JP2000086215A - Lithium vanadium phosphate composite compound and positive electrode material made of that composite compound for lithium ion secondary cell - Google Patents
Lithium vanadium phosphate composite compound and positive electrode material made of that composite compound for lithium ion secondary cellInfo
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- JP2000086215A JP2000086215A JP10261930A JP26193098A JP2000086215A JP 2000086215 A JP2000086215 A JP 2000086215A JP 10261930 A JP10261930 A JP 10261930A JP 26193098 A JP26193098 A JP 26193098A JP 2000086215 A JP2000086215 A JP 2000086215A
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- Prior art keywords
- composite compound
- lithium
- positive electrode
- compound
- electrode material
- Prior art date
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【０００２】本発明は、燐酸リチウム・バナジウム複合
化合物及び同複合化合物からなるリチウムイオン二次電
池用正極材料に関する。The present invention relates to a lithium-vanadium phosphate composite compound and a positive electrode material for a lithium ion secondary battery comprising the composite compound.
【０００３】従来、リチウムイオン二次電池用正極材料
としてバナジウムイオン含有リチウム燐酸化合物が検討
されている。正極特性は、充放電の際のＬｉイオンのイ
ンタカレーションが容易かどうか、即ち、電荷移動が容
易かどうかのみならず、正極材料中でＬｉイオンの拡散
が容易かどうかによって大きく影響を受けることが知ら
れている。Ｌｉ3 Ｖ2 （ＰＯ4 ）3 の理論容量は１３
１．５ｍＡｈ／ｇであるが、これまでせいぜい６０％し
か利用できなかった。 また、β―Ｆｅ２（ＳＯ 4 ）3
構造を持つＬｉ3 Ｖ2 （ＰＯ4 ）３は、温度によって３
つの相を呈し、高温相は高いイオン伝導性を示すことが
知られている。Ｓ．Ｏｋａｄａ，Ｈ．Ａｓａｋｕｒａ，
Ｙ．Ｓａｋｕｒａｉ，Ｊ．Ｙａｍａｋｉ，Ｋ．Ｓ．Ｎａ
ｎｊｕｎｄａｓｗａｍｙ、Ａ．Ｋ．Ｐａｄｈｉ，Ｃ．Ｎ
ａｓｑｕａｌｉｅｒ ＆ Ｊ．Ｂ．Ｇｏｏｄｅｎｅｕｇ
ｈ，“Characteristics of 3D Framework Cathodes wit
h the (X04)n- Polyanions", The 37th Battery Sympos
ium in Japan, Abstract, 19(1996)参照。Conventionally, cathode materials for lithium ion secondary batteries
Study of lithium phosphate compounds containing vanadium ions
Have been. Positive electrode characteristics are based on Li ion
Easy intercalation, i.e. charge transfer
Not only whether it is easy, but also diffusion of Li ions in the cathode material
Is known to be greatly affected by whether
Have been. LiThreeVTwo(POFour)ThreeTheoretical capacity of 13
1.5 mAh / g, but up to 60%
Or was not available. Also, β-Fe2 (SO Four)Three
Li with structureThreeVTwo(POFour3) is 3 depending on the temperature.
Phase and the high-temperature phase can exhibit high ionic conductivity.
Are known. S. Okada, H .; Asakura,
Y. Sakurai, J .; Yamaki, K .; S. Na
njundaswamy, A .; K. Padhi, C.I. N
asqualier & J.S. B. Goodeneg
h, “Characteristics of 3D Framework Cathodes wit
h the (X04) n- Polyanions ", The 37th Battery Sympos
See ium in Japan, Abstract, 19 (1996).
【０００４】本発明者は、バナジウムイオンあるいは鉄
イオン含有リチウム燐酸化合物の正極特性の改良を試み
る中で、バナジウムイオンあるいは鉄イオン含有リチウ
ム燐酸化合物において室温で安定した高イオン伝導性を
達成できれば、優れた充放電特性を有する正極材料が得
られることを期待できることに着目した。The inventor of the present invention has attempted to improve the positive electrode characteristics of a vanadium ion or iron ion-containing lithium phosphate compound. It is expected that a positive electrode material having good charge / discharge characteristics can be expected.
【０００５】従って、本発明は優れた充放電特性を有す
る正極材料として用いることができるリチウムイオン二
次電池用正極材料としてのバナジウムイオン含有リチウ
ム燐酸化合物及び該バナジウムイオン含有リチウム燐酸
化合物からなるリチウムイオン二次電池用正極材料を提
供することを目的とする。Accordingly, the present invention provides a vanadium ion-containing lithium phosphate compound and a lithium ion comprising the vanadium ion-containing lithium phosphate compound as a cathode material for a lithium ion secondary battery which can be used as a cathode material having excellent charge / discharge characteristics. An object is to provide a positive electrode material for a secondary battery.
【０００６】本発明の燐酸リチウム・バナジウム複合化
合物は、下記一般式（１）で表されることを特徴とす
る。 Ｌｉy （Ｖ1-x Ｍx ）2 （ＰＯ4 ）3 ここに、Ｍはアルミニウム、チタニウム及びジルコニウ
ムから選ばれた２価以上の陽イオンのうち少なくとも１
種類であり、０＜ｘ≦０．２であり、ｙはＭがアルミニ
ウムの場合はｙは３、Ｍがチタニウムあるいはジルコニ
ウムの場合はｙは３−２ｘである。[0006] The lithium-vanadium phosphate composite compound of the present invention is characterized by being represented by the following general formula (1). Li y (V 1-x M x ) 2 (PO 4 ) 3 where M is at least one of divalent or higher cations selected from aluminum, titanium and zirconium.
0 <x ≦ 0.2, y is 3 when M is aluminum, and y is 3-2x when M is titanium or zirconium.
【０００７】また、本発明のリチウム二次電池用正極材
料は、下記一般式（１）で表される燐酸リチウム・バナ
ジウム複合化合物からなることを特徴とする。 Ｌｉy （Ｖ1-x Ｍx ）2 （ＰＯ4 ）3 ここに、Ｍはアルミニウム、チタニウム及びジルコニウ
ムから選ばれた２価以上の陽イオンのうち少なくとも１
種類であり、０＜ｘ≦０．２であり、ｙはＭがアルミニ
ウムの場合はｙは３、Ｍがチタニウムあるいはジルコニ
ウムの場合はｙは３−２ｘである。Further, the positive electrode material for a lithium secondary battery of the present invention is characterized by comprising a lithium-vanadium phosphate composite compound represented by the following general formula (1). Li y (V 1-x M x ) 2 (PO 4 ) 3 where M is at least one of divalent or higher cations selected from aluminum, titanium and zirconium.
0 <x ≦ 0.2, y is 3 when M is aluminum, and y is 3-2x when M is titanium or zirconium.
【０００８】なお、上記式（１）はＭがＡｌ，Ｔｉ，Ｚ
ｒの場合、即ちＬｉy （Ｖ1-x1-X2- X3Ａｌx1ＴｉX2Ｚｒ
X3）2 （ＰＯ4 ）3 の場合、ｙは（３−２Ｘ2 −２
Ｘ3 ）であることを示す場合も含むことは言うまでもな
い（（Ｘ＝Ｘ1 ＋Ｘ2 ＋Ｘ3 ））。In the above equation (1), M is Al, Ti, Z
r, that is, Li y (V 1-x1- X2- X3 Al x1 Ti X2 Zr
X3) 2 (PO 4) For 3, y is (3-2x 2 -2
It goes without saying that includes also indicate that X 3) is a ((X = X 1 + X 2 + X 3)).
【０００９】本発明の燐酸リチウム・バナジウム複合化
合物は、バナジウムの一部をＺｒ，Ｔｉ及び／またはＡ
ｌで置換することにより、従来高温で安定な高温相が室
温においても安定化され、従って室温において安定化さ
れた高温相によりその正極特性が著しく向上する。即
ち、本願発明では、イオン伝導性及びイオン拡散性の高
い高温相を室温下で安定化することによってＬｉ3 Ｖ2
（ＰＯ4 ）3 及びＬｉ3Ｆｅ2 （ＰＯ4 ）3 の欠点であ
る低充放電容量を向上させている。In the lithium-vanadium phosphate composite compound of the present invention, a part of vanadium is converted to Zr, Ti and / or A
By substituting with l, the high-temperature phase, which is conventionally stable at a high temperature, is also stabilized at room temperature, and thus the positive-electrode properties are significantly improved by the high-temperature phase stabilized at room temperature. That is, in the present invention, Li 3 V 2 is stabilized by stabilizing a high-temperature phase having high ion conductivity and ion diffusion at room temperature.
The low charge / discharge capacity, which is a disadvantage of (PO 4 ) 3 and Li 3 Fe 2 (PO 4 ) 3 , is improved.
【００１０】なお、本発明の燐酸リチウム・バナジウム
複合化合物は、連続固溶体を形成している。ここに、連
続固溶体とは、化合物の組成を連続的に変化させてもそ
の基本構造が全く変化しない一群の化合物のことを言う
が、その構造の最小単位である単位格子の大きさは, 組
成の変化に対応して連続的に変化するものを言う。ま
た、本発明の燐酸リチウム・バナジウム複合化合物はア
ルミニウム、チタニウム及びジルコニウム以外の元素を
全く含まないというのではなく、本願発明の所望の効果
が失われない限りにおいて不純物等の他の元素が含まれ
ていても構わない。The lithium-vanadium phosphate composite compound of the present invention forms a continuous solid solution. Here, a continuous solid solution refers to a group of compounds whose basic structure does not change at all even when the composition of the compound is continuously changed, and the size of the unit cell, which is the minimum unit of the structure, is determined by the composition That changes continuously in response to changes in In addition, the lithium-vanadium phosphate composite compound of the present invention does not mean that it does not contain any element other than aluminum, titanium and zirconium, but contains other elements such as impurities as long as the desired effect of the present invention is not lost. It does not matter.
【００１１】本発明の燐酸リチウム・バナジウム複合化
合物及び同複合化合物からなるリチウムイオン二次電池
用正極材料は以下のようにして得られる。以下の方法は
例示であって、本発明の燐酸リチウム・バナジウム複合
化合物及び同複合化合物からなるリチウムイオン二次電
池用正極材料は以下の方法によって製造されたものに限
られないことは言うまでもない。The lithium-vanadium phosphate composite compound of the present invention and the cathode material for a lithium ion secondary battery comprising the composite compound are obtained as follows. The following method is an exemplification, and it goes without saying that the lithium-vanadium phosphate composite compound of the present invention and the positive electrode material for a lithium ion secondary battery comprising the composite compound are not limited to those produced by the following method.
【００１２】（１）燐酸リチウム・バナジウム複合化合
物 目的とする燐酸リチウム・バナジウム複合化合物の化学
組成に従って、リチウム化合物、バナジウム化合物、並
びに燐酸塩化合物、チタン化合物、ジルコニウム化合物
及び／またはアルミニウム化合物を所定の混合比で混合
し、２００℃−４００℃の温度範囲で空気雰囲気中で１
気圧の圧力の下１−５時間熱分解し、その後３０Ｍｐａ
の圧力下で直径１５ｍｍの円形型ペレットを加圧成形し
加圧成形体をアルゴン等の不活性雰囲気中で７００℃−
１１００℃の温度範囲で焼成することによって燒結体と
しての燐酸リチウム・バナジウム複合化合物を得る。本
願の燐酸リチウム・バナジウム複合化合物は、燒結体で
も粉末でも良いが、本発明で最終的にリチウム二次電池
用正極材料として用いる場合には、粉末の形態で用い
る。従って、この場合最初から粉体の形態で複合化合物
が得られれば良いが、単一相の化合物を短時間で得るに
は、燒結体の形態とした方がより簡単に合成が可能であ
る。(1) Lithium-vanadium complex compound According to the chemical composition of the target lithium-vanadium complex compound, a lithium compound, a vanadium compound, and a phosphate compound, a titanium compound, a zirconium compound and / or an aluminum compound are converted into a predetermined compound. Mix at a mixing ratio, and in a temperature range of 200 ° C
Pyrolyze for 1-5 hours under atmospheric pressure, then 30Mpa
A 15 mm-diameter circular pellet is pressure-formed under a pressure of 700 ° C. in an inert atmosphere such as argon at 700 ° C.
By firing in a temperature range of 1100 ° C, a lithium-vanadium phosphate composite compound as a sintered body is obtained. The lithium-vanadium phosphate composite compound of the present invention may be a sintered body or a powder, but when it is finally used as a positive electrode material for a lithium secondary battery in the present invention, it is used in the form of a powder. Therefore, in this case, it is sufficient that the composite compound is obtained in the form of a powder from the beginning, but in order to obtain a single-phase compound in a short time, it is easier to synthesize in the form of a sintered body.
【００１３】燐酸リチウム・バナジウム複合化合物を得
る別の方法としては、出発原料にＬｉ2 ＣＯ3 、ＶＯ
（Ｏ−ｉＰｒ）3 、Ｔｉ（Ｏ−ｉＰｒ）4 、Ａｌ（Ｏ−
ｉＰｒ）3 、Ｐ（ＯＣＨ3 ）3 、ＺｒＯ（ＣＨ3 ＣＯ
Ｏ）2 を所望の化学組成に得るべく所定の量で混合し、
得られた混合物にクエン酸とエチレングリコールとを混
合することによって目的とする化学組成を有する化合物
の沈殿物を得る錯体重合法がある。詳細は図４に示す。As another method for obtaining a lithium-vanadium composite compound, Li 2 CO 3 , VO
(O-iPr) 3 , Ti (O-iPr) 4 , Al (O-
iPr) 3 , P (OCH 3 ) 3 , ZrO (CH 3 CO
O) 2 is mixed in a predetermined amount to obtain a desired chemical composition;
There is a complex polymerization method in which a precipitate of a compound having a desired chemical composition is obtained by mixing citric acid and ethylene glycol into the obtained mixture. Details are shown in FIG.
【００１４】なお、上記各方法において出発原料は粒子
が小さい程反応面積が広く、また、粒形が整っている程
結晶骨格の並びが整うため、リチウムの出入りの際，骨
格が壊れにくい。即ち，出来るだけ粒子が小さく粒径が
整っている原料を使用することが放電容量及びサイクル
特性の向上という観点から好ましい。In each of the above methods, the starting material has a larger reaction area as the particles are smaller, and the crystal skeleton is more aligned as the grain shape is more regular, so that the skeleton is less likely to break when lithium enters or leaves. That is, it is preferable to use a raw material having as small particles as possible and having a uniform particle size from the viewpoint of improving discharge capacity and cycle characteristics.
【００１５】（２）燐酸リチウム・バナジウム複合化合
物からなるリチウムイオン二次電池用正極材料 燐酸リチウム・バナジウム複合化合物からなるリチウム
イオン二次電池用正極材料は、上記燐酸リチウム・バナ
ジウム複合化合物からなる燒結体を粉砕してペレット状
に加圧成形することによって加圧成形体として得られ
る。正極材料を加圧成形するにあったっては、正極材料
を得る場合に通常用いる導電助剤と結着剤とを混合す
る。より詳しく述べると、上記燐酸リチウム・バナジウ
ム複合化合物からなる燒結体を粉砕して粉末状とし（粒
度範囲は, 例えば粒径０．４−２．０ミクロン）、これ
に導電助剤と結着剤を混合し、３０ＭＰａ等の圧力で加
圧成形することによってリチウムイオン二次電池用正極
材料を得る。この際、上記燐酸リチウム・バナジウム複
合化合物からなる燒結体の粉砕粉末、導電助剤及び結着
剤は重量比でそれぞれ７０−８０重量部、１５−２５重
量部及び２−１０重量部の割合で混合することが好まし
い。例えば７０：２５：５の割合で混合し、３０ＭＰａ
の圧力下で成形する。また、得られる正極材料の成形体
の形状としては，例えば断面積１ｃｍ2 の円形型ペレッ
トとすることができる。(2) A positive electrode material for a lithium ion secondary battery comprising a lithium-vanadium phosphate composite compound A positive electrode material for a lithium ion secondary battery comprising a lithium-vanadium composite compound is a sintered material comprising the above-mentioned lithium-vanadium composite compound. The body is pulverized and pressure-formed into pellets to obtain a pressure-formed body. When the positive electrode material is subjected to pressure molding, a conductive auxiliary and a binder, which are usually used for obtaining a positive electrode material, are mixed. More specifically, the sintered body composed of the lithium-phosphate-vanadium composite compound is pulverized into a powder (for example, a particle size range of 0.4 to 2.0 microns), and a conductive additive and a binder are added thereto. Are mixed and pressed under a pressure of 30 MPa or the like to obtain a positive electrode material for a lithium ion secondary battery. At this time, the pulverized powder of the sintered body composed of the lithium-vanadium complex compound, the conductive additive and the binder were added in a weight ratio of 70-80 parts by weight, 15-25 parts by weight and 2-10 parts by weight, respectively. Mixing is preferred. For example, mixing at a ratio of 70: 25: 5, 30MPa
Molded under pressure. The shape of the obtained molded body of the positive electrode material may be, for example, a circular pellet having a cross-sectional area of 1 cm 2 .
【００１６】正極電極中でリード線と正極材料（複合化
合物）との間で電子の授受をしなければならないが、本
発明の正極材料も含め一般に正極材料は元来電子伝導性
に乏しいので、軽量で導電性のあるアセチレンブラック
等の導電助剤を混合する。現在用いられているリチウム
イオン電池では、アセチレンブラックが主に使用されて
いる。Electrons must be exchanged between the lead wire and the positive electrode material (composite compound) in the positive electrode. However, since the positive electrode material including the positive electrode material of the present invention generally has poor electron conductivity, A conductive additive such as acetylene black, which is lightweight and conductive, is mixed. Acetylene black is mainly used in currently used lithium ion batteries.
【００１７】正極中では、正極材料と導電助剤とは常に
接触を保つ必要があり、それを可能とするためにポリテ
トラフルオロエチレン等の結着剤を添加して正極を形成
することが行われている。ポリテトラフルオロエチレン
の他にはポリ弗化ビニリデン、Ｎ−メチルー２−ピロリ
ドン、ブタジエン- スチレンゴム等を使用できる。In the positive electrode, it is necessary to keep the positive electrode material and the conductive auxiliary in constant contact. To enable this, it is necessary to add a binder such as polytetrafluoroethylene to form the positive electrode. Have been done. In addition to polytetrafluoroethylene, polyvinylidene fluoride, N-methyl-2-pyrrolidone, butadiene-styrene rubber and the like can be used.
【００１８】リチウム化合物としては、Ｌｉ2 ＣＯ3 、
ＬｉＯＨ、ＬｉＨＣＯ3 、Ｌｉ2 ＣＯ3 、リチウム酢酸
塩を用いることができる。バナジウム化合物としてはＶ
2 Ｏ 3 、ＶＯ，ＶＯ2 、Ｖ2 Ｏ4 を用いることができ
る。また、燐酸塩化合物としては、ＮＨ4 Ｈ2 ＰＯ4 、
（ＮＨ4 ）2 ＨＰＯ4 、（ＮＨ4 ）3 ＰＯ4 を用いるこ
とができる。チタン化合物としては、ＴｉＯ2 、Ｔｉ
Ｏ、Ｔｉ2 Ｏ3 、チタン酢酸塩を用いることができる。
また、ジルコニウム化合物としてはＺｒＯ2 、ジルコニ
ウム酢酸塩を用いることができ、アルミニウム化合物と
してはＡｌ2 Ｏ3 、Ａｌ（ＯＨ）3 を用いることができ
る。基本的には、Ａｌは３価、Ｚｒ，Ｔｉは４価の形で
置換させたいので、例えばＴｉＯを出発材料に用いると
Ｔｉは２価であるのでアルゴン雰囲気の代わりに酸素雰
囲気等を用いて酸化できる雰囲気を用いることが好まし
い。As the lithium compound, LiTwoCOThree,
LiOH, LiHCOThree, LiTwoCOThree, Lithium acetic acid
Salts can be used. V as a vanadium compound
TwoO Three, VO, VOTwo, VTwoOFourCan be used
You. Further, as the phosphate compound, NH 3FourHTwoPOFour,
(NHFour)TwoHPOFour, (NHFour)ThreePOFourUsing
Can be. As the titanium compound, TiOTwo, Ti
O, TiTwoOThree, Titanium acetate can be used.
Zirconium compounds include ZrOTwo, Zirconi
Can be used, and aluminum compound and
AlTwoOThree, Al (OH)ThreeCan be used
You. Basically, Al is trivalent, and Zr and Ti are tetravalent.
For example, if TiO is used as a starting material,
Since Ti is divalent, an oxygen atmosphere is used instead of an argon atmosphere.
It is preferable to use an atmosphere that can be oxidized using an atmosphere or the like.
No.
【００１９】以下に, 本発明について実施例に基づいて
詳細に述べるが、本発明はこれらの実施例によって何ら
限定されるものではない。。まず、粉末状で粒径が０．
４−２．０μｍであるＬｉ2 ＣＯ3 、Ｖ2 Ｏ3 、ＮＨ4
Ｈ2 ＰＯ4 、ＴｉＯ2 、ＺｒＯ2 、Ａｌ2 Ｏ3 を各サン
プルでチタニウム、ジルコニウム、アルミニウムのいず
れかをバナジウムに対する置換率が０ｍｏｌ％、５ｍｏ
ｌ％，１０ｍｏｌ％、１５ｍｏｌ％，２０ｍｏｌ％の割
合となるように混合し、２００℃−４００℃の温度範囲
で空気雰囲気中で１気圧の圧力下１−５時間熱分解し、
その後、３０ＭＰａの圧力下で直径１５ｍｍ，厚さ約１
ｍｍの円板状ペレットに加圧成形し、加圧成形体をアル
ゴン不活性雰囲気中で７００℃−１１００℃の温度で６
−１２時間焼成した。得られた、サンプルの化学構造体
は、粉末Ｘ線回折の結果からＬｉy （Ｖ1-x Ｍx ）
2 （ＰＯ4 ）3 （ＭはＺｒ，Ａｌ、Ｔｉのいずれかであ
り、０＜ｘ≦０．２であり、ｙはＭがアルミニウムの場
合はｙは３、Ｍがチタニウムあるいはジルコニウムの場
合はｙは３−２ｘである）の連続固溶体であることが分
かった。Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to these examples. . First, it is powdery and has a particle size of 0.1.
4-2.0 μm Li 2 CO 3 , V 2 O 3 , NH 4
H 2 PO 4 , TiO 2 , ZrO 2 , and Al 2 O 3 were replaced with titanium, zirconium, or aluminum in each sample with a substitution rate of 0 mol% for vanadium and 5 mol.
1%, 10 mol%, 15 mol%, and 20 mol%, and thermally decomposed under a pressure of 1 atm in an air atmosphere in a temperature range of 200 ° C to 400 ° C for 1 to 5 hours.
Then, under a pressure of 30 MPa, a diameter of 15 mm and a thickness of about 1
mm disc-shaped pellets, and press-formed at a temperature of 700 ° C. to 1100 ° C. in an argon inert atmosphere.
Fired for -12 hours. From the result of powder X-ray diffraction, the obtained chemical structure of the sample was obtained using Li y (V 1-x M x ).
2 (PO 4 ) 3 (M is any one of Zr, Al and Ti, 0 <x ≦ 0.2, y is 3 when M is aluminum, and y is 3 when M is titanium or zirconium. y is 3-2x).
【００２０】また、正極材料は、上で得られたサンプル
を砕いて得た粉末の一部を用いた。このとき、この粉末
試料と、導電助剤のアセチレンブラック及び接着剤のポ
リテトラフルオロエチレンとを重量比で７０：２５：５
となるように混ぜ、３０ＭＰａで加圧し、円形ペレット
状にして使用した。A part of the powder obtained by crushing the sample obtained above was used as the positive electrode material. At this time, this powder sample was mixed with acetylene black as a conductive additive and polytetrafluoroethylene as an adhesive in a weight ratio of 70: 25: 5.
And pressurized at 30 MPa to form a circular pellet.
【００２１】なお、ジルコニウムイオン及びチタンイオ
ンの二種類のイオンで置換した化学式Ｌｉ2.8 （Ｖ0.9
Ｚｒ0.05Ｔｉ0.05）2 （ＰＯ4 ）3 で表される化合物の
合成を行ったが，正極特性の振る舞いは一種類置換化合
物と比べ大差は無かった。The chemical formula Li 2.8 (V 0.9) substituted with two kinds of ions, zirconium ion and titanium ion.
Was synthesized compound represented by Zr 0.05 Ti 0.05) 2 (PO 4) 3 , but much different than behavior one type substituted compound of positive electrode characteristics were not.
【００２２】上で得た各サンプルについて, 以下の試験
を行った。正極特性の評価は，０．５ｍＡ／ｃｍ２の電
流密度での法充電特性の測定によって行った。 （１−１）イオン伝導度の測定 イオン伝導度の測定は以下のように行った。燒結体を粉
砕して粉末状し、０．１ｇを計り取り４９０Ｍｐａで直
径９ｍｍのペレットに加圧成形し、次に１０００℃で６
時間不活性ガスであるアルゴンガス雰囲気中で燒結し、
ペレットの両面に白金をスパッタリングすることにより
電極を形成した。このペレットに対し５Ｈｚから１３Ｈ
ｚの周波数範囲で複素インピーダンス測定を行い試料の
全伝導度を求めた。同じペレットについて二端子直流法
を用いて試料の電子伝導度を求めた。試料のイオン伝導
度は、全伝導度から電子伝導度を差し引いて求めた。結
果を図１および下記表１に示す。The following tests were performed on each of the samples obtained above. Evaluation of the positive electrode characteristics was performed by measuring normal charging characteristics at a current density of 0.5 mA / cm 2. (1-1) Measurement of ionic conductivity The measurement of ionic conductivity was performed as follows. The sintered body was pulverized to a powder, 0.1 g was weighed out, pressed at 490 Mpa into a pellet having a diameter of 9 mm, and then pressed at 1000 ° C. for 6 hours.
Sintering in an argon gas atmosphere, which is an inert gas for a time,
Electrodes were formed by sputtering platinum on both surfaces of the pellet. 5Hz to 13H for this pellet
Complex impedance was measured in the frequency range of z to determine the total conductivity of the sample. The electronic conductivity of the sample was determined for the same pellet using a two-terminal direct current method. The ionic conductivity of the sample was determined by subtracting the electronic conductivity from the total conductivity. The results are shown in FIG. 1 and Table 1 below.
【００２３】[0023]
【表１】 [Table 1]
【００２４】（１−２）充放電曲線の決定 充放電特性の測定は、コインタイプセル法を用いた。正
極材料は、放電特性を求める前に、電流密度が一定にな
るように断面積を加工した。ここに、断面積の加工と
は、通常のペレット成形機で成形後、円形の型抜きを使
用して所望の断面積を持つ円盤状に切り取ることを意味
する。次に、集電材としてこの正極材料と同じ面積に切
り取ったニッケルメッシュを正極材料と重ねて３０ＭＰ
ａで加圧し、正極材料と集電材とを完全に密着させた。
負極には正極材料と同じ面積に切り取った金属リチウム
箔を同様にして正極材料に密着させて形成した。電解液
は、炭酸プロピレン（ＰＣ）とジメトキシエタン（ＤＭ
Ｅ）を体積比で１：１となるように混合し、混合液に濃
度が１ｍｏｌ／ｌとなるようにＬｉＣｌＯ4 を溶解し
た。充放電の測定は、二端子法にて、３．０−４．４Ｖ
の範囲で電流密度０．５ｍＡ／ｃｍ2 で行った。また、
放電容量は，電圧変化が４．４Ｖから３．０Ｖまで変化
するのに要する時間に電流をかけた結果から求めた。結
果を図２に示す。(1-2) Determination of Charge / Discharge Curve The charge / discharge characteristics were measured by a coin type cell method. Before obtaining the discharge characteristics, the cross-sectional area of the positive electrode material was processed so that the current density became constant. Here, the processing of the cross-sectional area means that, after forming with a normal pellet forming machine, the disc is cut into a disk shape having a desired cross-sectional area using a circular die. Next, as a current collector, a nickel mesh cut to the same area as the positive electrode material was superimposed on the positive electrode material to form a 30 MP.
The pressure was applied by a to completely contact the positive electrode material and the current collector.
The negative electrode was formed by attaching a metallic lithium foil cut to the same area as the positive electrode material in close contact with the positive electrode material. The electrolyte is propylene carbonate (PC) and dimethoxyethane (DM
E) was mixed at a volume ratio of 1: 1 and LiClO 4 was dissolved in the mixture at a concentration of 1 mol / l. The charge / discharge measurement was performed by a two-terminal method at 3.0 to 4.4 V.
And the current density was 0.5 mA / cm 2 . Also,
The discharge capacity was determined from the result of applying a current to the time required for the voltage change to change from 4.4 V to 3.0 V. The results are shown in FIG.
【００２５】（１−３）電流密度０．５ｍＡ／ｃｍ2 に
おける３．０と４．４Ｖの間での第１サイクルに対する
置換率と放電容量との関係 結果を図３に示す。(1-3) Relationship between replacement rate and discharge capacity for the first cycle between 3.0 and 4.4 V at a current density of 0.5 mA / cm 2 The results are shown in FIG.
【００２６】上記試験結果を図１乃至図３を参照しつつ
説明する。 （２−１）図１（置換率とイオン伝導度との関係） バナジウムイオンの一部をジルコニウムイオン、チタン
ニウムイオン, アルミニウムイオンでそれぞれ置換した
いずれのサンプルにおいても、無置換のものと比べてイ
オン伝導度が向上しているのが分かる。特に、５ｍｏｌ
％から１３ｍｏｌ％位の間の置換率でイオン伝導度が大
きく向上しているのが分かる。これは、高温イオン伝導
相であるガンマ相がヒツオンで安定化しているためと考
えられる。特にＺｒ4+の１０ｍｏｌ％置換サンプルにお
いては約１０-5Ｓｃｍ-1というこの系におけるイオン伝
導度の最高値を示した。これまで報告された空気中で安
定な化合物のうちでも、この数値は極めて良好なイオン
伝導性を示すものである。The test results will be described with reference to FIGS. (2-1) FIG. 1 (Relationship between Substitution Rate and Ion Conductivity) In all samples in which a part of vanadium ions were replaced with zirconium ions, titanium ions, and aluminum ions, respectively, compared with the unsubstituted samples. It can be seen that the ionic conductivity has been improved. Especially 5mol
It can be seen that the ionic conductivity is greatly improved at a substitution rate between about 13% and about 13 mol%. This is considered to be because the gamma phase, which is a high-temperature ionic conductive phase, is stabilized by hitson. In particular, the 10 mol% substitution sample of Zr 4+ exhibited the highest value of ionic conductivity in this system of about 10 −5 Scm −1 . Among the air-stable compounds reported so far, this value indicates extremely good ionic conductivity.
【００２７】（２−２）図２（電流密度０．５ｍＡ／ｃ
ｍ2 におけるＺｒ置換サンプルの充放電曲線） 上記得られたジルコニウム置換サンプルを正極材料とし
て用いた場合の電流密度０．５ｍＡ／ｃｍ2 で測定した
充放電曲線を示す。結果から、いずれの置換率において
も３．０−４．４Ｖの間の充放電容量が各段に向上する
ことが分かる。また、無置換体には、充電曲線と放電曲
線に２つのプラトーが現れるがジルコニウムで置換する
ことによって、このプラトーが消失する傾向が見られ
る。この傾向はサイクル特性の向上を促すものであり、
特にＺｒ4+が５％の置換サンプルにおいては，放電容量
が最高の値を示した。この結果も、ジルコニウム置換に
よってＬｉ3 Ｖ2 （ＰＯ4 ）3 の高温相が室温でも安定
化されていることを示すものである。また、伝導性の向
上が充放電特性に大きく関与していることを示すもので
ある。(2-2) FIG. 2 (current density 0.5 mA / c)
Charge / Discharge Curve of Zr-Substituted Sample at m 2 ) A charge / discharge curve measured at a current density of 0.5 mA / cm 2 when the zirconium-substituted sample obtained above was used as a positive electrode material. From the results, it can be seen that the charging / discharging capacity between 3.0 and 4.4 V is improved in each stage at any replacement ratio. In addition, in the unsubstituted product, two plateaus appear on the charge curve and the discharge curve, but there is a tendency that the plateau disappears by substitution with zirconium. This tendency promotes improvement of cycle characteristics.
In particular, in the substitution sample in which Zr 4+ was 5%, the discharge capacity showed the highest value. This result also indicates that the high-temperature phase of Li 3 V 2 (PO 4 ) 3 is stabilized at room temperature by zirconium substitution. It also shows that the improvement in conductivity greatly affects the charge / discharge characteristics.
【００２８】（２−３）図３：電流密度０．５ｍＡ／ｃ
ｍ2 における３．０と４．４Ｖの間での第１サイクルに
対する置換率と放電容量との関係 いずれの置換サンプルにおいても放電容量が各段に向上
しているのが分かる。特に各イオンの置換率が５ｍｏｌ
％のサンプルにおいては、この系の放電容量の最高値を
示した。これは、イオン伝導度と対応するものである。
即ち、イオン伝導度の向上はイオン拡散性と直接結びつ
くパラメータであることから、置換によりリチウムイオ
ンの拡散性が向上することによって放電容量が大きくな
ったものと考えられる。(2-3) FIG. 3: Current density 0.5 mA / c
Relation between Displacement Rate and Discharge Capacity for First Cycle between 3.0 and 4.4 V at m 2 It can be seen that the discharge capacity is improved in each stage in each of the substituted samples. Especially the substitution rate of each ion is 5mol
% Sample showed the highest value of the discharge capacity of this system. This corresponds to the ionic conductivity.
That is, since the improvement of the ion conductivity is a parameter directly linked to the ion diffusivity, it is considered that the discharge capacity is increased by the improvement of the lithium ion diffusivity by the substitution.
【００２９】[0029]
【発明の効果】本発明の燐酸リチウム・バナジウム複合
化合物及び同複合化合物からなるリチウムイオン二次電
池用正極材料によれば、バナジウムをアルミニウム、チ
タン及びジルコニウムから選ばれた２価以上の陽イオン
のうち少なくとも１種類の陽イオンを所定の量で置換す
ることによって、高温で安定であったイオン伝導相を室
温でも安定化し、それによってイオン導電度を向上し、
イオン拡散性を高め、充放電容量を向上させている。し
たがって、本発明の燐酸リチウム・バナジウム複合化合
物は、優れた正極特性を有するリチウムイオン二次電池
用正極材料として用いることができる。According to the lithium-vanadium phosphate composite compound of the present invention and the positive electrode material for a lithium ion secondary battery comprising the composite compound, vanadium is converted to a divalent or higher cation selected from aluminum, titanium and zirconium. By replacing at least one of the cations with a predetermined amount, the ionic conductive phase, which was stable at a high temperature, is stabilized at room temperature, thereby improving the ionic conductivity.
The ion diffusivity is improved, and the charge / discharge capacity is improved. Therefore, the lithium-vanadium phosphate composite compound of the present invention can be used as a positive electrode material for a lithium ion secondary battery having excellent positive electrode characteristics.
【図１】。ジルコニウム、チタニウムあるいはアルミニ
ウムのバナジウムの置換率とイオン伝導度との関係を示
す。FIG. The relationship between the ion exchange rate and the vanadium substitution rate of zirconium, titanium or aluminum is shown.
【図２】電流密度０．５ｍＡ／ｃｍ2 におけるＺｒ置換
サンプルの放電曲線を示す。FIG. 2 shows a discharge curve of a Zr-substituted sample at a current density of 0.5 mA / cm 2 .
【図３】電流密度０．５ｍＡ／ｃｍ2 における３．０と
４．４Ｖの間での第１サイクルに対する置換率と放電容
量との関係を示す。FIG. 3 shows the relationship between the replacement rate and the discharge capacity for the first cycle between 3.0 and 4.4 V at a current density of 0.5 mA / cm 2 .
【図４】Ｌｉy （Ｖ1-x Ｍx ）2 （ＰＯ4 ）3 （Ｍ＝Ｚ
ｒ，Ｔｉ，Ａｌ）作製のフローチャートを示す。FIG. 4 Li y (V 1−x M x ) 2 (PO 4 ) 3 (M = Z
3 shows a flowchart of (r, Ti, Al) production.
Claims (2)
ム・バナジウム複合化合物。 Ｌｉy （Ｖ1-x Ｍx ）2 （ＰＯ4 ）3 （１） ここに、Ｍはアルミニウム、チタニウム及びジルコニウ
ムから選ばれた２価以上の陽イオンのうち少なくとも１
種類であり、０＜ｘ≦０．２であり、ｙはＭがアルミニ
ウムの場合はｙは３、Ｍがチタニウムあるいはジルコニ
ウムの場合はｙは３−２ｘである。1. A lithium-vanadium phosphate composite compound represented by the following general formula (1). Li y (V 1-x M x ) 2 (PO 4 ) 3 (1) wherein M is at least one of divalent or higher cations selected from aluminum, titanium and zirconium.
0 <x ≦ 0.2, y is 3 when M is aluminum, and y is 3-2x when M is titanium or zirconium.
ム・バナジウム複合化合物からなるリチウム二次電池用
正極材料。 Ｌｉy （Ｖ1-x Ｍx ）2 （ＰＯ4 ）3 （１） ここに、Ｍはアルミニウム、チタニウム及びジルコニウ
ムから選ばれた２価以上の陽イオンのうち少なくとも１
種類であり、０＜ｘ≦０．２であり、ｙはＭがアルミニ
ウムの場合はｙは３、Ｍがチタニウムあるいはジルコニ
ウムの場合はｙは３−２ｘである。2. A positive electrode material for a lithium secondary battery comprising a lithium phosphate / vanadium composite compound represented by the following general formula (1). Li y (V 1-x M x ) 2 (PO 4 ) 3 (1) wherein M is at least one of divalent or higher cations selected from aluminum, titanium and zirconium.
0 <x ≦ 0.2, y is 3 when M is aluminum, and y is 3-2x when M is titanium or zirconium.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10261930A JP2949229B1 (en) | 1998-09-16 | 1998-09-16 | Lithium-vanadium phosphate composite compound and cathode material for lithium ion secondary battery comprising the composite compound |
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| Publication Number | Publication Date |
|---|---|
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| JP2000086215A true JP2000086215A (en) | 2000-03-28 |
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ID=17368688
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| US6720110B2 (en) | 1996-09-23 | 2004-04-13 | Valence Technology, Inc. | Lithium-containing phosphates, method of preparation, and uses thereof |
| JP2008052970A (en) * | 2006-08-23 | 2008-03-06 | Sumitomo Osaka Cement Co Ltd | Manufacturing method of electrode material, positive electrode material, and battery |
| JP2008262745A (en) * | 2007-04-10 | 2008-10-30 | Toyota Central R&D Labs Inc | Aqueous lithium secondary battery |
| US7482097B2 (en) | 2002-04-03 | 2009-01-27 | Valence Technology, Inc. | Alkali-transition metal phosphates having a +3 valence non-transition element and related electrode active materials |
| JP2009522749A (en) * | 2006-01-09 | 2009-06-11 | コノコフィリップス・カンパニー | Preparation of carbon-coated lithium metal polyanionic powder |
| JP2010540393A (en) * | 2007-10-01 | 2010-12-24 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing porous lithium-, vanadium-, and phosphate-containing materials |
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| JP2013539167A (en) * | 2010-08-12 | 2013-10-17 | リサーチ インスティチュート オブ インダストリアル サイエンス アンド テクノロジー | Method for producing olivine-based positive electrode material for lithium secondary battery |
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| US6720110B2 (en) | 1996-09-23 | 2004-04-13 | Valence Technology, Inc. | Lithium-containing phosphates, method of preparation, and uses thereof |
| US7482097B2 (en) | 2002-04-03 | 2009-01-27 | Valence Technology, Inc. | Alkali-transition metal phosphates having a +3 valence non-transition element and related electrode active materials |
| JP2009522749A (en) * | 2006-01-09 | 2009-06-11 | コノコフィリップス・カンパニー | Preparation of carbon-coated lithium metal polyanionic powder |
| JP2008052970A (en) * | 2006-08-23 | 2008-03-06 | Sumitomo Osaka Cement Co Ltd | Manufacturing method of electrode material, positive electrode material, and battery |
| JP2008262745A (en) * | 2007-04-10 | 2008-10-30 | Toyota Central R&D Labs Inc | Aqueous lithium secondary battery |
| JP2010540393A (en) * | 2007-10-01 | 2010-12-24 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing porous lithium-, vanadium-, and phosphate-containing materials |
| JP2010540394A (en) * | 2007-10-01 | 2010-12-24 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing crystalline lithium-, vanadium-, and phosphate-containing materials |
| JP2013539167A (en) * | 2010-08-12 | 2013-10-17 | リサーチ インスティチュート オブ インダストリアル サイエンス アンド テクノロジー | Method for producing olivine-based positive electrode material for lithium secondary battery |
| EP2575199A1 (en) * | 2011-09-30 | 2013-04-03 | Fuji Jukogyo Kabushiki Kaisha | Lithium-ion secondary battery |
| US10270098B2 (en) * | 2014-05-16 | 2019-04-23 | Dongguk University Industry-Academic Cooperation Foundation | Positive electrode active material for lithium ion battery, containing lithium vanadium zirconium phosphate, and lithium ion battery comprising same |
| EP3147975A4 (en) * | 2014-05-23 | 2017-05-31 | Nippon Chemi-Con Corporation | Positive electrode material, secondary battery, method for manufacturing positive electrode material, and method for manufacturing secondary battery |
| WO2019167783A1 (en) * | 2018-02-27 | 2019-09-06 | Tdk株式会社 | Active material and all-solid secondary battery |
| CN111742432A (en) * | 2018-02-27 | 2020-10-02 | Tdk株式会社 | Active material and all-solid-state secondary battery |
| JPWO2019167783A1 (en) * | 2018-02-27 | 2021-02-12 | Tdk株式会社 | Active material and all-solid-state secondary battery |
| JP7327380B2 (en) | 2018-02-27 | 2023-08-16 | Tdk株式会社 | Active materials and all-solid secondary batteries |
| CN111742432B (en) * | 2018-02-27 | 2024-04-16 | Tdk株式会社 | Active material and all-solid secondary battery |
| WO2020175632A1 (en) * | 2019-02-27 | 2020-09-03 | Tdk株式会社 | All-solid-state battery |
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| JP2949229B1 (en) | 1999-09-13 |
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