JPS61142669A - Positive pole material for solid cell - Google Patents
Positive pole material for solid cellInfo
- Publication number
- JPS61142669A JPS61142669A JP59265015A JP26501584A JPS61142669A JP S61142669 A JPS61142669 A JP S61142669A JP 59265015 A JP59265015 A JP 59265015A JP 26501584 A JP26501584 A JP 26501584A JP S61142669 A JPS61142669 A JP S61142669A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- conductivity
- solid
- battery
- range
- 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.)
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Links
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
-
- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
【発明の詳細な説明】
〔発明の分野〕
本発明は固体電池用正極材料、さらに詳しくはリチウム
固体電池に用いる正極活物質材料に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to positive electrode materials for solid-state batteries, and more particularly to positive electrode active materials used in lithium solid-state batteries.
従来、リチウム固体電池の正極活物質としてはＰｂＩ
＠ 、＾ｇＩなどの沃化物や沃素錯体ｈｓ ｚ 、Ｔａ
Ｓ ＠ 、 ＭｏＳ ２のような硫化物が用いられてい
る。Conventionally, PbI has been used as a positive electrode active material for lithium solid-state batteries.
Iodides such as @ , ＾gI and iodine complexes hs z , Ta
Sulfides such as S@, MoS2 are used.
従来固体電池はこれらの正極活物質の粉末を加圧し、さ
らに固体電解質粉末を重ね、その上にＬｉ箔あるいはＬ
ｉ粉末などの負極活物質を重ねて加圧成形することによ
って、作製されている。しかし、従来においては固体電
解質を用いて電池構成要素が全て固体である電池を作製
した特徴の一つである小型薄型にできるという利点が充
分に生かされていないという欠点があった。Conventional solid-state batteries press these positive electrode active material powders, layer solid electrolyte powder on top, and then layer Li foil or L on top of the solid electrolyte powder.
It is produced by layering negative electrode active materials such as i-powder and press-molding them. However, in the past, one of the characteristics of producing a battery in which all battery components are solid using a solid electrolyte, which is that it can be made small and thin, has not been fully utilized.
すなわち電池を小型、薄型化するには、まず正極活物質
の上に薄膜を形成することが必要であり、さらに正極活
物質についても基板上に薄膜を形成するか、あるいは基
板そのものを正極活物質で作るかの２つの方法で小型薄
膜型の固体電池が作製可能である。この後者の方法にお
いては薄膜形成の仮定が１つ少ないので構造的にも作製
上からも簡単であるが、これまで基板となり得るような
ｔ極活物質材料がなく、事実上製造が不可能であった。In other words, in order to make a battery smaller and thinner, it is first necessary to form a thin film on the positive electrode active material, and then either to form a thin film on the substrate for the positive electrode active material, or to replace the substrate itself with the positive electrode active material. Small thin-film solid-state batteries can be manufactured using two methods: In this latter method, there is one less assumption for thin film formation, so it is simpler in terms of structure and production. there were.
すなわち、このような基板となりうるためには焼結性が
良好なこと、また正極活物質として働くためには電子伝
導性が良好なことが必要であるが、たとえば上述のＴｉ
Ｓ ＠などは焼結性が悪（焼結体かえられないし、Ｐｂ
Ｉ ｔ 、ＢｉＩ ｓなども同様に焼結性が悪く、また
電子伝導性も悪く、正極基板となるようなものは得られ
ていなかった。In other words, in order to be able to serve as such a substrate, it is necessary to have good sinterability, and in order to work as a positive electrode active material, it is necessary to have good electronic conductivity.
S@ etc. have poor sinterability (the sintered body cannot be changed, and Pb
It, BiIs, etc. similarly have poor sinterability and poor electronic conductivity, and have not been able to be used as positive electrode substrates.
本発明は上述の点に鑑みなされたものであり、正極活物
質としての特性が良好で、導電性が良く、かつ基板とな
りえるほど焼結性の良好な固体電池用活物質材料を提供
することを目的とするものである。The present invention has been made in view of the above points, and an object of the present invention is to provide an active material for a solid battery that has good characteristics as a positive electrode active material, good conductivity, and has good sinterability so that it can be used as a substrate. The purpose is to
したがって本発明による固体電池用正極材料は一般式、
（Ｃｕｌ−ｘＭｘ） ｅＶ ＊０７ （ただし河は５
ＣＳＹ ｓ ５ａＳＧｄＳＤｙの希土類元素、およびＣ
ｒ、Ｇａｓ Ｍｎ、、Ｆｅ５Ｂｉｓ Ｓｂの３価元素、
χは０．０１≦ｘ≦０．２なる範囲の実数）で示される
ことを特徴とするものである。Therefore, the positive electrode material for solid-state batteries according to the present invention has the general formula:
(Cul-xMx) eV *07 (However, the river is 5
CSY s 5aSGdSDy rare earth elements, and C
r, Gas Mn,, trivalent element of Fe5Bis Sb,
χ is a real number in the range of 0.01≦x≦0.2).
また本発明による第二の固体電池用正極材料は一般式、
Ｃｌｌ！ （Ｖ ｘ −ｙＸ ｙ） ２Ｏ ？ （
ただしＸはＭＯ％ Ｈ、Ｃｒｓの６価元素、ｙは０．０
１≦ｙ≦０．２なる範囲の実数）で示されることを特徴
とするも□のである。Further, the second positive electrode material for solid-state batteries according to the present invention has the general formula:
Cll! (V x −yX y) 2O? (
However, X is a hexavalent element of MO% H, Crs, and y is 0.0
It is characterized by being represented by a real number in the range of 1≦y≦0.2).
さらに本発明による第三の固体電池用正極材料は、一般
式、（Ｃｕｌ −ｘＭ ｘ）’ｔ （Ｖ ｘ −ｙＸ
ｙ）ｉｏｙ（ただしＮは５ｃＳＹ ％ Ｓａ＋、Ｇｄ
、 ＤＦの希土類元素、およびＣｒｓ Ｇａ５Ｍｎ１Ｆ
ｅ１１１１ Ｓｂの３価元素、χは０．０１≦ｘ≦０．
２なる範囲の実数、Ｘは６０、Ｗ ＳＣｒの６価元素、
ｙは０．０１≦ｙ≦０．２なる範囲の実数）で示される
ことを特徴とする。Furthermore, the third positive electrode material for solid batteries according to the present invention has the general formula: (Cul -xM x)'t (V x -yX
y) ioy (N is 5cSY% Sa+, Gd
, DF rare earth elements, and Crs Ga5Mn1F
e1111 Trivalent element of Sb, χ is 0.01≦x≦0.
A real number in the range of 2, X is 60, a hexavalent element of W SCr,
y is a real number in the range of 0.01≦y≦0.2).
本発明によれば、リチウム電池用正極材料としての特性
が良好で導電性がよく、かつ焼結性も良好であ゛るので
固体電池作製の正極基板として利用可能である。このた
め比較的簡便な方法で薄型固体電池を製造可能になると
いう利点がある。According to the present invention, the material has good characteristics as a positive electrode material for lithium batteries, has good conductivity, and has good sinterability, and can be used as a positive electrode substrate for producing solid batteries. Therefore, there is an advantage that a thin solid state battery can be manufactured by a relatively simple method.
本発明をさらに詳しく説明する。 The present invention will be explained in more detail.
本発明による固体電池用正極材料はリチウム二次電池用
正極活物質として良好な特性を示すＣｕ２Ｖ２０７に着
目し、この材料の導電性の改良、焼結性の改良のため、
Ｃｕの一部を５ｃＳＳＩＩ％Ｇｄなどの希土類元素やＣ
ｒｓ Ｇａ等の３価の元素で置換することにより、ある
いはＶの一部をｌｌｏ、 Ｈ、Ｏｒなどの６価元素で置
換することにより得た磁器組成物にしたものである。The positive electrode material for solid-state batteries according to the present invention focuses on Cu2V207, which exhibits good characteristics as a positive electrode active material for lithium secondary batteries, and in order to improve the conductivity and sinterability of this material,
A part of Cu is replaced by a rare earth element such as 5cSSII%Gd or C.
This is a ceramic composition obtained by substituting a trivalent element such as rs Ga or by substituting a part of V with a hexavalent element such as llo, H, Or, etc.
すなわち本発明によれば、
（１） 一般式、（Ｃｕｌ −ｘＭ ｘ） ｅＶ ２
Ｏ ７ （ただしｎは５０％ Ｙ ％ ５ｌｌｓ Ｇ
ｄｓ Ｄｙの希土類元素、およびＣｒｓ Ｇａｓ Ｍｎ
、Ｆｅ５Ｂｉ、 Ｓｂの３価元素、χは０．０１≦ｘ≦
０．２なる範囲の実数）で示される固体電池用正極材料
、
（２） 一般式、Ｃｕｅ （Ｖｚ−ｙＸｙ）ｓ０７
（ただしＸはＭＯ％ Ｗ 、Ｃｒ、の６価元素、ｙは
０．０１≦ｙ≦０．２なる範囲の実数）で示される固体
電池用正極材料、
（３） 一般式、（Ｃｕｔ −ｘＨｘ） ｔ （Ｖ
ｘ −ｙＸｙ）ｉｏｙ（ただしｈは５ｃＳＹ ５Ｓｔ
ａＳＧｄｓ Ｄｙの希土類元素、およびＣｒＳＧａ５Ｍ
ｎ５ Ｆｅｓ ８１％ Ｓｂの３価元素、χは０．０１
≦ｘ≦０．２なる範囲の実数、ＸはＭＯＳＷ 、Ｃｒの
６価元素、ｙは０．０１≦ｙ≦０．２なる範囲の実数）
で示される固体電池用正極材料を提供するものである。That is, according to the present invention, (1) General formula, (Cul -xM x) eV 2
O 7 (However, n is 50% Y % 5lls G
ds Dy rare earth elements, and Crs Gas Mn
, Fe5Bi, Sb trivalent elements, χ is 0.01≦x≦
(2) General formula, Cue (Vz-yXy)s07
(where X is a hexavalent element of MO% W, Cr, and y is a real number in the range of 0.01≦y≦0.2), (3) General formula, (Cut −xHx ) t (V
x -yXy) ioy (h is 5cSY 5St
aSGds Dy rare earth elements, and CrSGa5M
n5 Fes 81% Trivalent element of Sb, χ is 0.01
(Real number in the range ≦x≦0.2, X is a hexavalent element of MOSW, Cr, y is a real number in the range 0.01≦y≦0.2)
The object of the present invention is to provide a positive electrode material for a solid battery shown in the following.
上述の式においてＸおよびｙは０．０１≦Ｘ＋３’≦０
゜２の範囲にあるが、χ、ｙがこの範囲を逸脱すると後
述の実施例に示すように焼結性が悪化したり、導電性が
低下するからである。In the above formula, X and y are 0.01≦X+3'≦0
If χ and y are within the range of .degree.
上記に示した固体電池用正極材料は、たとえば下記のよ
うに製造することができる。The solid battery positive electrode material shown above can be manufactured, for example, as follows.
まず原料としてＣｕＯＳＶ ＠ Ｏｓ 、Ｍ ！ Ｏａ
（Ｓｃｔ Ｏａ 、ＳＩｌ＄＋ ０３、Ｃｒｓ Ｏ
ａ 、Ｇａｙ Ｏａなど）およびＸ ０３（Ｍｏ０３
、ＷＯａ 、Ｃｒ０３など）を上記式（１）、（２）、
（３）に基づいて混合し、空気中で６００℃で２４時間
仮焼成し、Ｉｔ／−の圧力で成形し、これを６２０℃で
１０時間焼成して焼結体を得る、あるいは仮焼粉末を成
形した後、６２０℃で２時間、４００Ｋｇ／ａｄの圧力
でホットプレスを行う等の方法にｊり通常焼成法により
緻密な焼結体が得られる。First, CuOSV@Os, M! Oa
(Sct Oa, SIl$+ 03, Crs O
a, Gay Oa, etc.) and X03 (Mo03
, WOa, Cr03, etc.) using the above formulas (1), (2),
(3), calcined in air at 600℃ for 24 hours, molded at a pressure of It/-, and calcined at 620℃ for 10 hours to obtain a sintered body, or calcined powder. After molding, a dense sintered body can be obtained by a normal firing method such as hot pressing at 620° C. for 2 hours at a pressure of 400 kg/ad.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
実施例Ｉ
Ｃｕを置換する３価の元素としてＳｃを採り上げ、（Ｃ
ｕｌ −ｘＳｃｘ ） ｔ Ｖ ｓＩｏ ７なる式にお
いて、０≦ｘ≦０．３０の範囲の試料について上記通常
磁器焼成法により作成した。Example I Taking Sc as a trivalent element to replace Cu, (C
In the formula ul - x Scx ) t V sIo 7, samples in the range of 0≦x≦0.30 were prepared by the above-mentioned normal porcelain firing method.
これらの試料はＳｃ量が２％程度から焼結性が良好にな
り、特に５〜２０％の範囲の試料がよく焼結することが
わかった。２０℃における導電率と組成の関係を第１図
に示す、この第１図より明らかなように、Ｓｃが０．５
％から１３％の範囲でＳｃを添加していないＣｕｂ Ｖ
２０７の２０倍以上の導電性を示しており、１０％を
過ぎると減少してくるが、それでも２０％においてＣｕ
２ Ｖ ＠ ０７と同じ程度になる。It was found that the sinterability of these samples becomes good when the Sc content is around 2%, and the samples in which the Sc content is in the range of 5 to 20% sinter well. Figure 1 shows the relationship between conductivity and composition at 20°C.As is clear from Figure 1, when Sc is 0.5
Cub V with no added Sc in the range of % to 13%
The conductivity is more than 20 times that of 207, and it decreases after 10%, but still, at 20%, Cu
It will be about the same as 2 V @ 07.
この導電率の減少はＳｃがＣｕ２ Ｖ ｔ ０７に固溶
できず、ＳｃＶ ＯａとなってＣｕ２Ｖ１０７の結晶相
に混在してくるからであると考えられる。This decrease in electrical conductivity is thought to be because Sc cannot form a solid solution in Cu2Vt07, and becomes ScVOa, which is mixed in the crystal phase of Cu2V107.
この（Ｃｕｌ −ｘＳｃｘ） ＊ Ｖ ２Ｏ ７では、
０．０２≦ｘ≦０．１５の範囲で焼結性も良く、導電性
も良い。In this (Cul -xScx) *V 2O 7,
In the range of 0.02≦x≦0.15, the sinterability is good and the conductivity is also good.
しかし、０．０１≦ｘ≦０．０２の範囲でも導電性は充
分に大きく、ホットプレス法によって焼結体を得ること
が可能である。しかしながらχ＜０．０１となると焼結
体を得るのが困難になる。 ０．１５＜χ≦０．２の範
囲では導電率は０．０１≦ｘ≦０．１５に比較して小さ
くなるが、Ｃｕ２ Ｖ ＠ ０７より大きく、焼結性は
良好であるので正極基板として使用することが可能であ
る。However, even in the range of 0.01≦x≦0.02, the conductivity is sufficiently high, and it is possible to obtain a sintered body by hot pressing. However, when χ<0.01, it becomes difficult to obtain a sintered body. In the range of 0.15<χ≦0.2, the conductivity is smaller than that in 0.01≦x≦0.15, but it is higher than Cu2V@07 and has good sinterability, so it can be used as a positive electrode substrate. It is possible to use.
実施例２
実施例１と同様にＣｕを置換する元素としてＣｒ ５Ｇ
ａｓ Ｍｎ５Ｆｅｓ ＢＩＳＳｂを用い、上記の方法に
よって焼結した。これらの材料にっても導電率と組成に
関係は実施例１と同様の傾向を示した。焼結性において
も０．Ｏ１≦ｘ≦０．２の範囲において良好であった。Example 2 Similar to Example 1, Cr 5G was used as an element to replace Cu.
As Mn5Fes BISSb was used and sintered by the method described above. These materials also showed the same tendency as Example 1 in terms of the relationship between conductivity and composition. The sinterability is also 0. Good results were obtained within the range of O1≦x≦0.2.
実施例３
実施例１と同様な方法で、Ｃむ （Ｖ １−γＸγ）２
Ｏ７なる式に基づいて、ＸとしてＦＩｏＳ賀、Ｃｒを用
いて、０５Ｖ≦０．３の範囲で焼結体を製造した。Example 3 In the same manner as in Example 1, Cmu (V1-γXγ)2
Based on the formula O7, a sintered body was manufactured using FIoS and Cr as X in the range of 05V≦0.3.
ｙ ＞０．２の範囲ではＣｕ２ Ｖ ２０７相以外の相
との混合相になり導電性が低下する。焼結性に関しては
ｙ ＜０．０１ではＣｕｇＶｓ＋Ｏｖと同様焼結性が悪
（、焼結体は得られなかった。ｏ、ｏｉ≦ｙ≦０．２の
範囲では比較的焼結性が良く、また導電性もＣｕ２ｖ２
０７よりも大きくなる。In the range of y>0.2, a mixed phase with phases other than the Cu2V207 phase is formed, and the conductivity decreases. Regarding sinterability, when y < 0.01, the sinterability was poor (no sintered body was obtained), similar to CugVs+Ov. In the range of o, oi≦y≦0.2, the sinterability was relatively good; Also, the conductivity is Cu2v2
It becomes larger than 07.
実施例４
（Ｃｕｌ −ｘＭ ｘ） ｔ （Ｖ １−ｙ Ｘｙ）
＊Ｏｔなる式に基づき、台としてＳｃ、 Ｇｄｓ Ｃｒ
ｓ Ｇａ５Ｍｎ、 Ｆｅ５ＢｉＳＳｂＳｘとしてＭｏ
Ｓ−を用い、上記の方法で焼結体を作成した。代表的な
試料の室温における導電率を第１表に示す。Example 4 (Cul -xM x) t (V 1-y Xy)
*Based on the formula Ot, Sc, Gds Cr as the base
s Ga5Mn, Mo as Fe5BiSSbSx
A sintered body was produced using S- by the method described above. Table 1 shows the electrical conductivity of typical samples at room temperature.
第１表
いずれもＣｕ２Ｖ２０７の５ ｘｌＯ−２（Ｓ ／ｍ
）に比較して導電率が１桁以上大きくなっていた。Table 1 shows 5xlO-2 (S/m) of Cu2V207.
), the electrical conductivity was greater than 1 digit.
また焼結性においても、Ｍ、Ｘを０．０５≦ｘ；ｙ≦０
゜２の範囲で添加した場合、良好であった。Also, regarding sinterability, M and X are 0.05≦x; y≦0
Good results were obtained when the amount was added within the range of 2°C.
実施例１、実施例２、実施例３、実施例４で述ベた代表
的なものの導電率の温度依存性を第２図に示す。番号１
．２．３．４．５．６．７．８．９．１０はそれぞれ（
Ｃｕ（１３Ｓｃａ、Ｊ ２ Ｖ ｉｔ Ｏ？、（Ｃｕｏ
ＪＧａａｏ＋） Ｓ！ Ｖ ｔ ０７、（Ｃｕｇ１Ｍｎ
ａｏ＋） ｗ Ｖ ｔ ０７、（ＣｕｆｉＪＣｒ＋ｕ＋
＋） ｆｆ１ｖ ＩＩＯｒ、Ｃｕｔ （ＶａｎＭＯａ
ａ＋） ｔ０７ 、Ｃｕｇ （Ｖ 、、Ｗ １ｏｔ）
２０７、（Ｃｕ４３Ｓｃａｘ） ｔ Ｖ２Ｏ７、（Ｃ
ｕＩＬ、Ｇａ１Ｌｘ） ！ Ｖ ＊ ０７ 、Ｃｕｇ
（Ｖ ６，５Ｎ。FIG. 2 shows the temperature dependence of the conductivity of the typical materials described in Examples 1, 2, 3, and 4. number 1
．． 2.3.4.5.6.7.8.9.10 are respectively (
Cu(13Sca, J 2 V it O?, (Cuo
JGaao+) S! V t 07, (Cug1Mn
ao+) w V t 07, (CufiJCr+u+
+) ff1v IIOr, Cut (VanMOa
a+) t07, Cug (V,, W 1ot)
207, (Cu43Scax) t V2O7, (C
uIL, Ga1Lx)! V*07, Cug
(V 6,5N.
０．１） ｗ Ｏｌ−、（Ｃｕｏ３Ｓｃｏ、ｘ） ２（
Ｖ ｇＭｏａｏ＋） ２０７であり、比較のためＣｕ１
Ｖ１０７を１１として示ピた。0.1) w Ol-, (Cuo3Sco, x) 2(
V gMoao+) 207, and Cu1 for comparison
V107 was shown as 11.
実施例５
実施例１で述べた材料の１つである（Ｃｕｏ、５ＳＣａ
□） ２Ｖ ｅｏ ？を正極材料に用い、有機電解液を
用 。Example 5 One of the materials mentioned in Example 1 (Cuo, 5SCa
□) 2Veo? is used as the positive electrode material, and an organic electrolyte is used.
いたＰ電池を作成し、その電池特性を調べた。A P battery was prepared and its battery characteristics were investigated.
電池は次ぎのようにして作成した。まず、正極活物質に
導電剤としてケッチェンブラックＥＣおよびポリテトラ
フルオロエチレンを重量比で７５ ： ２５：５の割合
で混合し、正極混合物を厚み０．６ｆｌ、系１６關の円
盤系に成型し、これをステンレス製の正極容器に入れ、
径１８鰭のＮｉの網で固定し、さらにセパレータを重ね
、電解液としてｌＮ−ＬｉＣｌ０ａ／ＰＣ＋ＤＭＥ
（プロピレンカーボネイト＋１，２−ジェトキシエタン
の等容積混合溶媒）を適量注入し、その上にＬｉ金属を
圧着した負極容器をかぶせて、かしめ、径２３龍、厚さ
２ｆｉのコイン型電池を作成した。The battery was created as follows. First, Ketjenblack EC and polytetrafluoroethylene as conductive agents were mixed with the positive electrode active material in a weight ratio of 75:25:5, and the positive electrode mixture was molded into a disk with a thickness of 0.6 fl and a diameter of 16 mm. , put this in a stainless steel cathode container,
It was fixed with a Ni net with a diameter of 18 fins, a separator was further layered, and lN-LiCl0a/PC+DME was used as the electrolyte.
(equal volume mixed solvent of propylene carbonate + 1,2-jethoxyethane) was injected, and a negative electrode container with Li metal crimped was placed on top of the negative electrode container to create a coin-shaped battery with a diameter of 23mm and a thickness of 2fi.
このように作製された電池を１ ｍＡで定電流放電を行
ったところ、第３図のへのような放電曲線になった。電
池電圧が２ｖに低下するまでの正極活物質の放電容量密
度は３３０ Ａｈ／Ｉｇ、エネルギ密度は８６１Ｗｈ
／Ｋｇであり、電圧が１ｖに低下するまでの放電容量密
度は５２０ Ａｈ／にｇ、エネルギ密度は１ｊ−５０賀
ｈ ／Ｋｇであった。When the battery thus prepared was subjected to constant current discharge at 1 mA, a discharge curve as shown in Fig. 3 was obtained. The discharge capacity density of the positive electrode active material until the battery voltage drops to 2V is 330 Ah/Ig, and the energy density is 861Wh.
/Kg, the discharge capacity density was 520 Ah/Kg until the voltage decreased to 1V, and the energy density was 1j-50Ah/Kg.
また比較のため、Ｃｕ１Ｖ１０７を正極活物質に用いた
このコイン型電池を用いて、１ ｍＡの定電流で充放電
を行った。充放電サイクルは放電１５時間、休止１時間
、充電１５時間、休止１時間である。第４図は充放電の
結果を示す図である０曲線＾、Ｂ ％Ｃ，Ｄはそれぞれ
第１回目、第２回目、第１０回目、第２０回目の放電充
電の様子を示している。For comparison, this coin-shaped battery using Cu1V107 as the positive electrode active material was charged and discharged at a constant current of 1 mA. The charge/discharge cycle is 15 hours of discharging, 1 hour of rest, 15 hours of charging, and 1 hour of rest. FIG. 4 is a diagram showing the results of charging and discharging. 0 curve ^, B%C, and D show the states of the first, second, tenth, and 20th discharging and charging, respectively.
このように（ＣＬｌａｓＳＣａｌ） ＊ Ｖ ｔ ０７
を正極活物質として用いたコイン型電池は放電電圧の平
坦製、放電容′量の大きさ、充放電のサイクル性で優れ
た特性を示している。すなわち、（ＣｕａｓＳｃａｚ）
ｔ Ｖ２Ｏ７はリチウム二次電池の正極材料として優
れた特性を有していることがわかった。Like this (CLlasSCal) * V t 07
Coin-type batteries using this as the positive electrode active material have shown excellent characteristics in terms of flat discharge voltage, large discharge capacity, and charge/discharge cycle performance. That is, (CuasScaz)
It was found that tV2O7 has excellent properties as a positive electrode material for lithium secondary batteries.
実施例６
実施例５で述べたように（ＣｕａｓＳｃｏ、ｘ） ２
Ｖ ２０７はリチウム二次電池の正極活物質として良好
な特性を示すので、この材料を用い、固体電池を作製し
た。まず、この（Ｃｕ４３Ｓｃａｘ） ｅ Ｖ ｅ ０
７を通常焼成法で作製し、粉砕し、成形した後、ホット
プレス法により、直径２５ｕ＋、厚み８鶴程度の円盤を
作製した。これをスライスし研磨して、Ｑ、３ｍｍ厚の
基板を作製した。この基板の表面に電解質としてＬｉ３
Ｚｎｇ、５ＧｅＯａ非晶質膜を５０００人はどスパッ
タ法により堆積させた。裏面には正極側集電極としてＡ
ｕのスパッタ膜を約１０００人程度付着させた。Example 6 As stated in Example 5 (CuasSco, x) 2
Since V207 exhibits good properties as a positive electrode active material for lithium secondary batteries, a solid battery was fabricated using this material. First, this (Cu43Scax) e V e 0
7 was produced by a normal firing method, crushed and molded, and then a disk having a diameter of 25 U+ and a thickness of about 8 cranes was produced by a hot pressing method. This was sliced and polished to produce a substrate Q with a thickness of 3 mm. Li3 is used as an electrolyte on the surface of this substrate.
A Zng, 5GeOa amorphous film was deposited by sputtering using 5,000 people. On the back side, there is A as a positive collector electrode.
Approximately 1,000 sputtered films of u were deposited.
この電解質を付着させた正極基板を８鶴角の正方形に切
り出し、この電解質薄膜の上側に面積０゜２ｃｊのＬｉ
極を形成し、電池を構成させた。負極側集電極としてＮ
ｉ板を重ねた。The positive electrode substrate to which this electrolyte was adhered was cut into an 8-square square, and Li with an area of 0°2cj was placed on top of this electrolyte thin film.
The poles were formed and the battery was constructed. N as negative electrode side collector electrode
I stacked the i-boards.
この電池を用いて放電試験を行った結果を第５図に示す
。放電電流密度は５μＡ／−であった。FIG. 5 shows the results of a discharge test conducted using this battery. The discharge current density was 5 μA/−.
図のように２ｖ以上を保持する放電容量は、単位面積あ
たり、２００μＡｈ以上であり、電池の厚みが０．３
ｗ程度の非常に薄い電池として良好な電池特性を示して
いた。As shown in the figure, the discharge capacity to maintain 2V or more is 200μAh or more per unit area, and the battery thickness is 0.3V or more.
It showed good battery characteristics as a very thin battery of about 200 lbs.
以上説明したように、本発明による固体電池用正極材料
は、リチウム電池用正極材料としての特性が良好で、か
つ導電性がよく、焼結性が良好であるので、固体電池作
製の正極基板として利用することができる。これにより
、比較的簡単な手順で薄型固体電池の作製が可能になる
。As explained above, the positive electrode material for solid-state batteries according to the present invention has good characteristics as a positive electrode material for lithium batteries, has good conductivity, and has good sinterability, so it can be used as a positive electrode substrate for manufacturing solid-state batteries. can be used. This makes it possible to manufacture thin solid-state batteries using relatively simple procedures.
第１図は本発明による一実施例の（Ｃｕ１− ｘ ５ｃ
Ｘ）２Ｖ ２Ｏ ７の２０℃における導電率と組成の関
係を示した図、第２図は本発明における代表的材料の導
電率の温度依存性を示した図、第３図は本発明における
（Ｃｕｏ、３Ｓｃｏ、１） ２ Ｖ ２０７を正極材料
を用いたリチウム電池の放電試験の結果を示す図、第４
図は本発明による（Ｃｕ（１，５Ｓｃｏ、ｚ） ｆｆｉ
Ｖ ｔ ０７を正極材料に用いたリチウム電池の充放
電試験の結果を示す図、第５図は本発明による（Ｃｕｇ
、３ＳＣａｘ ）１！ＶＩ１０７を正極材料として用い
た固体電池の放電特性を示す図である。
出願人代理人 雨 宮 正 季第１図
ｓｃ シ資加１１ （０ム ）
１０００／Ｔ （に ）
臂 Ｍ （Ｎ ｅ−。
（＾）Ｖ番）Ｓ凄Ｉ
（＾）１″ｉＩＰ♀ｆ車
第５図
江電容’ｌ（ｙＡｈ）FIG. 1 shows one embodiment of the present invention (Cu1- x 5c
X) A diagram showing the relationship between the conductivity and composition of 2V 2O 7 at 20°C, Figure 2 is a diagram showing the temperature dependence of the conductivity of representative materials in the present invention, and Figure 3 is a diagram showing the relationship between the conductivity and composition of (X) 2V 2O 7 in the present invention. Cuo, 3Sco, 1) Figure 4 showing the results of a discharge test of a lithium battery using 2V 207 as a positive electrode material.
The figure is according to the present invention (Cu(1,5Sco,z) ffi
Figure 5 is a diagram showing the results of a charge/discharge test of a lithium battery using V t 07 as the positive electrode material.
,3SCax)1! FIG. 3 is a diagram showing the discharge characteristics of a solid battery using VI107 as a positive electrode material. Applicant's agent Masaki Amemiya Figure 1 SC Shishika 11 (0mu) 1000/T (ni) Arm M (Ne-. Car Figure 5 Jiangden Yong'l (yAh)
Claims (3)
Ｏ＿７（ただしＭはＳｃ、Ｙ、Ｓｍ、Ｇｄ、Ｄｙの希土
類元素、およびＣｒ、Ｇａ、Ｍｎ、Ｆｅ、Ｂｉ、Ｓｂの
３価元素、ｘは０．０１≦ｘ≦０．２なる範囲の実数）
で示されることを特徴とする固体電池用正極材料。(1) General formula, (Cu_1_−_xM_x)_2V_2
O_7 (M is a rare earth element of Sc, Y, Sm, Gd, Dy, and a trivalent element of Cr, Ga, Mn, Fe, Bi, Sb, x is a real number in the range of 0.01≦x≦0.2 )
A positive electrode material for solid-state batteries characterized by:
Ｏ＿７（ただしｘはＭｏ、Ｗ、Ｃｒ、の６価元素、ｙは
０．０１≦ｙ≦０．２なる範囲の実数）で示されること
を特徴とする固体電池用正極材料。(2) General formula, Cu_2(V_1_−_yX_y)_2
A positive electrode material for a solid battery, characterized in that it is represented by O_7 (where x is a hexavalent element such as Mo, W, or Cr, and y is a real number in the range of 0.01≦y≦0.2).
１＿−＿ｙＸ＿ｙ）＿２Ｏ＿７（ただしｎはＳｃ、Ｙ、
Ｓｍ、Ｇｄ、Ｄｙの希土類元素、およびＣｒ、Ｇａ、Ｍ
ｎ、Ｆｅ、Ｂｉ、Ｓｂの３価元素、ｘは０．０１≦ｘ≦
０．２なる範囲の実数、ＸはＭｏ、Ｗ、Ｃｒの６価元素
、ｙは０．０１≦ｙ≦０．２なる範囲の実数）で示され
ることを特徴とする固体電池用正極材料。(3) General formula, (Cu_1_−_xM_x)_2(V_
1_-_yX_y)_2O_7 (where n is Sc, Y,
Rare earth elements Sm, Gd, Dy, and Cr, Ga, M
n, trivalent elements of Fe, Bi, and Sb, x is 0.01≦x≦
A positive electrode material for a solid battery, characterized in that X is a hexavalent element such as Mo, W, or Cr, and y is a real number in the range of 0.01≦y≦0.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59265015A JPS61142669A (en) | 1984-12-14 | 1984-12-14 | Positive pole material for solid cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59265015A JPS61142669A (en) | 1984-12-14 | 1984-12-14 | Positive pole material for solid cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61142669A true JPS61142669A (en) | 1986-06-30 |
| JPH0329128B2 JPH0329128B2 (en) | 1991-04-23 |
Family
ID=17411392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59265015A Granted JPS61142669A (en) | 1984-12-14 | 1984-12-14 | Positive pole material for solid cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61142669A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0423117A1 (en) * | 1987-11-25 | 1991-04-24 | DURACELL INC. (a Delaware corporation) | Electrochemical cells |
| JP2013058479A (en) * | 2011-09-08 | 2013-03-28 | Eaglepicher Technologies Llc | High-rate and high-energy cathode material for lithium cell |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5512675A (en) * | 1978-07-12 | 1980-01-29 | Sanyo Electric Co Ltd | Nonaqueous electrolyte cell |
-
1984
- 1984-12-14 JP JP59265015A patent/JPS61142669A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5512675A (en) * | 1978-07-12 | 1980-01-29 | Sanyo Electric Co Ltd | Nonaqueous electrolyte cell |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0423117A1 (en) * | 1987-11-25 | 1991-04-24 | DURACELL INC. (a Delaware corporation) | Electrochemical cells |
| JP2013058479A (en) * | 2011-09-08 | 2013-03-28 | Eaglepicher Technologies Llc | High-rate and high-energy cathode material for lithium cell |
| CN103022455A (en) * | 2011-09-08 | 2013-04-03 | 伊格皮切尔科技有限责任公司 | High rate and energy cathode material for lithium batteries |
| EP2568525A3 (en) * | 2011-09-08 | 2014-04-02 | EaglePicher Technologies, LLC | High rate and energy cathode material for lithium batteries |
| US10355306B2 (en) | 2011-09-08 | 2019-07-16 | Eaglepicher Technologies, Llc | High rate and energy cathode material for lithium batteries |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0329128B2 (en) | 1991-04-23 |
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