JP2002151074A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JP2002151074A JP2002151074A JP2000345124A JP2000345124A JP2002151074A JP 2002151074 A JP2002151074 A JP 2002151074A JP 2000345124 A JP2000345124 A JP 2000345124A JP 2000345124 A JP2000345124 A JP 2000345124A JP 2002151074 A JP2002151074 A JP 2002151074A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- electrolyte secondary
- secondary battery
- aqueous electrolyte
- negative electrode
- 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 56
- 239000007774 positive electrode material Substances 0.000 claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007773 negative electrode material Substances 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 11
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 10
- 229910021314 NaFeO 2 Inorganic materials 0.000 claims description 7
- 229910000676 Si alloy Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract 1
- -1 vinylene carbonate Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 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
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-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
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、正極と、負極
と、有機溶媒を用いた非水電解質とを備えた非水電解質
二次電池に係り、特に、その正極に用いる正極材料を改
善して、電池容量の高い非水電解質二次電池が得られる
ようにした点に特徴を有するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery including a positive electrode, a negative electrode, and a non-aqueous electrolyte using an organic solvent. And a non-aqueous electrolyte secondary battery having a high battery capacity.
【０００２】[0002]
【従来の技術】近年、高出力，高エネルギー密度の新型
電池の１つとして、有機溶媒を用いた非水電解質を用
い、リチウムイオンを正極と負極との間で移動させて充
放電を行うようにした非水電解質二次電池が利用される
ようになった。2. Description of the Related Art In recent years, as one of new batteries with high output and high energy density, a non-aqueous electrolyte using an organic solvent is used to perform charge and discharge by moving lithium ions between a positive electrode and a negative electrode. Non-aqueous electrolyte secondary batteries have been used.
【０００３】そして、このような非水電解質二次電池に
おいては、一般に、正極における正極材料にＬｉＣｏＯ
2 等のリチウムの吸蔵，放出が可能なリチウム−遷移金
属複合酸化物が使用されており、また負極における負極
材料に黒鉛等の炭素材料が広く使用されていた。In such a non-aqueous electrolyte secondary battery, generally, LiCoO
Lithium-transition metal composite oxides capable of absorbing and releasing lithium, such as 2, have been used, and carbon materials such as graphite have been widely used as negative electrode materials in negative electrodes.
【０００４】ここで、このような非水電解質二次電池に
おいて、負極材料として用いられる黒鉛の比容量は約３
７０ｍＡｈ／ｇであるのに対して、正極材料として用い
られるＬｉＣｏＯ2 の場合、ＬｉＣｏＯ2 中におけるＬ
ｉが十分に放出されず、比容量は１５０ｍＡｈ／ｇ程度
になっており、このような非水電解質二次電池における
エネルギー密度は１５０Ｗｈ／ｋｇ程度であった。Here, in such a nonaqueous electrolyte secondary battery, the specific capacity of graphite used as a negative electrode material is about 3
Whereas it is 70 mAh / g, if the LiCoO 2 used as the positive electrode material, L in the LiCoO 2
i was not sufficiently released, the specific capacity was about 150 mAh / g, and the energy density of such a nonaqueous electrolyte secondary battery was about 150 Wh / kg.
【０００５】しかし、近年においては、このような非水
電解質二次電池が携帯電話やパーソナルコンピュータ等
の電源として広く使用されるようになり、非水電解質二
次電池におけるエネルギー密度をさらに高めて、高い電
池容量を得られるようにすることが要望されている。However, in recent years, such non-aqueous electrolyte secondary batteries have been widely used as power sources for mobile phones, personal computers and the like, and the energy density of the non-aqueous electrolyte secondary batteries has been further increased. There is a demand for obtaining a high battery capacity.
【０００６】[0006]
【発明が解決しようとする課題】この発明は、正極と、
負極と、有機溶媒を用いた非水電解質とを備えた非水電
解質二次電池において、正極に用いる正極材料の比容量
を向上させて、エネルギー密度を高め、電池容量の高い
非水電解質二次電池重が得られるようにすることを課題
とするものである。SUMMARY OF THE INVENTION The present invention provides a positive electrode,
In a non-aqueous electrolyte secondary battery including a negative electrode and a non-aqueous electrolyte using an organic solvent, the specific capacity of the positive electrode material used for the positive electrode is increased, the energy density is increased, and the non-aqueous electrolyte secondary It is an object to obtain a battery weight.
【０００７】[0007]
【課題を解決するための手段】この発明における非水電
解質二次電池においては、上記のような課題を解決する
ため、正極と、負極と、有機溶媒を用いた非水電解質と
を備えた非水電解質二次電池において、上記の正極にお
ける正極材料に、空間群Ｒ３ｍの結晶構造を有する遷移
金属酸化物（但し、ＬｉＣｏＯ2 を除く。）を用いると
共に、負極にリチウムを含有する負極材料を用いるよう
にしたのである。In order to solve the above-mentioned problems, a non-aqueous electrolyte secondary battery according to the present invention has a non-aqueous electrolyte including a positive electrode, a negative electrode, and a non-aqueous electrolyte using an organic solvent. In the water electrolyte secondary battery, a transition metal oxide having a crystal structure of a space group R3m (excluding LiCoO 2 ) is used as a positive electrode material of the positive electrode, and a negative electrode material containing lithium is used as a negative electrode. I did it.
【０００８】ここで、この発明における非水電解質二次
電池においては、先ず放電を行って、負極における負極
材料に含まれているリチウムを、上記の空間群Ｒ３ｍの
結晶構造を有する遷移金属酸化物（但し、ＬｉＣｏＯ2
を除く。）を用いた正極材料に挿入させ、その後、この
正極と負極との間でリチウムイオンを移動させて充放電
を行うようになっている。In the non-aqueous electrolyte secondary battery according to the present invention, first, discharge is performed to replace lithium contained in the negative electrode material of the negative electrode with a transition metal oxide having a crystal structure of the above space group R3m. (However, LiCoO 2
except for. ), And then charge and discharge by moving lithium ions between the positive electrode and the negative electrode.
【０００９】ここで、上記のように先ず放電を行って、
負極における負極材料に含まれているリチウムを、空間
群Ｒ３ｍの結晶構造を有する遷移金属酸化物（但し、Ｌ
ｉＣｏＯ2 を除く。）を用いた正極材料に挿入させるよ
うにすると、多くの量のリチウムを充放電に関与させる
ことができるようになり、正極材料における比容量が高
くなってエネルギー密度が向上し、電池容量の高い非水
電解質二次電池が得られるようになる。Here, first, as described above, discharge is performed,
Lithium contained in the negative electrode material of the negative electrode is replaced with a transition metal oxide having a crystal structure of a space group R3m (L
Excludes iCoO 2 . ) Allows a large amount of lithium to be involved in charge and discharge, increasing the specific capacity of the positive electrode material, improving the energy density, and increasing the battery capacity. A non-aqueous electrolyte secondary battery can be obtained.
【００１０】ここで、空間群Ｒ３ｍの結晶構造を有する
遷移金属酸化物としては、ＮａＦｅＯ2 ，ＬｉＮｉ
Ｏ2 ，ＬｉＣｏＯ2 等が存在するが、この発明における
非水電解質二次電池において、ＬｉＣｏＯ2 を除いたの
は、ＬｉＣｏＯ2 の場合、先の放電によって負極材料に
含まれているリチウムを挿入させると、その後、正極か
らリチウムが放出されなくなって、充放電が行えなくな
るためである。これは、リチウムの挿入によりＬｉＣｏ
Ｏ2 の結晶構造が変化したためであると考えられる。Here, transition metal oxides having a crystal structure of space group R3m include NaFeO 2 , LiNi
Although O 2 , LiCoO 2, etc. are present, in the non-aqueous electrolyte secondary battery of the present invention, LiCoO 2 is excluded in the case of LiCoO 2 , in which lithium contained in the negative electrode material is inserted by the previous discharge. Then, lithium is no longer released from the positive electrode, and charging and discharging cannot be performed. This is due to the LiCo
This is probably because the crystal structure of O 2 changed.
【００１１】これに対して、空間群Ｒ３ｍの結晶構造を
有する他の遷移金属酸化物の場合、特にＮａＦｅＯ2 の
場合には、先の放電によって負極材料に含まれているリ
チウムを挿入させた後においても、正極からリチウムが
適切に放出されて、正極材料における比容量が非常に高
くなり、エネルギー密度が著しく向上して、電池容量の
高い非水電解質二次電池が得られるようになる。On the other hand, in the case of another transition metal oxide having a crystal structure of the space group R3m, especially in the case of NaFeO 2 , after the lithium contained in the negative electrode material is inserted by the previous discharge, In this case, lithium is appropriately released from the positive electrode, the specific capacity of the positive electrode material becomes extremely high, the energy density is remarkably improved, and a nonaqueous electrolyte secondary battery having a high battery capacity can be obtained.
【００１２】また、この発明における非水電解質二次電
池において、負極に用いる負極材料は、上記のようにリ
チウムを含有しており、先の放電によりリチウムを上記
の正極材料に供給できるものであればよく、例えば、金
属リチウムや各種のリチウム合金を用いることができる
他、リチウムを吸蔵させた炭素材料等を用いることもで
き、特に、比容量の高いＬｉ−Ｓｉ合金を用いることが
好ましい。In the non-aqueous electrolyte secondary battery according to the present invention, the negative electrode material used for the negative electrode contains lithium as described above, and any material capable of supplying lithium to the positive electrode material by the previous discharge. For example, metallic lithium or various lithium alloys can be used, and a carbon material in which lithium is occluded can be used. In particular, a Li—Si alloy having a high specific capacity is preferably used.
【００１３】また、この発明における非水電解質二次電
池において、上記の有機溶媒を用いた非水電解質として
は、従来より一般に使用されているものを用いることが
できる。Further, in the non-aqueous electrolyte secondary battery of the present invention, as the non-aqueous electrolyte using the above-mentioned organic solvent, a conventionally used non-aqueous electrolyte can be used.
【００１４】そして、その有機溶媒としては、非水電解
液において従来より一般に使用されている公知の有機溶
媒を使用することができ、例えば、エチレンカーボネー
ト、プロピレンカーボネート、ブチレンカーボネート、
ビニレンカーボネート等の環状炭酸エステルや、ジメチ
ルカーボネート、ジエチルカーボネート、ジプロピルカ
ーボネート、エチルメチルカーボネート、エチルプロピ
ルカーボネート等の鎖状炭酸エステル等を１種又は複数
混合させたものを用いることができる。As the organic solvent, known organic solvents conventionally used in nonaqueous electrolytes can be used. Examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate, and the like.
A cyclic carbonate such as vinylene carbonate, or a chain carbonate such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, ethyl propyl carbonate or the like may be used alone or in combination.
【００１５】また、この非水電解質において、上記の有
機溶媒に溶解させる溶質としても公知のものを使用する
ことができ、例えば、トリフルオロメタンスルホン酸リ
チウムＬｉＣＦ3 ＳＯ3 ，ヘキサフルオロリン酸リチウ
ムＬｉＰＦ6 ，過塩素酸リチウムＬｉＣｌＯ4 ，テトラ
フルオロホウ酸リチウムＬｉＢＦ4 ，トリフルオロメタ
ンスルホン酸イミドリチウムＬｉＮ（ＣＦ3 ＳＯ2 ）2
等のリチウム化合物を用いることができる。In the non-aqueous electrolyte, known solutes to be dissolved in the above-mentioned organic solvent can be used. For example, lithium trifluoromethanesulfonate LiCF 3 SO 3 and lithium hexafluorophosphate LiPF 6 , Lithium perchlorate LiClO 4 , lithium tetrafluoroborate LiBF 4 , lithium trifluoromethanesulfonate LiN (CF 3 SO 2 ) 2
And the like.
【００１６】さらに、この発明における非水電解質二次
電池においては、正極と負極とを分離させるセパレータ
等についても従来より一般に使用されている公知のもの
を用いることができる。Further, in the non-aqueous electrolyte secondary battery according to the present invention, as the separator for separating the positive electrode and the negative electrode, a known one generally used conventionally can be used.
【００１７】[0017]
【実施例】以下、この発明の非水電解質二次電池につい
て、実施例を挙げて具体的に説明すると共に、この実施
例における非水電解質二次電池の場合、正極材料におけ
る比容量が大きくなってエネルギー密度が向上し、高い
電池容量が得られるようになることを、実験に基づいて
明らかにする。なお、この発明における非水電解質二次
電池は、下記の実施例に示したものに限定されず、その
要旨を変更しない範囲において適宜変更して実施できる
ものである。EXAMPLES Hereinafter, the nonaqueous electrolyte secondary battery of the present invention will be specifically described with reference to examples, and in the case of the nonaqueous electrolyte secondary battery in this example, the specific capacity of the positive electrode material will increase. It is clarified based on experiments that the energy density is improved and a high battery capacity can be obtained. The non-aqueous electrolyte secondary battery according to the present invention is not limited to those described in the following examples, and can be implemented by appropriately changing the scope of the invention without changing its gist.
【００１８】この実施例においては、下記のようにして
作製した正極と非水電解液とを用いるようにした。In this example, a positive electrode and a non-aqueous electrolyte prepared as described below were used.
【００１９】［正極の作製］正極を作製するにあたって
は、正極材料に空間群Ｒ３ｍの結晶構造を有する遷移金
属酸化物であるＮａＦｅＯ2 を用い、このＮａＦｅＯ2
が４０重量部、導電剤であるアセチレンブラックが４０
重量部、結着剤であるポリテトラフルオロエチレンが２
０重量部の割合になるように混合した後、これを直径が
１６ｍｍ、厚みが０．１ｍｍの円板状に加圧成形し、こ
れを１１０℃で真空乾燥させて正極を作製した。[0019] In preparing the positive electrode fabricated positive electrode uses a NaFeO 2 is a transition metal oxide having a crystal structure of the space group R3m the positive electrode material, the NaFeO 2
Is 40 parts by weight, and acetylene black as a conductive agent is 40 parts by weight.
2 parts by weight of polytetrafluoroethylene as a binder
After mixing so as to have a ratio of 0 parts by weight, this was press-formed into a disk having a diameter of 16 mm and a thickness of 0.1 mm, and this was vacuum-dried at 110 ° C. to produce a positive electrode.
【００２０】［非水電解液の作製］非水電解液を作製す
るにあたっては、エチレンカーボネートとジメチルカー
ボネートとを１：１の体積比で混合させた混合溶媒に、
６フッ化リン酸リチウムＬｉＰＦ6 を１ｍｏｌ／ｋｇの
割合で溶解させて非水電解液を作製した。[Preparation of Non-Aqueous Electrolyte] In preparing a non-aqueous electrolyte, a mixed solvent obtained by mixing ethylene carbonate and dimethyl carbonate at a volume ratio of 1: 1 was used.
Lithium hexafluorophosphate LiPF 6 was dissolved at a rate of 1 mol / kg to prepare a non-aqueous electrolyte.
【００２１】そして、図１に示すように、試験セル１０
内に、上記のようにして作製した非水電解液１４を収容
させると共に、上記のようにして作製した正極を作用極
１１に用い、負極になる対極１２と、参照極１３とにそ
れぞれ金属リチウムを用いるようにした。Then, as shown in FIG.
The non-aqueous electrolyte 14 prepared as described above is accommodated therein, and the positive electrode prepared as described above is used for the working electrode 11, and the counter electrode 12 serving as the negative electrode and the reference electrode 13 are each made of metallic lithium. Was used.
【００２２】そして、上記の試験セル１０において、先
ず、放電電流２ｍＡで参照極１３に対する作用極１１の
電位が０．５Ｖになるまで放電を行った後、充電電流２
ｍＡで参照極１３に対する作用極１１の電位が４．０Ｖ
になるまで充電を行った。その後も、同様にして放電と
充電とを繰り返して行った。図２において、第１回目の
放電時における電圧と正極における正極材料の比容量
（ｍＡｈ／ｇ）との関係を示す放電曲線を破線で、第１
回目の充電時における電圧と正極における正極材料の比
容量（ｍＡｈ／ｇ）との関係を示す充電曲線を実線で示
した。また、図３において、第２回目の放電時における
電圧と正極における正極材料の比容量（ｍＡｈ／ｇ）と
の関係を示す放電曲線を破線で、第２回目の充電時にお
ける電圧と正極における正極材料の比容量（ｍＡｈ／
ｇ）との関係を示す充電曲線を実線で示した。Then, in the test cell 10 described above, first, the discharge is performed at a discharge current of 2 mA until the potential of the working electrode 11 with respect to the reference electrode 13 becomes 0.5 V, and then the charge current 2
At mA, the potential of the working electrode 11 with respect to the reference electrode 13 is 4.0 V
The battery was charged until it became. Thereafter, the discharging and charging were repeated in the same manner. In FIG. 2, the discharge curve showing the relationship between the voltage at the time of the first discharge and the specific capacity (mAh / g) of the positive electrode material in the positive electrode is represented by a broken line,
A solid curve shows a charging curve showing the relationship between the voltage at the time of the second charging and the specific capacity (mAh / g) of the positive electrode material in the positive electrode. In FIG. 3, a broken line represents a discharge curve indicating the relationship between the voltage at the time of the second discharge and the specific capacity (mAh / g) of the positive electrode material at the positive electrode, and the voltage at the time of the second charge and the positive electrode at the positive electrode. Specific capacity of material (mAh /
The charging curve showing the relationship with g) was shown by a solid line.
【００２３】また、上記のような放電と充電とを１サイ
クルとして、放電と充電とを繰り返して行い、各サイク
ルの放電時における正極材料の比容量（ｍＡｈ／ｇ）を
求め、その結果を図４に示した。Further, the discharge and charge as described above are regarded as one cycle, and the discharge and charge are repeatedly performed, and the specific capacity (mAh / g) of the positive electrode material at the time of discharge in each cycle is obtained. The results are shown in FIG.
【００２４】さらに、各サイクルにおける放電容量に対
する充電容量の比率、すなわち放充電効率（％）を求
め、その結果を図５に示した。Further, the ratio of the charge capacity to the discharge capacity in each cycle, that is, the discharge / charge efficiency (%) was determined, and the results are shown in FIG.
【００２５】これらの結果から明らかなように、正極材
料に空間群Ｒ３ｍの結晶構造を有する遷移金属酸化物で
あるＮａＦｅＯ2 を用いた場合、第１回目の放電時にお
いては、正極材料の比容量が９９３ｍＡｈ／ｇと非常に
高くなっており、また第１回目と第２回目との間におい
ては正極材料の比容量が大きく低下したが、このように
比容量が大きく低下した２回目以降においても、従来の
比容量が１５０ｍＡｈ／ｇ程度のＬｉＣｏＯ2 に比べる
と、非常に高い比容量を示した。As is apparent from these results, when NaFeO 2 , which is a transition metal oxide having a crystal structure of space group R3m, is used as the cathode material, the specific capacity of the cathode material during the first discharge Is very high at 993 mAh / g, and the specific capacity of the positive electrode material is significantly reduced between the first and second times. In comparison with the conventional LiCoO 2 having a specific capacity of about 150 mAh / g, the specific capacity was very high.
【００２６】また、第２回目以降においては、正極材料
の比容量の低下は非常に少なく、放充電効率も１００％
に近い値になっており、高い容量で安定した充放電が行
えるようになっていた。In the second and subsequent times, the decrease in the specific capacity of the positive electrode material is very small, and the discharge / charge efficiency is 100%.
, And stable charge and discharge can be performed with a high capacity.
【００２７】次に、正極材料に比容量が９９３ｍＡｈ／
ｇになった上記のＮａＦｅＯ2 を用いると共に、負極材
料に特願２０００−３２１２００号や特願２０００−３
２１２０１号に示す比容量が３０００ｍＡｈ／ｇになっ
たＬｉ−Ｓｉ合金を用いた実施例の非水電解質二次電池
と、正極材料に比容量が１５０ｍＡｈ／ｇになったＬｉ
ＣｏＯ2 を用いると共に、負極材料に比容量が３７０ｍ
Ａｈ／ｇになった黒鉛を用いた比較例の非水電解質二次
電池において、電池電圧を求めると共に、第１回目のサ
イクル時における容量密度（Ａｈ／ｋｇ）を下記の式
（１）により求め、さらにエネルギー密度（Ｗｈ／ｋ
ｇ）を下記の式（２）によって求め、その結果を下記の
表１に示した。Next, the specific capacity of the positive electrode material is 993 mAh /
g of the above-mentioned NaFeO 2 and the negative electrode material as disclosed in Japanese Patent Application Nos. 2000-321200 and 2000-3
Non-aqueous electrolyte secondary battery of Example using a Li-Si alloy having a specific capacity of 3000 mAh / g shown in No. 21201, and Li having a specific capacity of 150 mAh / g for a positive electrode material
Using CoO 2 , the specific capacity of the negative electrode material is 370 m
In the non-aqueous electrolyte secondary battery of Comparative Example using Ah / g of graphite, the battery voltage was determined, and the capacity density (Ah / kg) at the first cycle was determined by the following equation (1). , And the energy density (Wh / k
g) was determined by the following equation (2), and the results are shown in Table 1 below.
【００２８】 容量密度＝（正極材料の比容量×負極材料の比容量）／（正極材料の比容量＋負 極材料の比容量） …（１）Capacity density = (specific capacity of positive electrode material × specific capacity of negative electrode material) / (specific capacity of positive electrode material + specific capacity of negative electrode material) (1)
【００２９】 エネルギー密度＝容量密度×電池電圧 …（２）Energy density = capacity density × battery voltage (2)
【００３０】[0030]
【表１】 [Table 1]
【００３１】この結果から明らかなように、実施例の非
水電解質二次電池は、比較例の非水電解質二次電池に比
べて、容量密度及びエネルギー密度が大きく向上してい
た。As is apparent from the results, the nonaqueous electrolyte secondary batteries of the examples had greatly improved capacity density and energy density as compared with the nonaqueous electrolyte secondary batteries of the comparative examples.
【００３２】[0032]
【発明の効果】以上詳述したように、この発明における
非水電解質二次電池においては、正極における正極材料
に、空間群Ｒ３ｍの結晶構造を有する遷移金属酸化物
（但し、ＬｉＣｏＯ2 を除く。）を用いると共に、負極
にリチウムを含有する負極材料を用いるようにし、先ず
放電を行って、負極材料に含まれているリチウムを上記
の正極材料に挿入させた後、この正極と負極との間でリ
チウムイオンを移動させて充放電を行うようにしたた
め、多くの量のリチウムを充放電に関与させることがで
きるようになり、正極材料における比容量が高くなっ
て、エネルギー密度が向上し、高い電池容量をもつ非水
電解質二次電池が得られるようになった。As described in detail above, in the nonaqueous electrolyte secondary battery according to the present invention, the positive electrode material of the positive electrode is a transition metal oxide having a crystal structure of the space group R3m (excluding LiCoO 2 ). ) And using a negative electrode material containing lithium for the negative electrode. First, discharge is performed to insert the lithium contained in the negative electrode material into the above positive electrode material, and then between the positive electrode and the negative electrode. In order to perform charge and discharge by moving lithium ions, a large amount of lithium can be involved in charge and discharge, the specific capacity of the positive electrode material is increased, the energy density is improved, and the A non-aqueous electrolyte secondary battery having a battery capacity has been obtained.
【図１】この発明の実施例において使用した試験セルの
概略説明図である。FIG. 1 is a schematic explanatory view of a test cell used in an embodiment of the present invention.
【図２】上記の実施例の試験セルにおいて、１サイクル
目における放電及び充電の特性を示した図である。FIG. 2 is a diagram showing discharge and charge characteristics in a first cycle in the test cell of the above embodiment.
【図３】上記の実施例の試験セルにおいて、２サイクル
目における放電及び充電の特性を示した図である。FIG. 3 is a diagram showing discharge and charge characteristics in a second cycle in the test cell of the above example.
【図４】上記の実施例の試験セルにおいて、サイクル数
と正極材料の比容量との関係を示した図である。FIG. 4 is a diagram showing the relationship between the number of cycles and the specific capacity of a positive electrode material in the test cell of the above example.
【図５】上記の実施例の試験セルにおいて、サイクル数
と放充電効率との関係を示した図である。FIG. 5 is a diagram showing the relationship between the number of cycles and the discharge / charge efficiency in the test cell of the above embodiment.
１０ 試験セル １１ 作用極（正極） １２ 対極（負極） １３ 参照極 １４ 非水電解液（非水電解質） 10 Test cell 11 Working electrode (positive electrode) 12 Counter electrode (negative electrode) 13 Reference electrode 14 Non-aqueous electrolyte (non-aqueous electrolyte)
───────────────────────────────────────────────────── フロントページの続き (72)発明者 藤谷 伸 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 Ｆターム(参考） 5H029 AJ03 AK03 AL12 AM03 AM05 AM07 DJ17 5H050 AA08 BA16 CA07 CA08 CB12 FA19 HA02 HA13 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shin Fujitani 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. F-term (reference) 5H029 AJ03 AK03 AL12 AM03 AM05 AM07 DJ17 5H050 AA08 BA16 CA07 CA08 CB12 FA19 HA02 HA13
Claims (4)
電解質とを備えた非水電解質二次電池において、上記の
正極における正極材料に、空間群Ｒ３ｍの結晶構造を有
する遷移金属酸化物（但し、ＬｉＣｏＯ2 を除く。）を
用いると共に、負極にリチウムを含有する負極材料を用
いたことを特徴とする非水電解質二次電池。1. A non-aqueous electrolyte secondary battery including a positive electrode, a negative electrode, and a non-aqueous electrolyte using an organic solvent, wherein the positive electrode material of the positive electrode has a transition metal oxide having a crystal structure of a space group R3m. A non-aqueous electrolyte secondary battery using a material (however, excluding LiCoO 2 ) and using a negative electrode material containing lithium for the negative electrode.
において、上記の負極における負極材料に、金属リチウ
ム又はリチウム合金を用いたことを特徴とする非水電解
質二次電池。2. The non-aqueous electrolyte secondary battery according to claim 1, wherein lithium metal or a lithium alloy is used as a negative electrode material in the negative electrode.
次電池において、上記の空間群Ｒ３ｍの結晶構造を有す
る遷移金属酸化物がＮａＦｅＯ2 であることを特徴とす
る非水電解質二次電池。3. The non-aqueous electrolyte secondary battery according to claim 1, wherein the transition metal oxide having a crystal structure of the space group R3m is NaFeO 2. battery.
水電解質二次電池において、上記の負極材料が、Ｌｉ−
Ｓｉ合金であることを特徴とする非水電解質二次電池。4. The non-aqueous electrolyte secondary battery according to claim 1, wherein the negative electrode material is Li-
A non-aqueous electrolyte secondary battery comprising a Si alloy.
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| US10/632,834 US20040029007A1 (en) | 2000-11-13 | 2003-08-04 | Non-aqueous electrolyte battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009060828A1 (en) | 2007-11-09 | 2009-05-14 | Sumitomo Chemical Company, Limited | Complex metal oxide and sodium secondary battery |
| US7794879B2 (en) | 2004-03-31 | 2010-09-14 | Jun-ichi Yamaki | Positive electrode active material for non-aqueous electrolyte secondary cell |
| US9502714B2 (en) | 2009-03-13 | 2016-11-22 | Sumitomo Chemical Company, Limited | Mixed metal oxide, electrode, and sodium secondary battery |
| JP2023031127A (en) * | 2021-08-24 | 2023-03-08 | トヨタ自動車株式会社 | Manufacturing method for battery |
-
2000
- 2000-11-13 JP JP2000345124A patent/JP3778794B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7794879B2 (en) | 2004-03-31 | 2010-09-14 | Jun-ichi Yamaki | Positive electrode active material for non-aqueous electrolyte secondary cell |
| KR101245535B1 (en) | 2004-03-31 | 2013-03-21 | 스미또모 가가꾸 가부시키가이샤 | Positive electrode active material for non-aqueous electrolyte secondary battery |
| WO2009060828A1 (en) | 2007-11-09 | 2009-05-14 | Sumitomo Chemical Company, Limited | Complex metal oxide and sodium secondary battery |
| US9502714B2 (en) | 2009-03-13 | 2016-11-22 | Sumitomo Chemical Company, Limited | Mixed metal oxide, electrode, and sodium secondary battery |
| JP2023031127A (en) * | 2021-08-24 | 2023-03-08 | トヨタ自動車株式会社 | Manufacturing method for battery |
| JP7655148B2 (en) | 2021-08-24 | 2025-04-02 | トヨタ自動車株式会社 | Battery manufacturing method |
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