JPS6313268A - Battery active material - Google Patents
Battery active materialInfo
- Publication number
- JPS6313268A JPS6313268A JP61158549A JP15854986A JPS6313268A JP S6313268 A JPS6313268 A JP S6313268A JP 61158549 A JP61158549 A JP 61158549A JP 15854986 A JP15854986 A JP 15854986A JP S6313268 A JPS6313268 A JP S6313268A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- decomposition temperature
- battery active
- heat decomposition
- fluorine
- 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
- 239000011149 active material Substances 0.000 title claims abstract description 26
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 26
- 239000011737 fluorine Substances 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 25
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000012298 atmosphere Substances 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract 6
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 abstract 5
- 239000007789 gas Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000013256 coordination polymer Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000003682 fluorination reaction Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000004580 weight loss Effects 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明はある特定のフッ化黒鉛よりなる放電特性の改良
された電池活物質に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a battery active material with improved discharge characteristics, which is made of a specific fluorinated graphite.
［従来の技術］
黒鉛をフッ素化してえられるフッ化黒鉛として、今まで
式（ＣＰ）ｎで表されるものおよび式（Ｃ２Ｆ）１１で
表されるものが確認されており、またそれらは両者を含
む組成物の形態で存在することも知られている。しかし
、その実態は今だ不明な点が多い。このフッ素黒鉛が電
池活物質としてすぐれた特性を有することはつぎに述べ
るようによく知られている。[Prior Art] As fluorinated graphite obtained by fluorinating graphite, those represented by formula (CP)n and that represented by formula (C2F)11 have been confirmed so far, and both of them are It is also known to exist in the form of compositions containing. However, there are still many aspects of the situation that are unclear. It is well known that this fluorine graphite has excellent properties as a battery active material, as described below.
たとえば特公昭４８−２５５８５公報には、電池の正極
活物質として固体状のフッ化黒鉛（ＣＦｘ）ｎ （ただ
し０．５≦Ｘ≦１）、とくにＸが１または１に近いフッ
化黒鉛を用いることにより、活物質としての利用率が高
く、電圧の平坦性にすぐれ、かつ保存寿命の良好な高エ
ネルギー密度の一次電池を与えることが記載されている
。For example, Japanese Patent Publication No. 48-25585 states that solid fluorinated graphite (CFx) n (however, 0.5≦X≦1), especially fluorinated graphite with X of 1 or close to 1, is used as the positive electrode active material of a battery. It is described that this provides a high energy density primary battery that has a high utilization rate as an active material, excellent voltage flatness, and a good shelf life.
また特開昭５３−１０２８９３号公報には、前記式（Ｃ
： Ｆ）ｎで表される新規フッ化黒鉛（以下、単に（Ｃ
２Ｆ）ｎという）およびその製法が記載されており、こ
の（Ｃ２Ｆ）ｎは６００℃のフッ素雰囲気下加熱処理を
行なってもフッ素の増加が認められないものであって、
この新規（Ｃ２Ｆ）ｎが電池活物質として用いられるこ
とも示唆されている。Furthermore, in Japanese Patent Application Laid-open No. 53-102893, the formula (C
: F) New fluorinated graphite represented by n (hereinafter simply referred to as (C
2F)n) and its manufacturing method are described, and this (C2F)n shows no increase in fluorine even after heat treatment in a fluorine atmosphere at 600°C.
It has also been suggested that this new (C2F)n can be used as a battery active material.
また特開昭５５−２８２４８号公報において、該（Ｃ２
Ｐ）ｎが前記式（ＣＦ） ｎで表されるフッ素黒鉛（以
下、単に（ＣＦ）ｎという）よりも高い放電電位を示す
ことが記載されている。Furthermore, in Japanese Patent Application Laid-open No. 55-28248, the (C2
It is described that P)n exhibits a higher discharge potential than fluorine graphite (hereinafter simply referred to as (CF)n) represented by the formula (CF)n.
さらに特開昭５７−８４５７０号公報には（ＣＦ）ｎと
（Ｃ！ Ｆ）ｎを混合して電池の正極活物質として用い
ることにより、（ＣＰ）ｎの問題点である放電初期にお
ける電圧の一時的な低下が改善されることが提案されて
おり、また特開昭５８−１８４６８号公報は人造黒鉛を
フッ素と反応させてえられる（Ｃ２Ｐ）ｎを主成分とす
る電池活物質に関するもので、そこには好ましい態様と
して原料として人造黒鉛を生成物の重量増加がなくなる
までフッ素と反応させてえられる（Ｃ２Ｐ）ｎを主成分
とする電池活物質が記載されており、それが高い放電電
位を示すことが明らかにされている。Furthermore, Japanese Patent Application Laid-Open No. 57-84570 discloses that by mixing (CF)n and (C! It has been proposed that temporary deterioration can be improved, and Japanese Patent Application Laid-Open No. 18468/1983 relates to a battery active material whose main component is (C2P)n, which is obtained by reacting artificial graphite with fluorine. , which describes a preferred embodiment of a battery active material whose main component is (C2P)n, which is obtained by reacting artificial graphite as a raw material with fluorine until there is no increase in the weight of the product, and which has a high discharge potential. It has been revealed that this shows that
［発明が解決しようとする問題点］
本発明者らは、より高い放電電位をもつ電池活物質をう
るべく、これらフッ化黒鉛の生成反応について各種の研
究を行なったところ、炭素原料のフッ素化反応の生成物
の窒素雰囲気下における熱分解温度が低いほど高い放電
電位を示すという意外な事実を見出し、本発明を完成す
るに至った。[Problems to be Solved by the Invention] In order to obtain a battery active material with a higher discharge potential, the present inventors conducted various studies on the formation reactions of these fluorinated graphites, and found that the fluorination of carbon raw materials The inventors have discovered the surprising fact that the lower the thermal decomposition temperature of the reaction product in a nitrogen atmosphere, the higher the discharge potential, leading to the completion of the present invention.
［問題点を解決するための手段］
本発明は、炭素材料をフッ素化してえられるフッ化黒鉛
であって、窒素雰囲気下での熱分解温度が５９５°Ｃ以
下の範囲にあることを特徴とする電池活物質に関する。[Means for Solving the Problems] The present invention is a fluorinated graphite obtained by fluorinating a carbon material, which is characterized by having a thermal decomposition temperature in a range of 595°C or less in a nitrogen atmosphere. This invention relates to battery active materials.
［作用および好ましい実施態様］
フッ化黒鉛は窒素中での熱により熱分解（熱分解温度は
通常６００℃以上）する。その反応はつぎの反応式（１
）、（２に従う。[Function and preferred embodiments] Fluorinated graphite is thermally decomposed by heat in nitrogen (thermal decomposition temperature is usually 600° C. or higher). The reaction is expressed by the following reaction formula (1
), (follows 2.
％式％（１）
これらの式から明らかなように、フッ化黒鉛の熱分解時
には低分子量のフルオロカーボンガスが揮散するため重
量減少を呈す。実際の測定には熱重責分析法（ＴＧ法）
が用いられる。ＴＧ法でえられる結果（ＴＧ曲線）は昇
温速度および周囲雰囲気により微妙に変化する。% formula % (1) As is clear from these formulas, when fluorinated graphite is thermally decomposed, low molecular weight fluorocarbon gas is volatilized, resulting in weight loss. Thermal stress analysis method (TG method) is used for actual measurement.
is used. The results obtained by the TG method (TG curve) vary slightly depending on the temperature increase rate and the surrounding atmosphere.
本発明でいう熱分解温度は、窒素雰囲気下に昇温温度１
０℃／ｗｉｎの条件で測定したときの値である。ＴＧ法
における熱分解温度は、７０曲線の傾きが極小（負に最
大）となるときの温度であり、換言すればＴＧ曲線の一
次微分曲線のピーク位置（下に凸）の温度である。The thermal decomposition temperature in the present invention is a heating temperature of 1
This is the value when measured under the condition of 0°C/win. The thermal decomposition temperature in the TG method is the temperature at which the slope of the 70 curve becomes minimum (maximum negative), in other words, it is the temperature at the peak position (convex downward) of the first-order differential curve of the TG curve.
熱分解温度が低いほど放電電圧が高くなる理由について
は明らかではないが、熱分解温度が低いことはフッ化黒
鉛の結晶構造がより不安定であることを示し、その不安
定さがより高い放電電圧を与えているものと考えられる
。It is not clear why the lower the pyrolysis temperature, the higher the discharge voltage. However, a lower pyrolysis temperature indicates that the crystal structure of fluorinated graphite is more unstable, and the instability leads to a higher discharge voltage. It is thought that voltage is being applied.
本発明の電池活物質の熱分解温度は５９５℃以下でなけ
ればならない。それ以上の熱分解温度を有するフッ化黒
鉛は放電電圧が低く実用的でない。一方、下限は特に限
定されないが、概ね５３０℃程度である。The thermal decomposition temperature of the battery active material of the present invention must be 595°C or lower. Fluorinated graphite having a thermal decomposition temperature higher than this has a low discharge voltage and is not practical. On the other hand, the lower limit is not particularly limited, but is approximately 530°C.
フッ化黒鉛の熱分解温度は炭素材料、製造条件により大
きく異なり、各炭素材料により適宜それらを選定するこ
とが好ましい。しかしながら、どのような炭素材料や製
造条件を採用したとしても、熱分解温度が５９５℃以下
であれば高い放電電圧を示す。The thermal decomposition temperature of fluorinated graphite varies greatly depending on the carbon material and manufacturing conditions, and it is preferable to select it appropriately depending on each carbon material. However, no matter what carbon material or manufacturing conditions are used, if the thermal decomposition temperature is 595° C. or lower, a high discharge voltage will be exhibited.
本発明の電池活物質は、（ＣＦ）ｎまたは（Ｃ２Ｐ）ｎ
のいずれであってもよい。また（Ｃ２Ｐ）ｎの生成時に
は（ＣＦ）ｎの副生がみられるが、このような（ＣＰ）
ｎと（Ｃ２Ｆ）ｎの混合物も本発明の電池活物質に含ま
れる。The battery active material of the present invention is (CF)n or (C2P)n
It may be either. Also, when (C2P)n is produced, (CF)n is a by-product, but such (CP)
A mixture of n and (C2F)n is also included in the battery active material of the present invention.
フッ素の含を量としては４０〜６４％（重量％、以下同
様）が好ましい。フッ素含有量が少なくなると通常放電
容量が小さくなり、好ましくない。そのようなものは、
たとえばフッ素化反応の初期にえられるフッ化黒鉛にみ
られる。４０％という下限は放電電圧との関係では重要
な限界ではないが、一般に前記のごとく放電容量が小さ
くなったり、未反応の炭素材料が残存したりしているた
め好ましくない。The content of fluorine is preferably 40 to 64% (by weight, hereinafter the same). When the fluorine content decreases, the discharge capacity usually decreases, which is not preferable. Such things are
For example, it can be seen in fluorinated graphite obtained at the beginning of a fluorination reaction. Although the lower limit of 40% is not an important limit in relation to the discharge voltage, it is generally not preferable because the discharge capacity becomes small and unreacted carbon material remains as described above.
上限の６４％は炭素材料とフッ素の反応における限界の
フッ素含有量であり、通常これ以上のフッ素含有ｆｆ１
（ＣＰ）ｎはえられない。（ＣＰ）ｎの組威武から算出
されるフッ素含有量は６１．２７％であるが、それ以上
の値かえられるのは（ＣＰ）ｎ粒子表面にＣＦ３やＣＦ
２などが存在するためであると考えられている。The upper limit of 64% is the limit fluorine content in the reaction between carbon materials and fluorine, and normally fluorine containing ff1 is higher than this.
(CP)n cannot be obtained. The fluorine content calculated from the group weight of (CP)n is 61.27%, but the values higher than that are CF3 and CF on the surface of (CP)n particles.
It is thought that this is due to the existence of 2 etc.
原料として用いる炭素材料は特に限定されず、たとえば
黒鉛、石油コークスなどがあげられる。The carbon material used as a raw material is not particularly limited, and examples include graphite and petroleum coke.
本発明の電池活物質は通常、原料炭素をフッ素ガス（必
要に応じてフッ素ガスは希釈ガスと混合して用いられる
）によりフッ素化して製造されるが、とくにこれに制限
されない。The battery active material of the present invention is usually produced by fluorinating raw material carbon with fluorine gas (fluorine gas is mixed with diluent gas if necessary), but is not particularly limited thereto.
フッ素ガスまたはフッ素ガスと希釈ガスとの混合ガスは
、フッ素ガスの分圧が０．１〜１ ａｔｌｌとなるよう
に反応器に室温で導入され、温度を室温から徐々に上昇
し、目的とする反応温度すなわち３００〜５００℃、好
ましくは３００〜４５０℃に維持する。または予め原料
炭素を反応温度にまで昇温しでおき、フッ素ガスを導入
してもよく、炭素材料の性質に応じて適宜決定される。Fluorine gas or a mixed gas of fluorine gas and diluent gas is introduced into the reactor at room temperature so that the partial pressure of fluorine gas is 0.1 to 1 atll, and the temperature is gradually raised from room temperature until the desired temperature is reached. The reaction temperature is maintained at 300-500°C, preferably 300-450°C. Alternatively, the raw material carbon may be heated to the reaction temperature in advance and fluorine gas may be introduced, which is determined as appropriate depending on the properties of the carbon material.
原料炭素は通常反応温度で脱気し、水分を除去しておく
ことが好ましい。The raw material carbon is preferably degassed at a normal reaction temperature to remove moisture.
フッ素ガスと混合する希釈ガスとしてはフッ素および原
料炭素と反応しないガスを用いる。As the diluent gas to be mixed with the fluorine gas, a gas that does not react with fluorine or raw carbon is used.
具体例としては、たとえばチッ素ガス、パーフルオロカ
ーボン、希ガスなどがあげられる。Specific examples include nitrogen gas, perfluorocarbon, rare gas, and the like.
本発明の電池活物質にバインダ、導電材を配合して電極
材かえられる。それらの配合割合は、フッ化黒鉛１０部
（重量部、以下同様）、バインダ１〜４部、導電材０．
５〜２部であるのが好ましい。The electrode material can be changed by adding a binder and a conductive material to the battery active material of the present invention. Their compounding ratio is 10 parts of fluorinated graphite (by weight, the same applies hereinafter), 1 to 4 parts of binder, and 0.5 parts of conductive material.
Preferably it is 5 to 2 parts.
バインダとしては、たとえばポリテトラフルオロエチレ
ン（ＰＴＦＥ）などがあげられ、導電材としてはたとえ
ばアセチレンブラック、ケッチェンブラックなどの高電
気伝導性のカーボンブラックあるいは天然黒鉛などがあ
げられる。Examples of the binder include polytetrafluoroethylene (PTFE), and examples of the conductive material include highly electrically conductive carbon black such as acetylene black and Ketjen black, or natural graphite.
本発明の電池活物質に用い°るばあい、本発明の電池活
物質を正極とし、負極にたとえばリチウム、マグネシウ
ム、アルミニウムを単独またはこれらを主成分とする合
金の形で用いることが好ましい。電解質としては用いる
負極の種類にもよるが、通常非水系を用いる。When used in the battery active material of the present invention, it is preferable to use the battery active material of the present invention as a positive electrode and, for example, as a negative electrode, using lithium, magnesium, or aluminum alone or in the form of an alloy containing these as main components. Although it depends on the type of negative electrode used as the electrolyte, a non-aqueous electrolyte is usually used.
つぎに実施例をあげて本発明の電池活物質を説明するが
、本発明はかかる実施例のみに限定されるものではない
。Next, the battery active material of the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.
実施例１
人造黒鉛を反応器に入れ反応温度で３０分間脱気して水
分を除去したのち、室温に冷却した。Example 1 Artificial graphite was placed in a reactor and degassed at reaction temperature for 30 minutes to remove moisture, and then cooled to room temperature.
ついでフッ素ガスを１ａＵで反応器に導入し、３８０℃
まで昇温しで１８時間反応せしめた。生成物は黒褐色の
粉末状であり、そのフッ素含有量は５２．９％であった
。このものを粉末Ｘ線回折法によって分析したところ、
（００１）面の回折角２θ（以下、単に２θという）に
おいて１０．５４度にピークが現れた。フッ素含有量と
２０から、生成物は（Ｃ２Ｐ）ｎと（ＣＦ）ｎとの混合
物と考えられる。このものの熱分解温度は５９０℃であ
った。Fluorine gas was then introduced into the reactor at 1 aU and heated to 380°C.
The temperature was raised to 100°C, and the reaction was continued for 18 hours. The product was a dark brown powder with a fluorine content of 52.9%. When this material was analyzed by powder X-ray diffraction method,
A peak appeared at a diffraction angle of 2θ (hereinafter simply referred to as 2θ) of the (001) plane at 10.54 degrees. Based on the fluorine content and 20, the product is considered to be a mixture of (C2P)n and (CF)n. The thermal decomposition temperature of this product was 590°C.
ついでこの生成物１０部、ＰＴＦＥ３部およびアセチレ
ンブラック１部を充分混練してニッケル網上にプレスし
、表面！ １．５７ ｃｊの正極を作製した。負極とし
てはリチウムブロックから切り出してニッケル網で保持
したものを用い、電解質には１モル／ｇのホウフッ化リ
チウムのγ−ブチロラクトン溶液を用いた。放電電圧の
測定は２５℃にてＩＯＫΩの定抵抗放電で行なった。え
られた端子電圧の経時変化を第１図に示す。放電には電
池活物質５０ｍｇを用いた。Next, 10 parts of this product, 3 parts of PTFE, and 1 part of acetylene black were thoroughly kneaded and pressed onto a nickel screen, and the surface! A positive electrode of 1.57 cj was produced. The negative electrode was cut from a lithium block and held in a nickel net, and the electrolyte was a 1 mol/g γ-butyrolactone solution of lithium fluoroborate. The discharge voltage was measured at 25° C. by constant resistance discharge of IOKΩ. Figure 1 shows the change in terminal voltage obtained over time. 50 mg of battery active material was used for discharging.
比較例１
反応を９０時間続けたほかは実施例１と同様にして人造
黒鉛をフッ素化した。生成物は灰褐色の粉末状であり、
フッ素含有量は５４．５％であった。２θは０．８９で
あり、（Ｃ２Ｆ）ｎと（ＣＦ） ｎの混合物であった。Comparative Example 1 Artificial graphite was fluorinated in the same manner as in Example 1, except that the reaction was continued for 90 hours. The product is a gray-brown powder;
The fluorine content was 54.5%. The 2θ was 0.89, and it was a mixture of (C2F)n and (CF)n.
このものの熱分解温度は６００℃であった。The thermal decomposition temperature of this product was 600°C.
ついでこの生成物を用い実施例１と同様にして電池を作
製し、端子電圧の経時変化を測定した。結果を第１表に
示す。A battery was then produced using this product in the same manner as in Example 1, and the change in terminal voltage over time was measured. The results are shown in Table 1.
実施例２〜４および比較例２〜４
第１表に示す炭素材料および反応条件を採用したほかは
実施例１と同様にしてフッ素化反応を行なった。各生成
物の性質を第１表に示す（実施例１および比較例１の結
果も示しである）。Examples 2 to 4 and Comparative Examples 2 to 4 Fluorination reactions were carried out in the same manner as in Example 1, except that the carbon materials and reaction conditions shown in Table 1 were used. The properties of each product are shown in Table 1 (the results of Example 1 and Comparative Example 1 are also shown).
さらにえられた生成物を用い実施例１と同様にして電池
を作製し、端子電圧の経時変化を測定した。結果を第２
図に示す。Furthermore, a battery was produced using the obtained product in the same manner as in Example 1, and the change in terminal voltage over time was measured. Second result
As shown in the figure.
［以下余白コ
［発明の効果］
本発明の電池活物質を用いるときは、放電電圧のより高
い電池を提供することができる。[See below for margins] [Effects of the Invention] When the battery active material of the present invention is used, a battery with higher discharge voltage can be provided.
第１図は実施例１および比較例１でそれぞれえられた電
池活物質を用いた電池の端子電圧の経時変化を示すグラ
フ、第２図は実施例２〜４および比較例２〜４でそれぞ
れえられた電池活物質を用いた電池の端子電圧の経時変
化を示すグラフである。
ボデデデ（〉）
（”） （’Ｊ Ｃ
ＩＪボデデ三（〉）
手続補正書印発）
昭和６１年９月１日FIG. 1 is a graph showing changes over time in terminal voltage of batteries using the battery active materials obtained in Example 1 and Comparative Example 1, respectively. 3 is a graph showing changes over time in terminal voltage of a battery using the obtained battery active material. Bodedede (〉) (”) ('J C
IJ Bodede 3 (〉) Procedural amendment signed) September 1, 1986
Claims (1)
鉛であって、窒素雰囲気下での熱分解温度が５９５℃以
下の範囲にあることを特徴とする電池活物質。 ２ フッ素含有量が４０〜６４重量％である特許請求の
範囲第１項記載の電池活物質。[Scope of Claims] 1. A battery active material which is fluorinated graphite obtained by fluorinating a carbon material with fluorine, and which has a thermal decomposition temperature in a range of 595° C. or lower in a nitrogen atmosphere. 2. The battery active material according to claim 1, which has a fluorine content of 40 to 64% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61158549A JPS6313268A (en) | 1986-07-04 | 1986-07-04 | Battery active material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61158549A JPS6313268A (en) | 1986-07-04 | 1986-07-04 | Battery active material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6313268A true JPS6313268A (en) | 1988-01-20 |
Family
ID=15674133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61158549A Pending JPS6313268A (en) | 1986-07-04 | 1986-07-04 | Battery active material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6313268A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009512133A (en) * | 2005-10-05 | 2009-03-19 | カリフォルニア インスティテュート オブ テクノロジー | Partially fluorinated graphite as an electrode material |
| WO2011010416A1 (en) * | 2009-07-21 | 2011-01-27 | パナソニック株式会社 | Lithium primary battery |
| US20120077090A1 (en) * | 2010-09-28 | 2012-03-29 | Daikin Industries, Ltd. | Positive electrode active material for lithium primary cell |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5887766A (en) * | 1981-11-17 | 1983-05-25 | Matsushita Electric Ind Co Ltd | Manufacture of organic electrolyte battery |
| JPS61116759A (en) * | 1984-11-12 | 1986-06-04 | Nobuatsu Watanabe | Active material for battery |
-
1986
- 1986-07-04 JP JP61158549A patent/JPS6313268A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5887766A (en) * | 1981-11-17 | 1983-05-25 | Matsushita Electric Ind Co Ltd | Manufacture of organic electrolyte battery |
| JPS61116759A (en) * | 1984-11-12 | 1986-06-04 | Nobuatsu Watanabe | Active material for battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009512133A (en) * | 2005-10-05 | 2009-03-19 | カリフォルニア インスティテュート オブ テクノロジー | Partially fluorinated graphite as an electrode material |
| WO2011010416A1 (en) * | 2009-07-21 | 2011-01-27 | パナソニック株式会社 | Lithium primary battery |
| JP2011044420A (en) * | 2009-07-21 | 2011-03-03 | Panasonic Corp | Lithium primary battery |
| US20120077090A1 (en) * | 2010-09-28 | 2012-03-29 | Daikin Industries, Ltd. | Positive electrode active material for lithium primary cell |
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