 2 mA, an upper limit charge voltage of 3.9 V, and a lower limit discharge voltage of 1.6 .
第３図はクロム酸化物にＣｒ３Ｏ８を用いた場合で、本
発明の実施例として平均粒度が１．４μｍのもの（実線
）、比較例として平均粒度が３．０μｍのもの（破線）
における各充放電サイクルでの放電容量をプロットした
図である。第３図より本発明の実施例では、比較例に対
し充放電サイクルでの容量劣化が小さいことがわかる。Figure 3 shows the case where Cr3O8 is used as the chromium oxide, with an example of the present invention having an average particle size of 1.4 μm (solid line), and a comparative example having an average particle size of 3.0 μm (dashed line).
It is a figure which plotted the discharge capacity in each charge-discharge cycle in . From FIG. 3, it can be seen that in the examples of the present invention, capacity deterioration during charge/discharge cycles is smaller than in the comparative examples.
ここで、容量維持率を次式のように定義する。Here, the capacity maintenance rate is defined as the following equation.
第１図はＣｒ３Ｏ８において平均粒度に対して容量維持
率をプロットした図であり、第２図は同様にＣｒ ２０
５の場合である。第１図および第２図よりＣＴａ Ｏｓ
、 Ｃｒ ２０ ｓのいずれにおいても、平均粒度が
１．７μｍを超えると容量維持率が急激に減少する。す
なわち、充放電サイクルでの容量劣化が大きくなること
がわかる。なお、Ｃｒ５ｏ５．Ｃｒ２０６の両者におい
て、平均粒度がいずれの場合でも１．７μｍを超えたと
ころで容量維持率が低下するのは、両者におけるＬｉ＋
の拡散係数がほぼ等しいことによる。Figure 1 is a diagram plotting the capacity retention rate against the average particle size for Cr3O8, and Figure 2 is a diagram plotting the capacity retention rate against the average particle size for Cr3O8.
This is the case of 5. From Figures 1 and 2, CTa Os
, Cr 20 s, when the average particle size exceeds 1.7 μm, the capacity retention rate decreases rapidly. That is, it can be seen that capacity deterioration during charge/discharge cycles increases. In addition, Cr5o5. In both cases of Cr206, the capacity retention rate decreases when the average particle size exceeds 1.7 μm in both Li+
This is due to the fact that their diffusion coefficients are almost equal.
発明の効果
以上のように本発明は、クロム酸化物の平均粒度を１．
７μｍ以下にしているため、充放電をくり返しても容量
劣化の小さい、信頼性の高い非水電解質二次電池を得る
ことができる。Effects of the Invention As described above, the present invention reduces the average particle size of chromium oxide to 1.
Since the thickness is 7 μm or less, it is possible to obtain a highly reliable non-aqueous electrolyte secondary battery with little capacity deterioration even after repeated charging and discharging.
第１図はＣｒ ｓＯｓにおいて平均粒度に対して容量維
持率をプロットした図、第２図はＣｒ２０６の平均粒度
に対する容量維持率を示す特性図、第３図は本発明の実
施例及び比較例の電池における充放電サイクルでの放電
容量特性図、第４図は本発明の実施例及び比較例にもち
いた扁平型電池の断面図である。
１・・・・・・正極集電体、２・・・・・・電池ケース
、３・・・・・・正極板、４・・・・・・負極集電体、
６・・・・・・封口板、６・・・・・・セパレータ。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名容量
雄特！！Ｐ（％）
む Ｂ
容量蛤将争（ｙ、）
税 も
丞電客量Ｃ＝ｇＡ＾） ８Figure 1 is a diagram plotting the capacity retention rate against the average particle size in Cr sOs, Figure 2 is a characteristic diagram showing the capacity retention rate against the average particle size of Cr206, and Figure 3 is a graph showing the capacity retention rate against the average particle size of Cr206. FIG. 4 is a sectional view of a flat type battery used in an example of the present invention and a comparative example. 1... Positive electrode current collector, 2... Battery case, 3... Positive electrode plate, 4... Negative electrode current collector,
6... Sealing plate, 6... Separator. Name of agent: Patent attorney Toshio Nakao and 1 other person: Capacity Yutoku! ! P (%) B Capacity war (y,) Tax Mojo electric customer volume C=gA^) 8
Claims (1)
点第２位を四捨五入する、ｘはＯ／Ｃｒ原子比を活物質
とする正極、アルカリ金属イオン導伝性の非水電解質、
及びアルカリ金属を活物質とする負極を構成要素とし、
前記クロム酸化物の平均粒度が１．７μｍ以下であるこ
とを特徴とする非水電解質二次電池。Chromium oxide (CrO_x, 2.7≧x≧2.5 rounded to the second decimal place, x is a positive electrode with an O/Cr atomic ratio as an active material, an alkali metal ion conductive nonaqueous electrolyte,
and a negative electrode containing an alkali metal as an active material,
A non-aqueous electrolyte secondary battery, wherein the chromium oxide has an average particle size of 1.7 μm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62291105A JPH01134863A (en) | 1987-11-18 | 1987-11-18 | Nonaqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62291105A JPH01134863A (en) | 1987-11-18 | 1987-11-18 | Nonaqueous electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01134863A true JPH01134863A (en) | 1989-05-26 |
Family
ID=17764515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62291105A Pending JPH01134863A (en) | 1987-11-18 | 1987-11-18 | Nonaqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01134863A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114467196A (en) * | 2019-10-04 | 2022-05-10 | 三洋电机株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
-
1987
- 1987-11-18 JP JP62291105A patent/JPH01134863A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114467196A (en) * | 2019-10-04 | 2022-05-10 | 三洋电机株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6223433B2 (en) | ||
| US5958622A (en) | Negative electrode material for lithium secondary batteries | |
| JPH0660887A (en) | Nonaqueous battery | |
| JPH11260400A (en) | Nonaqueous electrolyte secondary battery | |
| JP3440638B2 (en) | Non-aqueous electrolyte secondary battery | |
| JPH1186905A (en) | Nonaqueous electrolyte secondary battery | |
| JPH07201316A (en) | Nonaqueous electrolyte secondary battery | |
| JPH08250117A (en) | Carbon material for lithium secondary battery negative electrode, and manufacture thereof | |
| JP3641648B2 (en) | Lithium secondary battery | |
| JPH0821382B2 (en) | Non-aqueous electrolyte secondary battery | |
| JPH05307956A (en) | Nonaqueous group secondary battery | |
| JP3618492B2 (en) | Battery electrode material and secondary battery | |
| US20230261254A1 (en) | Solid-state electrolyte material comprising a chalcogenide-based ionic-conductive structure, particularly a sulfide-based ionic-conductive structure | |
| JPH01134863A (en) | Nonaqueous electrolyte secondary battery | |
| WO2022138451A1 (en) | Electrode, nonaqueous electrolyte battery, and battery pack | |
| JPS6259412B2 (en) | ||
| JPS6369154A (en) | Nonaqueous electrolyte secondary battery | |
| JPH06243870A (en) | Nonaqeous secondary battery | |
| JP3350114B2 (en) | Non-aqueous electrolyte secondary battery | |
| JPS61158665A (en) | Nonaqueous electrolyte secondary battery | |
| JP3152497B2 (en) | Non-aqueous electrolyte secondary battery | |
| JPH04188560A (en) | Manufacture of negative electrode for non-aqueous electrolyte secondary battery | |
| JPH05290845A (en) | Lithium battery | |
| JP2000235869A (en) | Nonaqueous electrolyte secondary battery | |
| JPH08138678A (en) | Positive electrode mix |