JP2003115296A - Lithium-containing electrode material and its manufacturing method, and electrochemical element using lithium-containing electrode material - Google Patents
Lithium-containing electrode material and its manufacturing method, and electrochemical element using lithium-containing electrode materialInfo
- Publication number
- JP2003115296A JP2003115296A JP2001279494A JP2001279494A JP2003115296A JP 2003115296 A JP2003115296 A JP 2003115296A JP 2001279494 A JP2001279494 A JP 2001279494A JP 2001279494 A JP2001279494 A JP 2001279494A JP 2003115296 A JP2003115296 A JP 2003115296A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- electrode material
- transition metal
- metal composite
- composite nitride
- 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
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
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【発明の属する技術分野】本発明は、リチウム二次電池
やキャパシタ等の電気化学素子に利用可能なリチウム含
有電極材料及びその製造方法、並びにそのリチウム含有
電極材料を負極に用いた電気化学素子に関するものであ
る。TECHNICAL FIELD The present invention relates to a lithium-containing electrode material that can be used in electrochemical devices such as lithium secondary batteries and capacitors, a method for producing the same, and an electrochemical device using the lithium-containing electrode material as a negative electrode. It is a thing.
【０００２】[0002]
【従来の技術】従来、非水電解質を備えた電気化学素子
の負極活物質として使用される電極材料としては、例え
ばリチウム二次電池では、リチウムを可逆的に挿入・脱
離することが可能な黒鉛等の層状化合物、あるいはリチ
ウムと合金を形成することが可能な金属又は金属酸化物
等が用いられていた。前者の黒鉛系負極材料では、充放
電に伴い層状化合物の層間へのリチウムの吸蔵・放出の
みが起こり、その結果、電極材料自体の結晶構造に大き
な変化が起こらないため、電気化学的な酸化還元サイク
ルに対して良い可逆性を示す。また、後者のリチウムと
の合金化を伴う負極材料では、例えばケイ素の場合、１
個のケイ素に対して３個以上のリチウムが反応するた
め、１０００ｍＡｈ／ｇを超える大きな放電容量を示
す。2. Description of the Related Art Conventionally, as an electrode material used as a negative electrode active material of an electrochemical device having a non-aqueous electrolyte, for example, in a lithium secondary battery, lithium can be reversibly inserted / desorbed. Layered compounds such as graphite, or metals or metal oxides capable of forming an alloy with lithium have been used. In the former graphite-based negative electrode material, only intercalation / desorption of lithium between the layers of the layered compound occurs with charge / discharge, and as a result, the crystal structure of the electrode material itself does not change significantly, so electrochemical redox is used. Shows good reversibility for cycling. Further, in the latter negative electrode material accompanied by alloying with lithium, for example, in the case of silicon, 1
Since three or more lithiums react with one silicon, a large discharge capacity exceeding 1000 mAh / g is exhibited.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、前記黒
鉛系負極材料は、層間へのリチウムの出入りを利用して
いることから、６個の炭素に対し最大でも１個のリチウ
ムしか反応できないため、理論的に３７２ｍＡｈ／ｇ以
上の容量が望めず、現状からの大きな高容量化は困難で
ある。また、前記合金化を伴う負極材料の場合、リチウ
ムとの合金化に伴う電極材料粒子の膨張・収縮の割合が
大きく、そのため電極材料粒子の微粉化などが生じて、
サイクル特性が悪くなるという欠点がある。However, since the graphite-based negative electrode material utilizes the inflow and outflow of lithium between the layers, it is possible to react at most one lithium with respect to six carbons. Therefore, a capacity of 372 mAh / g or more cannot be expected, and it is difficult to achieve a large capacity from the present situation. Further, in the case of the negative electrode material accompanied by the alloying, the rate of expansion and contraction of the electrode material particles due to the alloying with lithium is large, so that the electrode material particles are pulverized and the like.
There is a drawback that the cycle characteristics deteriorate.
【０００４】そこで、本発明は前記従来の問題を解決す
るためになされたものであり、高容量で且つサイクル特
性に優れた電気化学素子を構成することのできるリチウ
ム含有電極材料を提供することを目的とする。Therefore, the present invention has been made to solve the above-mentioned conventional problems, and provides a lithium-containing electrode material capable of forming an electrochemical device having a high capacity and excellent cycle characteristics. To aim.
【０００５】[0005]
【課題を解決するための手段】前記目的を達成するた
め、本発明のリチウム含有電極材料は、リチウム遷移金
属複合窒化物の粒子の少なくとも表層部に、リチウムと
合金を形成することができる元素を含有させたことを特
徴する。In order to achieve the above object, the lithium-containing electrode material of the present invention contains an element capable of forming an alloy with lithium in at least the surface layer portion of the particles of the lithium transition metal composite nitride. It is characterized by containing.
【０００６】また、本発明のリチウム含有電極材料は、
リチウム遷移金属複合窒化物の粒子の少なくとも表層部
に、酸素と、リチウムと合金を形成することができる元
素とを含有させたことを特徴する。Further, the lithium-containing electrode material of the present invention is
At least the surface layer portion of the particles of the lithium-transition metal composite nitride contains oxygen and an element capable of forming an alloy with lithium.
【０００７】本発明のリチウム含有電極材料の粒子は、
その骨格が、主として層構造を有する前記リチウム遷移
金属複合窒化物と同様の構造である。これにより、電気
化学的な酸化還元サイクルに伴うリチウムの挿入・脱離
に対して良い可逆性を示すとともに、高容量化を図るこ
とができる。また、前記リチウム含有電極材料の粒子に
は、リチウムと合金を形成することができる元素が含有
されている。このため、合金化により多くのリチウムを
吸蔵することもできる。更に、前記リチウム含有電極材
料の粒子の表層部に、少なくともリチウムと合金を形成
することができる元素を含有させることにより、リチウ
ム遷移金属複合窒化物が大気中の水分と接触することを
確実に低減させることができ、大気中で安定となり、取
扱いが容易な電極材料とすることができる。また、前記
リチウム含有電極材料の粒子の表層部に、酸素と、リチ
ウムと合金を形成することができる元素とを含有させる
ことにより、より一層大気中での安定性が向上する。The particles of the lithium-containing electrode material of the present invention are
Its skeleton has a structure mainly similar to that of the lithium-transition metal composite nitride having a layered structure. As a result, it is possible to show good reversibility with respect to the insertion / desorption of lithium that accompanies the electrochemical redox cycle, and to increase the capacity. Further, the particles of the lithium-containing electrode material contain an element capable of forming an alloy with lithium. Therefore, a large amount of lithium can be occluded by alloying. Furthermore, by including at least an element capable of forming an alloy with lithium in the surface layer portion of the particles of the lithium-containing electrode material, it is possible to reliably reduce contact of the lithium transition metal composite nitride with moisture in the atmosphere. It is possible to obtain an electrode material which is stable in the atmosphere and easy to handle. Further, by containing oxygen and an element capable of forming an alloy with lithium in the surface layer portion of the particles of the lithium-containing electrode material, the stability in the atmosphere is further improved.
【０００８】また、本発明のリチウム含有電極材料は、
リチウム遷移金属複合窒化物と、少なくともリチウムと
合金を形成することができる元素を含む化合物とを溶媒
中で混合するなどの方法により、前記リチウム遷移金属
複合窒化物の粒子の表面に、前記少なくともリチウムと
合金を形成することができる元素を含む化合物を付着さ
せた後、これを焼成することにより形成することができ
るものである。The lithium-containing electrode material of the present invention is
By a method such as mixing a lithium transition metal composite nitride and at least a compound containing an element capable of forming an alloy with lithium in a solvent, on the surface of the particles of the lithium transition metal composite nitride, the at least lithium It can be formed by depositing a compound containing an element capable of forming an alloy with and then firing it.
【０００９】また、本発明のリチウム含有電極材料は、
前記リチウム遷移金属複合窒化物を構成する遷移金属元
素が、コバルト、銅、鉄及びニッケルよりなる群から選
ばれた少なくとも１種の元素であることが好ましい。こ
れらの元素はＬｉ3Ｎの構造を維持しつつ、電気化学素
子として使用できるからである。The lithium-containing electrode material of the present invention is
The transition metal element forming the lithium-transition metal composite nitride is preferably at least one element selected from the group consisting of cobalt, copper, iron and nickel. This is because these elements can be used as an electrochemical element while maintaining the structure of Li 3 N.
【００１０】また、本発明のリチウム含有電極材料は、
前記リチウムと合金を形成することができる元素が、ケ
イ素、錫及びアルミニウムよりなる群から選ばれた少な
くとも１種の元素であることが好ましい。これらの元素
は化学的に安定で、且つ価格も安価だからである。Further, the lithium-containing electrode material of the present invention is
The element capable of forming an alloy with lithium is preferably at least one element selected from the group consisting of silicon, tin and aluminum. This is because these elements are chemically stable and inexpensive.
【００１１】また、本発明のリチウム含有電極材料は、
前記リチウム遷移金属複合窒化物の粒子の表層部に含有
されたリチウムと合金を形成することができる元素の含
有量が、前記リチウム遷移金属複合窒化物の粒子の表面
近傍から内部に向かって減少していることが好ましい。
これにより、電池等の製造時や充放電時にリチウム含有
電極材料に応力が加わっても、これに亀裂が生じて微粉
化が進行したり、リチウムと合金を形成することができ
る元素が脱離するなどの問題の発生を防ぐことができ、
長期間にわたって特性を維持できる。同様に、前記リチ
ウム遷移金属複合窒化物の粒子の表層部に含有された酸
素の含有量も、前記リチウム遷移金属複合窒化物の粒子
の表面近傍から内部に向かって減少していることが好ま
しい。The lithium-containing electrode material of the present invention is
The content of the element capable of forming an alloy with lithium contained in the surface layer portion of the particles of the lithium-transition metal composite nitride decreases from the vicinity of the surface of the particles of the lithium-transition metal composite nitride toward the inside. Preferably.
As a result, even when stress is applied to the lithium-containing electrode material at the time of manufacturing a battery or charging / discharging, a crack is generated in the lithium-containing electrode material, pulverization proceeds, or an element capable of forming an alloy with lithium is released. You can prevent the occurrence of problems such as
The characteristics can be maintained for a long period of time. Similarly, it is preferable that the content of oxygen contained in the surface layer portion of the particles of the lithium transition metal composite nitride also decreases from the vicinity of the surface of the particles of the lithium transition metal composite nitride toward the inside.
【００１２】また、前記リチウム遷移金属複合窒化物の
粒子に元々含有されているリチウム及び遷移金属元素の
分布態様については、特に制限されるものではないが、
リチウムは電極材料の表面近傍から内部に向かってほぼ
一様に分布していることが好ましく、一方、遷移金属元
素は電極材料の表面近傍から内部に向かって増加するの
がよい。The distribution mode of the lithium and the transition metal element originally contained in the particles of the lithium-transition metal composite nitride is not particularly limited,
It is preferable that lithium is substantially uniformly distributed from the vicinity of the surface of the electrode material toward the inside thereof, while the transition metal element is preferably increased from the vicinity of the surface of the electrode material toward the inside thereof.
【００１３】即ち、本発明のリチウム含有電極材料で
は、その表層部において、リチウムと合金を形成するこ
とができる元素、酸素あるいは遷移金属元素の含有量が
深さ方向に連続的に変化し、傾斜していることが望まし
い態様である。That is, in the lithium-containing electrode material of the present invention, the content of the element capable of forming an alloy with lithium, oxygen, or the transition metal element in the surface layer portion changes continuously in the depth direction, and the gradient is obtained. It is a desirable mode.
【００１４】なお、上記で「表面近傍から」としている
のは、粒子の表面から多少内部に入った部分から粒子内
部に向かって組成が上記のように変化していればよいこ
とを意味している。即ち、粒子表面のごく近傍部分（表
面から約１００ｎｍまでの深さの部分）については、必
ずしも上記のような組成変化でなくともよいことを意味
する。The expression "from the vicinity of the surface" as used above means that the composition may change as described above from the part slightly inside the surface of the particle to the inside of the particle. There is. That is, it means that the composition change as described above does not necessarily have to occur in a portion in the vicinity of the particle surface (a portion having a depth from the surface to about 100 nm).
【００１５】次に、本発明のリチウム含有電極材料の製
造方法は、リチウム遷移金属複合窒化物と、少なくとも
リチウムと合金を形成することができる元素を含む化合
物とを混合し、前記リチウム遷移金属複合窒化物の粒子
の表面に、前記少なくともリチウムと合金を形成するこ
とができる元素を含む化合物を付着させた後、これを焼
成することを特徴とする。Next, in the method for producing a lithium-containing electrode material of the present invention, the lithium-transition metal composite nitride is mixed with a compound containing an element capable of forming an alloy with at least lithium, and the lithium-transition metal composite material is mixed. It is characterized in that a compound containing an element capable of forming an alloy with at least lithium is attached to the surface of the particles of the nitride and then the compound is fired.
【００１６】また、本発明のリチウム含有電極材料の製
造方法は、前記リチウム遷移金属複合窒化物を構成する
遷移金属元素が、コバルト、銅、鉄及びニッケルよりな
る群から選ばれた少なくとも１種の元素であることが好
ましい。Further, in the method for producing a lithium-containing electrode material according to the present invention, the transition metal element constituting the lithium transition metal composite nitride is at least one selected from the group consisting of cobalt, copper, iron and nickel. It is preferably an element.
【００１７】また、本発明のリチウム含有電極材料の製
造方法は、前記リチウムと合金を形成することができる
元素が、ケイ素、錫及びアルミニウムよりなる群から選
ばれた少なくとも１種の元素であることが好ましい。Further, in the method for producing a lithium-containing electrode material of the present invention, the element capable of forming an alloy with lithium is at least one element selected from the group consisting of silicon, tin and aluminum. Is preferred.
【００１８】更に、本発明の電気化学素子は、前記リチ
ウム含有電極材料を負極に用いたことを特徴とする。こ
れにより、高容量且つサイクル特性に優れた電気化学素
子を容易に構成することができる。Further, the electrochemical element of the present invention is characterized in that the above-mentioned lithium-containing electrode material is used for the negative electrode. This makes it possible to easily configure an electrochemical device having a high capacity and excellent cycle characteristics.
【００１９】[0019]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.
【００２０】先ず、本発明のリチウム含有電極材料を説
明する。本発明のリチウム含有電極材料は、リチウム遷
移金属複合窒化物の粒子の少なくとも表層部に、酸素
と、リチウムと合金を形成することができる元素とを含
有させたものである。First, the lithium-containing electrode material of the present invention will be described. The lithium-containing electrode material of the present invention is one in which oxygen and an element capable of forming an alloy with lithium are contained in at least the surface layer portion of the particles of the lithium transition metal composite nitride.
【００２１】前記リチウム遷移金属複合窒化物として
は、例えば、ＬｉjＣｏkＮm、ＬｉjＣｕkＮm、ＬｉjＦ
ｅkＮm、ＬｉjＮｉkＮm等を用いることができる。ここ
で、一般にｊ、ｋ、ｍはｊ＞０、ｋ＞０、ｍ＞０の数で
あるが、好ましくは、０＜ｊ＜２０、０＜ｋ＜２０、０
＜ｍ＜２０の数であり、最も好ましくは、０＜ｊ＜７、
０＜ｋ＜２、０＜ｍ＜５の数である。また、２種以上の
遷移金属を含んだリチウム遷移金属複合窒化物として
は、例えば、ＬｉjＣｏkＮｉmＮn、ＬｉjＣｏkＣｕ
mＮn、ＬｉjＣｕkＮｉmＮn等を用いることができる。こ
こで、一般にｊ、ｋ、ｍ、ｎはｊ＞０、ｋ＞０、ｍ＞
０、ｎ＞０の数であるが、好ましくは、０＜ｊ＜５０、
０＜ｋ＜５０、０＜ｍ＜５０、０＜ｎ＜５０の数であ
り、最も好ましくは、０＜ｊ＜３０、０＜ｋ＜１０、０
＜ｍ＜５、０＜ｎ＜２０の数である。Examples of the lithium-transition metal composite nitride include Li j Co k N m , Li j Cu k N m , and Li j F.
e k N m , Li j Ni k N m, or the like can be used. Here, j, k, and m are generally numbers of j> 0, k> 0, and m> 0, but preferably 0 <j <20, 0 <k <20,0.
<M <20, most preferably 0 <j <7,
The numbers are 0 <k <2 and 0 <m <5. As the lithium transition metal composite nitride containing two or more transition metals, e.g., Li j Co k Ni m N n, Li j Co k Cu
m N n, it is possible to use Li j Cu k Ni m N n or the like. Here, in general, j, k, m, and n are j> 0, k> 0, and m>.
0, n> 0, but preferably 0 <j <50,
The numbers are 0 <k <50, 0 <m <50, 0 <n <50, and most preferably 0 <j <30, 0 <k <10, 0.
<M <5 and 0 <n <20.
【００２２】また、前記リチウム遷移金属複合窒化物の
粒子の粒径は、通常、０．１〜１００μｍであり、より
好ましくは、０．１〜２０μｍである。The particle size of the particles of the lithium-transition metal composite nitride is usually 0.1 to 100 μm, more preferably 0.1 to 20 μm.
【００２３】前記リチウム遷移金属複合窒化物の粒子に
含有される酸素、リチウムと合金を形成することができ
る元素は、少なくとも前記粒子の表層部に存在すればよ
く、表層部でのリチウム吸蔵・放出能力が保たれる範囲
内でその含有量を調整すればよい。具体的には、本発明
のリチウム含有電極材料の質量中、酸素では約０．０１
〜１５％、リチウムと合金を形成することができる元素
では約０．０１〜２０％と考えられ、より好ましくは、
酸素が０．０５〜１０％、リチウムと合金を形成するこ
とができる元素が０．０５〜１５％と考えられる。The oxygen contained in the particles of the lithium-transition metal composite nitride and the element capable of forming an alloy with lithium may be present at least in the surface layer portion of the particles, and the lithium occlusion / release in the surface layer portion. The content may be adjusted within the range in which the ability is maintained. Specifically, in the mass of the lithium-containing electrode material of the present invention, oxygen is about 0.01.
˜15%, about 0.01 to 20% for elements that can form an alloy with lithium, and more preferably,
It is considered that oxygen is 0.05 to 10% and the element capable of forming an alloy with lithium is 0.05 to 15%.
【００２４】また、前記リチウムと合金を形成すること
ができる元素としては、ケイ素、錫、アルミニウム等を
使用できる。As the element capable of forming an alloy with lithium, silicon, tin, aluminum or the like can be used.
【００２５】また、本発明のリチウム含有電極材料は、
前記リチウム遷移金属複合窒化物の粒子に含有された酸
素あるいはリチウムと合金を形成することができる元素
（以下、表層元素ともいう）の含有量が、前記リチウム
遷移金属複合窒化物の粒子の表面近傍から内部に向かっ
て減少していることが好ましい。これらの表層元素の含
有量が変化する範囲は、例えば、リチウム遷移金属複合
窒化物の粒子の粒径が約５〜２０μｍの場合では、表面
から内部に向かって約１０００ｎｍまでの範囲であるこ
とが好ましい。但し、これらの表層元素は、この１００
０ｎｍの範囲を超えて内部に存在してもよい。The lithium-containing electrode material of the present invention is
The content of an element capable of forming an alloy with oxygen or lithium contained in the particles of the lithium transition metal composite nitride (hereinafter, also referred to as a surface layer element) is near the surface of the particles of the lithium transition metal composite nitride. It is preferable to decrease from the inside to the inside. The range in which the content of these surface layer elements changes is, for example, in the case where the particle size of the particles of the lithium-transition metal composite nitride is about 5 to 20 μm, the range from the surface to the inside is about 1000 nm. preferable. However, these surface elements are 100
It may exist in the inside beyond the range of 0 nm.
【００２６】次に、本発明のリチウム含有電極材料の製
造方法は、リチウム遷移金属複合窒化物と、少なくとも
リチウムと合金を形成することができる元素を含む化合
物とを混合し、前記リチウム遷移金属複合窒化物の粒子
の表面に、前記少なくともリチウムと合金を形成するこ
とができる元素を含む化合物を付着させた後、これを焼
成するものである。Next, in the method for producing a lithium-containing electrode material of the present invention, the lithium transition metal composite nitride is mixed with a compound containing an element capable of forming an alloy with at least lithium, and the lithium transition metal composite nitride is mixed. A compound containing an element capable of forming an alloy with at least lithium is attached to the surface of the nitride particles, and then the compound is fired.
【００２７】ここで、本発明のリチウム含有電極材料の
製造方法についてより具体的に説明する。前記リチウム
遷移金属複合窒化物は、リチウム及びコバルト等の遷移
金属の単体、酸化物、窒化物、ハロゲン化物、炭酸塩等
を好適に組み合わせて、窒素ガス等の不活性ガス雰囲気
下、又は不活性ガスに水素ガスを混入した還元性ガス雰
囲気下で、約２００〜１０００℃の温度範囲で焼成する
等の方法で得ることができる。焼成後のリチウム含有電
極材料の粒径は、元のリチウム遷移金属複合窒化物の粒
子の粒径と同程度であるか、又は多少大きくなる。Here, the method for producing the lithium-containing electrode material of the present invention will be described more specifically. The lithium-transition metal composite nitride is preferably a combination of simple substances of transition metals such as lithium and cobalt, oxides, nitrides, halides, carbonates, etc., in an inert gas atmosphere such as nitrogen gas, or inactive. It can be obtained by a method such as firing in a temperature range of about 200 to 1000 ° C. in a reducing gas atmosphere in which hydrogen gas is mixed with gas. The particle size of the lithium-containing electrode material after firing is similar to or slightly larger than the particle size of the original particles of the lithium-transition metal composite nitride.
【００２８】次に、リチウムと合金を形成することがで
きる元素を含む化合物として、ケイ素、錫、アルミニウ
ム等の単体、酸化物、窒化物、ハロゲン化物、炭酸塩、
及びこれらの元素を含む有機化合物等を好適に組み合わ
せて反応させることにより、少なくともリチウムと合金
を形成することができる元素を含む化合物を合成する。
得られた少なくともリチウムと合金を形成することがで
きる元素を含む化合物を有機溶媒中に溶解し、その溶液
中に前記リチウム遷移金属複合窒化物を分散させる。続
いて、この分散液と、前記少なくともリチウムと合金を
形成することができる元素を含む化合物を溶解しない有
機溶媒とを混合させることにより、前記リチウム遷移金
属複合窒化物の表面に前記少なくともリチウムと合金を
形成することができる元素を含む化合物を析出させ、そ
の後に焼成することにより、リチウム遷移金属複合窒化
物の粒子の少なくとも表層部に、酸素と、リチウムと合
金を形成することができる元素とを含有させた本発明の
リチウム含有電極材料を得ることができる。Next, as compounds containing an element capable of forming an alloy with lithium, simple substances such as silicon, tin and aluminum, oxides, nitrides, halides, carbonates,
By appropriately combining and reacting an organic compound or the like containing these elements, a compound containing at least an element capable of forming an alloy with lithium is synthesized.
The obtained compound containing at least an element capable of forming an alloy with lithium is dissolved in an organic solvent, and the lithium transition metal composite nitride is dispersed in the solution. Subsequently, by mixing this dispersion liquid with an organic solvent that does not dissolve the compound containing an element capable of forming an alloy with at least lithium, the alloy of at least lithium is formed on the surface of the lithium-transition metal composite nitride. By precipitating a compound containing an element capable of forming, and then firing, at least the surface layer portion of the particles of the lithium transition metal composite nitride, oxygen, and an element capable of forming an alloy with lithium, It is possible to obtain the contained lithium-containing electrode material of the present invention.
【００２９】上記焼成は、窒素ガス等の不活性ガス雰囲
気下、又は不活性ガスに水素ガスを混入した還元性ガス
雰囲気下などで行うことができるが、上記リチウムと合
金を形成することができる元素を含む化合物として、酸
素を含有していない化合物を選択した場合は、酸素を含
む酸化性ガス雰囲気下で焼成を行えばよい。焼成温度は
特に限定されないが、一般に、２００〜１０００℃の範
囲内の温度が好ましい。焼成時間も特に限定されない
が、一般に、数十分間〜数時間の範囲内の焼成時間が好
ましい。焼成することにより、酸素、及びリチウムと合
金を形成することができる元素を、リチウム遷移金属複
合窒化物の粒子の少なくとも表層部に含有させることが
できる。また、前記表層元素は、この焼成により粒子の
表面から内部へと拡散するため、本発明により製造した
リチウム含有電極材料では、前記表層元素の含有量が、
前記リチウム遷移金属複合窒化物の粒子の表面近傍から
内部に向かって減少する傾斜構造を実現することができ
る。The calcination can be carried out in an atmosphere of an inert gas such as nitrogen gas or in a reducing gas atmosphere in which hydrogen gas is mixed with an inert gas, and an alloy can be formed with the lithium. When a compound containing no oxygen is selected as the compound containing an element, firing may be performed in an oxidizing gas atmosphere containing oxygen. The firing temperature is not particularly limited, but generally a temperature in the range of 200 to 1000 ° C is preferable. The firing time is not particularly limited, but generally, a firing time within the range of several tens of minutes to several hours is preferable. By firing, oxygen and an element capable of forming an alloy with lithium can be contained in at least the surface layer portion of the particles of the lithium-transition metal composite nitride. Further, since the surface layer element diffuses from the surface of the particle to the inside by this firing, the content of the surface layer element in the lithium-containing electrode material produced by the present invention is
It is possible to realize a graded structure that decreases from the vicinity of the surface of the particles of the lithium-transition metal composite nitride toward the inside.
【００３０】なお、リチウム遷移金属複合窒化物の粒子
の表面に酸素を含有していない化合物を付着させ、不活
性ガス雰囲気下又は還元性ガス雰囲気下など、酸素を含
んでいないガス雰囲気下でこれを焼成した場合には、表
層部にリチウムと合金を形成することができる元素を含
有するが、酸素を含有していないリチウム含有電極材料
が得られる。このような電極材料は、表層部に酸素をも
含有させたものに比べて大気中での安定性が多少劣る
が、本発明の目的とする効果は得られるため、このよう
な電極材料も本発明のリチウム含有電極材料に含まれ
る。上記表層部に酸素を含有しないリチウム含有電極材
料においても、リチウム遷移金属複合窒化物の粒子の粒
径、焼成の条件、表層部の傾斜構造などは前述したもの
と同様である。但し、本発明の目的をより効果的に達成
するためには、リチウムと合金を形成することができる
元素と酸素とをリチウム遷移金属複合窒化物の粒子の少
なくとも表層部に共に含有させることが望ましいのであ
り、本発明においてはそのようなリチウム含有電極材料
がより好ましい態様である。A compound containing no oxygen is adhered to the surface of the particles of the lithium-transition metal composite nitride, and this is applied under a gas atmosphere containing no oxygen such as an inert gas atmosphere or a reducing gas atmosphere. In the case of firing, a lithium-containing electrode material containing an element capable of forming an alloy with lithium in the surface layer portion but containing no oxygen is obtained. Such an electrode material has a little inferior stability in the atmosphere as compared with the one in which oxygen is also contained in the surface layer portion, but since the effect intended by the present invention can be obtained, such an electrode material is also It is included in the lithium-containing electrode material of the invention. Also in the lithium-containing electrode material containing no oxygen in the surface layer, the particle size of the particles of the lithium-transition metal composite nitride, the firing conditions, and the inclined structure of the surface layer are the same as those described above. However, in order to achieve the object of the present invention more effectively, it is desirable to include an element capable of forming an alloy with lithium and oxygen together in at least the surface layer portion of the particles of the lithium-transition metal composite nitride. Therefore, such a lithium-containing electrode material is a more preferable embodiment in the present invention.
【００３１】また、リチウムと合金を形成することがで
きる元素を含む化合物として、Ｓｉ−Ｎ（シラザン）結
合を有する化合物を用い、前記リチウム遷移金属複合窒
化物の粒子の表面に、前記Ｓｉ−Ｎ結合を有する化合物
を付着させた後、これを焼成する方法によっても、前述
と同様のリチウム含有電極材料を得ることができる。も
ちろん、Ｓｉ−Ｎ結合を有する化合物に酸素が含有され
ていない場合に、酸素を含んだ酸化性ガス雰囲気下で焼
成を行えば、リチウム含有電極材料の少なくとも表層部
にケイ素と酸素を含有させることができ、不活性ガス雰
囲気下又は還元性ガス雰囲気下で焼成を行えば、ケイ素
のみ含有させることができる点などは、前述と同様であ
る。A compound having a Si--N (silazane) bond is used as a compound containing an element capable of forming an alloy with lithium, and the Si--N is formed on the surface of the particles of the lithium transition metal composite nitride. The same lithium-containing electrode material as described above can also be obtained by a method in which a compound having a bond is attached and then fired. Of course, when oxygen is not contained in the compound having a Si-N bond, if firing is performed in an oxidizing gas atmosphere containing oxygen, silicon and oxygen should be contained in at least the surface layer of the lithium-containing electrode material. In addition, if firing is performed in an inert gas atmosphere or a reducing gas atmosphere, only silicon can be contained, which is the same as described above.
【００３２】本発明でリチウムと合金を形成することが
できる元素を含む化合物として用いるＳｉ−Ｎ（シラザ
ン）結合を有する化合物としては、ヘキサメチルジシラ
ザン及びペルヒドロポリシラザン等のポリシラザンが好
ましく用いられる。Polysilazanes such as hexamethyldisilazane and perhydropolysilazane are preferably used as the compound having an Si--N (silazane) bond used as a compound containing an element capable of forming an alloy with lithium in the present invention.
【００３３】ポリシラザンは、下記一般式（Ｉ）で表さ
れる構造単位からなる主骨格を有する数平均分子量１０
０〜５万の無機重合体である。The polysilazane has a number average molecular weight of 10 having a main skeleton composed of a structural unit represented by the following general formula (I).
It is an inorganic polymer of 0 to 50,000.
【００３４】[0034]
【化１】 [Chemical 1]
【００３５】上記式中、Ｒ1、Ｒ2及びＲ3は、それぞれ
独立に水素原子、アルキル基、アルケニル基、シクロア
ルキル基、アリール基、又はこれらの基以外でケイ素に
直結する基が炭素である基、アルキルシリル基、アルキ
ルアミノ基、アルコキシ基を表わす。ここで、前記リチ
ウム遷移金属複合窒化物の粒子の表面に、前記少なくと
もリチウムと合金を形成することができる元素を含む化
合物を緻密に付着させ、確実に前記リチウム遷移金属複
合窒化物の粒子の少なくとも表層部に、酸素と、リチウ
ムと合金を形成することができる元素とを含有させるた
めに、焼成により架橋構造を形成するポリシラザンであ
ることが好ましく、よってＲ1、Ｒ2及びＲ3の少なくと
も１つは水素原子であることが好ましい。In the above formula, R 1 , R 2 and R 3 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a group other than these groups which is directly bonded to silicon is carbon. Represents a group, an alkylsilyl group, an alkylamino group, and an alkoxy group. Here, a compound containing an element capable of forming an alloy with at least lithium is densely adhered to the surface of the particles of the lithium transition metal composite nitride, and at least the particles of the lithium transition metal composite nitride are securely attached. In order to contain oxygen and an element capable of forming an alloy with lithium in the surface layer portion, polysilazane that forms a crosslinked structure by firing is preferable, and therefore at least one of R 1 , R 2 and R 3 is used. Is preferably a hydrogen atom.
【００３６】また、上記ポリシラザンはそれ単独で使用
することもできるが、シラザン（モノマー）と他のモノ
マーとの共重合体や、ポリシラザンと他の化合物との混
合物としても使用できる。用いるポリシラザンには、鎖
状、環状又は架橋構造を有するもの、あるいは分子内に
これら複数の構造を同時に有するものがあり、これら単
独でも、あるいはこれらの混合物でも使用できる。中で
も、前記リチウム遷移金属複合窒化物の粒子の表面に緻
密に付着させることができるという点からはペルヒドロ
ポリシラザンが最も好ましい。前記一般式（Ｉ）におい
てＲ1、Ｒ2及びＲ3に水素原子を有するものが、ペルヒ
ドロポリシラザンであり、その製造法は、例えば特公昭
６３−１６３２５号公報、D. Seyferth らCommunicatio
n of Am.Cer. Soc., C-13, January（1983）などに報告
されている。ペルヒドロポリシラザンの構造の一例を以
下に示す。The polysilazane can be used alone, but it can also be used as a copolymer of silazane (monomer) and another monomer, or a mixture of polysilazane and another compound. The polysilazanes to be used include those having a chain structure, a cyclic structure, or a crosslinked structure, or those having a plurality of these structures simultaneously in the molecule, and these can be used alone or in a mixture thereof. Among them, perhydropolysilazane is most preferable because it can be densely adhered to the surface of the particles of the lithium transition metal composite nitride. Those having hydrogen atoms in R 1 , R 2 and R 3 in the general formula (I) are perhydropolysilazanes, and the production method thereof is, for example, Japanese Patent Publication No. 63-16325, D. Seyferth et al.
n of Am.Cer. Soc., C-13, January (1983). An example of the structure of perhydropolysilazane is shown below.
【００３７】[0037]
【化２】 [Chemical 2]
【００３８】前記一般式（Ｉ）においてＲ1及びＲ2に水
素原子、Ｒ3にメチル基を有するポリシラザンの製造方
法は、D. Seyferth らPolym. Prepr., Am. Chem. Soc.,
Div. Polym. Chem., 25, 10（1984）に報告されてい
る。この方法により得られるポリシラザンは、繰り返し
単位が −（ＳｉＨ2ＮＣＨ3）− の鎖状ポリマーと環状
ポリマーであり、いずれも架橋構造を持たない。A method for producing polysilazane having hydrogen atoms in R 1 and R 2 and a methyl group in R 3 in the general formula (I) is described in D. Seyferth et al., Polym. Prepr., Am. Chem. Soc.,
Div. Polym. Chem., 25 , 10 (1984). The polysilazane obtained by this method is a chain polymer having a repeating unit of — (SiH 2 NCH 3 ) — and a cyclic polymer, and neither has a crosslinked structure.
【００３９】また、前記一般式（Ｉ）でＲ1及びＲ3に水
素原子、Ｒ2に有機基を有するポリオルガノ（ヒドロ）
シラザンの製造法は、D. Seyferth らPolym. Prepr., A
m. Chem. Soc., Div. Polym. Chem., 25, 10（1984）、
又は特開昭６１−８９２３０号公報などに報告されてい
る。これらの方法により得られるポリシラザンには、−
（Ｒ2ＳｉＨＮＨ）− を繰り返し単位として、主として
重合度が３〜５の環状構造を有するものや、（Ｒ3Ｓｉ
ＨＮＨ）x〔（Ｒ2ＳｉＨ）1.5Ｎ〕1-x（０．４＜ｘ＜
１）の化学式で示される分子内に鎖状構造と環状構造を
同時に有するものがある。In the general formula (I), polyorgano (hydro) having a hydrogen atom in R 1 and R 3 and an organic group in R 2.
The method for producing silazanes is described by D. Seyferth et al., Polym. Prepr., A.
m. Chem. Soc., Div. Polym. Chem., 25 , 10 (1984),
Alternatively, it is reported in JP-A-61-89230. Polysilazanes obtained by these methods include-
(R 2 SiHNH)-as a repeating unit, having a cyclic structure mainly having a degree of polymerization of 3 to 5, or (R 3 SiHNH)-
HNH) x [(R 2 SiH) 1.5 N] 1-x (0.4 <x <
Some of the molecules represented by the chemical formula 1) have a chain structure and a cyclic structure at the same time.
【００４０】前記一般式（Ｉ）でＲ1に水素原子、Ｒ2及
びＲ3に有機基を有するポリシラザン、またＲ1及びＲ2
に有機基、Ｒ3に水素原子を有するポリシラザンは、−
（Ｒ1Ｒ2ＳｉＮＲ3）− を繰り返し単位として、主に重
合度が３〜５の環状構造を有している。In the above general formula (I), polysilazane having a hydrogen atom in R 1 and organic groups in R 2 and R 3 , and R 1 and R 2
An organic group in and a polysilazane having a hydrogen atom in R 3 are
It has a cyclic structure mainly having a degree of polymerization of 3 to 5 with (R 1 R 2 SiNR 3 ) − as a repeating unit.
【００４１】本発明に用いるポリシラザンは、前記一般
式（Ｉ）で表わされる単位からなる主骨格を有するが、
一般式（Ｉ）で表わされる単位は、上記にも明らかなよ
うに環状化することがあり、その場合にはその環状部分
が末端基となり、このような環状化がされない場合に
は、主骨格の末端はＲ1、Ｒ2、Ｒ3と同様の基又は水素
原子となる。The polysilazane used in the present invention has a main skeleton composed of the unit represented by the general formula (I),
The unit represented by the general formula (I) may be cyclized as is clear from the above, and in that case, the cyclic portion serves as a terminal group, and when such cyclization is not carried out, the main skeleton is Has a group similar to R 1 , R 2 and R 3 or a hydrogen atom.
【００４２】前記ポリオルガノ（ヒドロ）シラザンの中
には、D. Seyferth らCommunication of Am. Cer. So
c., C-132, July（1984）で報告されているような分子
内に架橋構造を有するものもある。また、特開昭４９−
６９７１７号公報に報告されているようなＲ1ＳｉＸ
3（Ｘ：ハロゲン）のアンモニア分解によって得られる
架橋構造を有するポリシラザン（Ｒ1Ｓｉ（ＮＨ）x）、
あるいはＲ1ＳｉＸ3及びＲ1Ｒ2ＳｉＸ2の共アンモニア
分解によって得られる下記の構造を有するポリシラザン
も出発材料として用いることができる。Among the polyorgano (hydro) silazanes, D. Seyferth et al. Communication of Am. Cer. So
Some have a crosslinked structure in the molecule as reported in c., C-132, July (1984). In addition, JP-A-49-
R 1 SiX as reported in Japanese Patent Publication No. 69717
A polysilazane (R 1 Si (NH) x ) having a crosslinked structure obtained by ammonia decomposition of 3 (X: halogen),
Alternatively, polysilazane having the following structure obtained by co-ammonia decomposition of R 1 SiX 3 and R 1 R 2 SiX 2 can also be used as a starting material.
【００４３】[0043]
【化３】 [Chemical 3]
【００４４】なお、上記式中、ｍ及びｎは正の整数であ
る。In the above formula, m and n are positive integers.
【００４５】また、本発明でリチウムと合金を形成する
ことができる元素を含む化合物として用いるＳｉ−Ｎ結
合を有する化合物として、ポリシラザンの変性物である
金属原子を含むポリメタロシラザンも用いることができ
る。その他、特開昭６２−１９５０２４号公報に報告さ
れているような繰り返し単位が〔（ＳｉＨ2）n（ＮＨ）
m〕及び〔（ＳｉＨ2）rＯ〕（式中、ｎ、ｍ、ｒはそれ
ぞれ１、２又は３である）で表されるポリシロキサザ
ン、特開平２−８４４３７号公報に報告されているよう
な耐熱性に優れたポリボロシラザン、特開昭６３−８１
１２２号、同６３−１９１８３２号、特開平２−７７４
２７号公報に報告されているようなポリメタロシラザ
ン、特開平１−１３８１０８号、同１−１３８１０７
号、同１−２０３４２９号、同１−２０３４３０号公報
に報告されているような分子量を増加させた改質ポリシ
ラザン、特開平４−６３８３３号、同３−３２０１６７
号公報に報告されているような耐加水分解性を向上させ
た改質ポリシラザン、特開平２−１７５７２６号、同５
−８６２００号、同５−３３１２９３号、同３−３１３
２６号公報に報告されているようなポリシラザンに有機
成分を導入した厚膜化に有利な共重合ポリシラザン、特
開平５−２３８８２７号、同６−１２２８５２号、同６
−２９９１８８号、同６−３０６３２９号、同６−２４
０２０８号、同７−１９６９８６号公報に報告されてい
るようなポリシラザンに酸化を促進するための触媒化合
物を付加又は添加した低温反応ポリシラザン等も同様に
使用できる。As the compound having an Si--N bond used as a compound containing an element capable of forming an alloy with lithium in the present invention, polymetallosilazane containing a metal atom which is a modified product of polysilazane can also be used. . In addition, a repeating unit as reported in JP-A-62-195024 is [(SiH 2 ) n (NH)
m ] and [(SiH 2 ) r O] (wherein n, m, and r are 1, 2 or 3 respectively), and polysiloxazane is reported in JP-A-2-84437. Such polyborosilazane having excellent heat resistance, JP-A-63-81
122, 63-191832, JP-A-2-774.
Polymetallosilazanes as reported in Japanese Patent Publication No. 27, JP-A-1-138108 and 1-138107.
No. 1,203,429, and No. 1-203430, the modified polysilazane having an increased molecular weight as disclosed in JP-A-4-63833 and JP-A-3-320167.
Modified polysilazanes having improved hydrolysis resistance as reported in JP-A-2-175726 and JP-A-5-175726.
-86200, 5-331293, 3-313.
No. 26, the copolymer polysilazane which is advantageous for thickening the film by introducing an organic component into polysilazane, JP-A-5-238827, JP-A-6-122852, and JP-A-6-122852.
-299188, 6-306329, 6-24
Similarly, low temperature reaction polysilazanes obtained by adding or adding a catalyst compound for promoting oxidation to polysilazanes as reported in JP-A-0208 and JP-A-7-196986 can be used.
【００４６】本発明における前記リチウム遷移金属複合
窒化物の粒子の表面へのＳｉ−Ｎ結合を有する化合物の
付着は、Ｓｉ−Ｎ結合を有する化合物（ポリシラザン
等）を溶剤に溶解させてコーティング用組成物を調製
し、これと前記リチウム遷移金属複合窒化物とを混合す
ることにより行われる。コーティング用組成物に用いら
れる溶剤としては、脂肪族炭化水素、脂環式炭化水素、
芳香族炭化水素の炭化水素溶剤、ハロゲン化メタン、ハ
ロゲン化エタン、ハロゲン化ベンゼン等のハロゲン化炭
化水素、脂肪族エーテル、脂環式エーテル等のエーテル
類を使用することができる。好ましい溶剤は、ペンタン
ヘキサン、イソヘキサン、メチルペンタン、ヘプタン、
イソヘプタン、オクタン、イソオクタン、シクロペンタ
ン、メチルシクロペンタン、シクロヘキサン、メチルシ
クロヘキサン、ベンゼン、トルエン、キシレン、エチル
ベンゼン、エチルシクロヘキサン、シクロヘキセン、ｐ
−メンタン、リモネン、デカリン、テトラリン、フェニ
ルシクロヘキサン、シクロヘキサノン、ノナン、デカ
ン、ｎ−ヘキサン、ペンタン、ジメチルジエトキシシラ
ン、メチルトリエトキシシラン等の炭化水素、塩化メチ
レン、クロロホルム、四塩化炭素、ブロモホルム、塩化
エチレン、塩化エチリデン、トリクロロエタン、テトラ
クロロエタン等のハロゲン化炭化水素、エチルエーテ
ル、イソプロピルエーテル、エチルブチルエーテル、ブ
チルエーテル、１，２−ジオキシエタン、ジオキサン、
ジメチルジオキサン、テトラヒドロフラン、テトラヒド
ロピラン等のエーテル類、等である。これらの溶剤を使
用する場合、ポリシラザンの溶解度や溶剤の蒸発速度を
調節するために、２種類以上の溶剤を混合してもよい。
溶剤の使用量（割合）はポリシラザンの平均分子量、分
子量分布、その構造によって異なるので、適宜、自由に
混合することができる。好ましくは固形分濃度で１〜５
０質量％の範囲で混合することができる。In the present invention, the compound having a Si--N bond is attached to the surface of the particles of the lithium transition metal composite nitride by dissolving the compound having a Si--N bond (polysilazane or the like) in a solvent to form a coating composition. It is carried out by preparing a product and mixing it with the lithium-transition metal composite nitride. As the solvent used in the coating composition, aliphatic hydrocarbons, alicyclic hydrocarbons,
Hydrocarbon solvents of aromatic hydrocarbons, halogenated hydrocarbons such as halogenated methane, halogenated ethane and halogenated benzene, and ethers such as aliphatic ethers and alicyclic ethers can be used. Preferred solvents are pentane hexane, isohexane, methyl pentane, heptane,
Isoheptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylcyclohexane, cyclohexene, p
Hydrocarbons such as menthane, limonene, decalin, tetralin, phenylcyclohexane, cyclohexanone, nonane, decane, n-hexane, pentane, dimethyldiethoxysilane, methyltriethoxysilane, methylene chloride, chloroform, carbon tetrachloride, bromoform, chloride Halogenated hydrocarbon such as ethylene, ethylidene chloride, trichloroethane, tetrachloroethane, etc., ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, 1,2-dioxyethane, dioxane,
Examples include ethers such as dimethyldioxane, tetrahydrofuran, and tetrahydropyran. When these solvents are used, two or more kinds of solvents may be mixed in order to adjust the solubility of polysilazane and the evaporation rate of the solvent.
The amount (ratio) of the solvent used varies depending on the average molecular weight of polysilazane, the molecular weight distribution, and the structure thereof, so that they can be freely mixed as appropriate. The solid content concentration is preferably 1 to 5
It can be mixed in the range of 0% by mass.
【００４７】Ｓｉ−Ｎ結合を有する化合物（ポリシラザ
ン等）を付着したリチウム遷移金属複合窒化物の焼成
は、窒素ガスに酸素ガスを混入した酸化性ガス雰囲気下
で行われる。これにより、ポリシラザン中の窒素及び水
素が酸素に置き換わることにより前記リチウム遷移金属
複合窒化物の粒子の少なくとも表層部に、酸素、及びリ
チウムと合金を形成することができる元素とを含有させ
ることができる。The firing of the lithium-transition metal composite nitride to which a compound having a Si--N bond (polysilazane or the like) is attached is performed in an oxidizing gas atmosphere in which oxygen gas is mixed with nitrogen gas. Thereby, oxygen and an element capable of forming an alloy with lithium can be contained in at least the surface layer portion of the particles of the lithium-transition metal composite nitride by replacing nitrogen and hydrogen in the polysilazane with oxygen. .
【００４８】焼成温度は特に限定されないが、一般に、
３００〜５００℃の範囲内の温度が好ましい。焼成時間
も特に限定されないが、一般に、０．５〜３時間の焼成
時間が好ましい。The firing temperature is not particularly limited, but in general,
Temperatures within the range of 300-500 ° C are preferred. The firing time is not particularly limited, but generally a firing time of 0.5 to 3 hours is preferable.
【００４９】次に、本発明の電気化学素子として、リチ
ウム二次電池について説明する。このリチウム二次電池
は、負極と、正極と、非水電解質を有し、負極と正極は
セパレータにより隔離されている。Next, a lithium secondary battery will be described as the electrochemical device of the present invention. This lithium secondary battery has a negative electrode, a positive electrode, and a nonaqueous electrolyte, and the negative electrode and the positive electrode are separated by a separator.
【００５０】負極は、前記リチウム含有電極材料に、必
要であれば導電助剤、更に結着剤を加えて混合し、得ら
れた合剤を適宜の手段で成形又は金属箔等の基体に塗布
することにより形成できる。For the negative electrode, the lithium-containing electrode material is mixed with a conductive auxiliary agent and a binder if necessary, and the resulting mixture is molded or applied to a base such as a metal foil by an appropriate means. Can be formed.
【００５１】前記導電助剤としては、構成されたリチウ
ム二次電池において化学変化を起こさない電子伝導性材
料であれば特に限定されない。通常、天然黒鉛（鱗状黒
鉛、鱗片状黒鉛、土状黒鉛等）、人造黒鉛、カーボンブ
ラック、アセチレンブラック、ケッチェンブラック、炭
素繊維、金属粉（銅粉、ニッケル粉、アルミニウム粉、
銀粉等）、金属繊維等、あるいは特開昭５９−２０９７
１号公報に記載のポリフェニレン誘導体等の導電性材料
を１種又はこれらの混合物として使用することができ
る。The conductive auxiliary agent is not particularly limited as long as it is an electron conductive material that does not cause a chemical change in the constructed lithium secondary battery. Usually, natural graphite (scaly graphite, flake graphite, earthy graphite, etc.), artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, metal powder (copper powder, nickel powder, aluminum powder,
Silver powder, etc.), metal fiber, etc., or JP-A-59-2097.
The conductive material such as the polyphenylene derivative described in JP-A-1 can be used alone or as a mixture thereof.
【００５２】前記結着剤としては、通常、でんぷん、ポ
リビニルアルコール、カルボキシメチルセルロース、ヒ
ドロキシプロピルセルロース、再生セルロース、ジアセ
チルセルロース、ポリビニルクロリド、ポリビニルピロ
リドン、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポ
リフッ化ビニリデン、ポリエチレン、ポリプロピレン、
エチレン−プロピレン−ジエンターポリマー（ＥＰＤ
Ｍ）、スルホン化ＥＰＤＭ、スチレンブタジエンゴム、
ブタジエンゴム、ポリブタジエン、フッ素ゴム、ポリエ
チレンオキシド、等の多糖類、熱可塑性樹脂、ゴム弾性
を有するポリマー等やこれらの変成体を用いることがで
きる。The binder is usually starch, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, regenerated cellulose, diacetyl cellulose, polyvinyl chloride, polyvinylpyrrolidone, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyethylene, polypropylene,
Ethylene-propylene-diene terpolymer (EPD
M), sulfonated EPDM, styrene-butadiene rubber,
Polysaccharides such as butadiene rubber, polybutadiene, fluororubber and polyethylene oxide, thermoplastic resins, polymers having rubber elasticity and the like, and modified products thereof can be used.
【００５３】正極材料としては、リチウムを含有する、
チタン、モリブデン、タングステン、ニオブ、バナジウ
ム、マンガン、鉄、クロム、ニッケル、コバルト等の遷
移金属の複合酸化物、複合硫化物、複合硫酸化物等を用
いることができる。例えば、ＬｉＣｏＯ2のような一般
式ＬｉＭＯ2（Ｍは遷移金属元素）で表されるＲ３ｍを
空間群に持つ層状酸化物、あるいはＬｉＭｎ2Ｏ4のよう
な一般式ＬｉＭ2Ｏ4（Ｍは遷移金属元素）で表されるＦ
ｄ３ｍを空間群に持つスピネル型酸化物等が正極材料と
しては好適である。The positive electrode material contains lithium,
Complex oxides, complex sulfides, complex sulfates and the like of transition metals such as titanium, molybdenum, tungsten, niobium, vanadium, manganese, iron, chromium, nickel and cobalt can be used. For example, a layered oxide having R3m in the space group represented by the general formula LiMO 2 (M is a transition metal element) such as LiCoO 2 , or a general formula LiM 2 O 4 (M is a transition) such as LiMn 2 O 4. F represented by (metal element)
A spinel type oxide having d3m in the space group is suitable as the positive electrode material.
【００５４】非水電解質としては、例えば、ＬｉＣＦ3
ＳＯ3、ＬｉＣｌＯ4、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣ4
Ｆ9ＳＯ3等より選ばれる電解質を、１，２−ジメトキシ
エタン、１，２−ジエトキシエタン、プロピレンカーボ
ネート、エチレンカーボネート、γ−ブチロラクトン、
テトラヒドロフラン、１，３−ジオキソラン、ジエチル
カーボネート、メチルエチルカーボネート等の有機溶媒
から選ばれる１種又は２種以上の混合溶媒に溶解した非
水電解液や、前記非水電解液を基材に含浸させてゲル化
させたポリマーゲル電解質等が用いられ、リチウム二次
電池に対する要求特性やその用途等に応じて適宜使い分
けられる。Examples of the non-aqueous electrolyte include LiCF 3
SO 3 , LiClO 4 , LiPF 6 , LiBF 4 , LiC 4
The electrolyte selected from F 9 SO 3 and the like is 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene carbonate, ethylene carbonate, γ-butyrolactone,
A non-aqueous electrolyte solution dissolved in one or more mixed solvents selected from organic solvents such as tetrahydrofuran, 1,3-dioxolane, diethyl carbonate, and methyl ethyl carbonate, or a base material impregnated with the non-aqueous electrolyte solution. A gelled polymer gel electrolyte or the like is used, and can be appropriately used depending on the required characteristics of the lithium secondary battery and its application.
【００５５】セパレータとしては、例えば不織布や微孔
性フィルムが用いられる。前記不織布の材質としては、
ポリプロピレン、ポリエチレン、ポリエチレンテレフタ
レート、ポリブチレンテレフタレート等がある。また、
前記微孔性フィルムの材質としては、ポリプロピレン、
ポリエチレン、エチレン−プロピレン共重合体等があ
る。As the separator, for example, non-woven fabric or microporous film is used. As the material of the non-woven fabric,
Examples include polypropylene, polyethylene, polyethylene terephthalate, and polybutylene terephthalate. Also,
The material of the microporous film, polypropylene,
Examples include polyethylene and ethylene-propylene copolymers.
【００５６】[0056]
【実施例】以下、本発明を実施例により説明する。但
し、本発明はそれら実施例のみに限定されるものではな
い。また、下記の記載において「部」及び「％」は、特
に断りがない限り、「質量部」及び「質量％」を意味す
る。EXAMPLES The present invention will be described below with reference to examples. However, the present invention is not limited to these examples. Moreover, in the following description, "part" and "%" mean "part by mass" and "% by mass" unless otherwise specified.
【００５７】先ず、酸素、及びリチウムと合金を形成す
ることができる元素を含む化合物１〜４を以下のように
合成した。First, compounds 1 to 4 containing oxygen and an element capable of forming an alloy with lithium were synthesized as follows.
【００５８】（化合物１の合成）窒素導入管を備え付け
た反応容器にテトラヒドロフラン（ＴＨＦ）２５０部及
びジメチルシロキサンと水酸基を有する反応性シリコー
ン（チッソ（株）製の“ＦＭ−４４１１”）８６．７部
を計り込み、窒素ガス雰囲気下で沸点まで昇温した。こ
の反応容器に４，４’−ジフェニルメタンジイソシアネ
ート１３．３部を１時間にわたって滴下し、滴下終了後
に還流しながら２．５時間反応させた。反応後の溶液
は、不揮発分６４％の少なくとも酸素、及びリチウムと
合金を形成することができるケイ素を含むウレタン系樹
脂化合物であった。(Synthesis of Compound 1) 86.7 parts of tetrahydrofuran (THF) and reactive silicone having dimethylsiloxane and a hydroxyl group (“FM-4411” manufactured by Chisso Corporation) 86.7 in a reaction vessel equipped with a nitrogen introducing tube. Parts were weighed in and heated to the boiling point under a nitrogen gas atmosphere. 13.3 parts of 4,4'-diphenylmethane diisocyanate was added dropwise to this reaction vessel over 1 hour, and after completion of the addition, the mixture was reacted for 2.5 hours under reflux. The solution after the reaction was a urethane-based resin compound containing at least oxygen having a nonvolatile content of 64% and silicon capable of forming an alloy with lithium.
【００５９】（化合物２の合成）窒素導入管を備え付け
た反応容器にＴＨＦ３００部及びジメチルシロキサンと
水酸基を有する反応性シリコーン（チッソ（株）製の
“ＦＭ−４４２１”）９８．０部を計り込み、窒素ガス
雰囲気下で沸点まで昇温した。この反応容器に４，４’
−ジフェニルメタンジイソシアネート２．０部を１時間
にわたって滴下し、滴下終了後に還流しながら３時間反
応させた。反応後の溶液は、不揮発分４９％の少なくと
も酸素、及びリチウムと合金を形成することができるケ
イ素を含むウレタン系樹脂化合物であった。(Synthesis of Compound 2) 300 parts of THF and 98.0 parts of reactive silicone having dimethylsiloxane and a hydroxyl group (“FM-4421” manufactured by Chisso Corporation) were weighed in a reaction vessel equipped with a nitrogen introducing tube. The temperature was raised to the boiling point under a nitrogen gas atmosphere. 4,4 'in this reaction vessel
-2.0 parts of diphenylmethane diisocyanate was added dropwise over 1 hour, and after the addition was completed, the mixture was reacted for 3 hours under reflux. The solution after the reaction was a urethane resin compound containing at least oxygen having a nonvolatile content of 49% and silicon capable of forming an alloy with lithium.
【００６０】（化合物３の合成）窒素導入管を備え付け
た反応容器にＴＨＦ１５０部、ジメチルシロキサンと水
酸基を有する反応性シリコーン（チッソ（株）製の“Ｆ
Ｍ−４４２５”）９８．８部及び４，４’−ジフェニル
メタンジイソシアネート１．２部を計り込み、窒素ガス
雰囲気下で沸点まで昇温した後、還流しながら３時間反
応させた。反応後の溶液は、不揮発分５８％の少なくと
も酸素、及びリチウムと合金を形成することができるケ
イ素を含むウレタン系樹脂化合物であった。(Synthesis of Compound 3) 150 parts of THF, a reactive silicone having dimethylsiloxane and a hydroxyl group (“F” manufactured by Chisso Corporation) were placed in a reaction vessel equipped with a nitrogen introducing tube.
M-4425 ″) 98.8 parts and 4,4′-diphenylmethane diisocyanate 1.2 parts were weighed in, heated to the boiling point in a nitrogen gas atmosphere, and then reacted under reflux for 3 hours. Was a urethane-based resin compound containing at least oxygen with a nonvolatile content of 58% and silicon capable of forming an alloy with lithium.
【００６１】（化合物４の合成）メチルアクリレート１
９．６部、ｎ−ブチルメタクリレート１５．４部、ラウ
リルメタクリレート１０．０部、スチレン３５．０部、
ジメチルシロキサンと炭素数３のアルキレン基とからな
るシリコーン系マクロモノマー（信越化学社製の“Ｘ−
２２−１７４ＤＸ”）２０．０部、パーオキシエステル
（日本油脂社製の“パーブチルＯ”）８．０部を混合し
て溶液を調製した。(Synthesis of Compound 4) Methyl Acrylate 1
9.6 parts, n-butyl methacrylate 15.4 parts, lauryl methacrylate 10.0 parts, styrene 35.0 parts,
Silicone macromonomer consisting of dimethyl siloxane and alkylene group having 3 carbon atoms (“X-
22-174DX ") 20.0 parts and peroxyester (NOF CORPORATION" Perbutyl O ") 8.0 parts were mixed to prepare a solution.
【００６２】次に、窒素導入管を備え付けた反応容器に
ＴＨＦ１００部を計り込み、窒素ガス雰囲気下で沸点ま
で昇温した。この反応容器に上記溶液全量を２時間にわ
たって滴下し、滴下終了後に還流しながら８時間反応さ
せた。反応後の溶液は、不揮発分６１％の少なくとも酸
素、及びリチウムと合金を形成することができるケイ素
を含むアクリル系樹脂化合物であった。Next, 100 parts of THF was weighed into a reaction vessel equipped with a nitrogen introducing tube, and the temperature was raised to the boiling point in a nitrogen gas atmosphere. The whole amount of the above solution was dropped into this reaction vessel over 2 hours, and after the dropping was completed, the reaction was carried out for 8 hours under reflux. The solution after the reaction was an acrylic resin compound containing at least oxygen having a nonvolatile content of 61% and silicon capable of forming an alloy with lithium.
【００６３】次に、以下のようにリチウム含有電極材料
を製造した。Next, a lithium-containing electrode material was manufactured as follows.
【００６４】（実施例１）窒化リチウム（Ｌｉ3Ｎ）と
金属コバルト（Ｃｏ）をモル比で２：１の割合で混合
し、その混合物を銅製のるつぼに入れ、窒素ガス雰囲気
下７００℃で６時間焼成し、リチウム遷移金属複合窒化
物（Ｌｉ5ＣｏＮ2）の粉末を得た。ＴＨＦ３ｇに前記化
合物１を１ｇ溶解させた溶液中に上記リチウム遷移金属
複合窒化物粉末１ｇを分散させ、ＴＨＦ２．５ｇ／ヘキ
サン２．５ｇの混合溶媒で希釈した。その後、この溶液
をヘキサン１０ｇ中に滴下することにより、表面に前記
化合物１を析出させたリチウム遷移金属複合窒化物の沈
澱を得た。沈殿物を回収し、溶媒を除去した後、その沈
殿物を銅製のるつぼに入れ、窒素ガス雰囲気下５００℃
で１時間焼成し、本発明のリチウム含有電極材料の粉末
を得た。得られた粉末の平均粒径は約１５μｍであっ
た。Example 1 Lithium nitride (Li 3 N) and metallic cobalt (Co) were mixed at a molar ratio of 2: 1, and the mixture was placed in a copper crucible at 700 ° C. under a nitrogen gas atmosphere. The powder was fired for 6 hours to obtain a powder of lithium transition metal composite nitride (Li 5 CoN 2 ). 1 g of the lithium-transition metal composite nitride powder was dispersed in a solution prepared by dissolving 1 g of the compound 1 in 3 g of THF, and diluted with a mixed solvent of 2.5 g of THF / 2.5 g of hexane. Then, this solution was added dropwise to 10 g of hexane to obtain a precipitate of the lithium-transition metal composite nitride having Compound 1 deposited on the surface. After recovering the precipitate and removing the solvent, the precipitate is placed in a copper crucible and placed under a nitrogen gas atmosphere at 500 ° C.
Then, it was baked for 1 hour to obtain a powder of the lithium-containing electrode material of the present invention. The average particle size of the obtained powder was about 15 μm.
【００６５】（実施例２）前記化合物１に代えて前記化
合物２を用いたこと以外は実施例１と同様の方法で、本
発明のリチウム含有電極材料の粉末を得た。得られた粉
末の平均粒径は約１５μｍであった。Example 2 A lithium-containing electrode material powder of the present invention was obtained in the same manner as in Example 1 except that the compound 2 was used instead of the compound 1. The average particle size of the obtained powder was about 15 μm.
【００６６】（実施例３）前記化合物１に代えて前記化
合物３を用いたこと以外は実施例１と同様の方法で、本
発明のリチウム含有電極材料の粉末を得た。得られた粉
末の平均粒径は約１５μｍであった。Example 3 A lithium-containing electrode material powder of the present invention was obtained in the same manner as in Example 1 except that the compound 3 was used in place of the compound 1. The average particle size of the obtained powder was about 15 μm.
【００６７】（実施例４）前記化合物１に代えて前記化
合物４を用いたこと以外は実施例１と同様の方法で、本
発明のリチウム含有電極材料の粉末を得た。得られた粉
末の平均粒径は約２０μｍであった。Example 4 A lithium-containing electrode material powder of the present invention was obtained in the same manner as in Example 1 except that the compound 4 was used in place of the compound 1. The average particle size of the obtained powder was about 20 μm.
【００６８】（実施例５）実施例１と同様の方法で、リ
チウム遷移金属複合窒化物の粉末を得た。次に、下記化
学式（化４）で表される化合物５と前記リチウム遷移金
属複合窒化物の粉末を各１ｇずつ混合し、この混合物を
銅製のるつぼに入れ、窒素ガス雰囲気下５００℃で１時
間焼成し、本発明のリチウム含有電極材料の粉末を得
た。得られた粉末の平均粒径は約２０μｍであった。Example 5 By the same method as in Example 1, a lithium-transition metal composite nitride powder was obtained. Next, 1 g of each of the compound 5 represented by the following chemical formula (Formula 4) and the powder of the lithium-transition metal composite nitride was mixed, and the mixture was put into a copper crucible, and the mixture was put in a nitrogen gas atmosphere at 500 ° C. for 1 hour. Firing was performed to obtain a powder of the lithium-containing electrode material of the present invention. The average particle size of the obtained powder was about 20 μm.
【００６９】[0069]
【化４】 [Chemical 4]
【００７０】（実施例６）実施例１と同様の方法で、リ
チウム遷移金属複合窒化物の粉末を得た。次に、得られ
た粉末をペルヒドロポリシラザン２０％含有キシレン溶
液に分散し、しばらく攪拌した後に沈降させることで、
表面にペルヒドロポリシラザンを付着させたリチウム遷
移金属複合窒化物を得た。これを窒素９５体積％、酸素
５体積％の混合ガス雰囲気下５００℃で１時間焼成し、
本発明のリチウム含有電極材料の粉末を得た。得られた
粉末の平均粒径は約１０μｍであり、ケイ素の含有量は
１１％であった。Example 6 In the same manner as in Example 1, a lithium transition metal composite nitride powder was obtained. Next, the obtained powder is dispersed in a xylene solution containing 20% of perhydropolysilazane, stirred for a while, and then allowed to settle,
A lithium transition metal composite nitride having perhydropolysilazane attached to the surface was obtained. This is fired at 500 ° C. for 1 hour in a mixed gas atmosphere of 95% by volume of nitrogen and 5% by volume of oxygen,
A powder of the lithium-containing electrode material of the present invention was obtained. The average particle size of the obtained powder was about 10 μm, and the content of silicon was 11%.
【００７１】（実施例７）実施例１と同様の方法で、リ
チウム遷移金属複合窒化物の粉末を得た。次に、得られ
た粉末を、あらかじめ重合させたテトラエトキシシラン
を溶解させたトルエン中に分散させ、ＳｉＯx（０＜ｘ
≦２）とＬｉ5ＣｏＮ2からなるスラリーを得た。得られ
たスラリーの溶媒を除去し、真空乾燥を行った後、その
混合物を銅製のるつぼに入れ、窒素ガス雰囲気下５００
℃で１時間焼成し、本発明のリチウム含有電極材料の粉
末を得た。得られた粉末の平均粒径は約２０μｍであっ
た。Example 7 In the same manner as in Example 1, a lithium transition metal composite nitride powder was obtained. Then, the obtained powder was dispersed in toluene in which tetraethoxysilane polymerized in advance was dissolved, and SiO x (0 <x
A slurry consisting of ≦ 2) and Li 5 CoN 2 was obtained. After removing the solvent of the obtained slurry and performing vacuum drying, the mixture was put into a copper crucible, and the mixture was put under a nitrogen gas atmosphere at 500.
The powder of the lithium-containing electrode material of the present invention was obtained by firing at 1 ° C. for 1 hour. The average particle size of the obtained powder was about 20 μm.
【００７２】（実施例８）窒化リチウム（Ｌｉ3Ｎ）と
金属銅（Ｃｕ）をモル比で２：１の割合で混合し、その
混合物を銅製のるつぼに入れ、窒素ガス雰囲気下６００
℃で６時間焼成し、リチウム遷移金属複合窒化物（Ｌｉ
5ＣｕＮ2）の粉末を得た。ＴＨＦ３ｇに前記化合物１を
１ｇ溶解させた溶液中に上記リチウム遷移金属複合窒化
物の粉末１ｇを分散させ、ＴＨＦ２．５ｇ／ヘキサン
２．５ｇの混合溶媒で希釈した。その後、この溶液をヘ
キサン１０ｇ中に滴下することにより、表面に前記化合
物１を析出させたリチウム遷移金属複合窒化物の沈澱を
得た。沈殿物を回収し、溶媒を除去した後、その沈殿物
を銅製のるつぼに入れ、窒素ガス雰囲気下５００℃で１
時間焼成し、本発明のリチウム含有電極材料の粉末を得
た。得られた粉末の平均粒径は約２０μｍであった。Example 8 Lithium nitride (Li 3 N) and metallic copper (Cu) were mixed at a molar ratio of 2: 1, and the mixture was put in a copper crucible and placed under a nitrogen gas atmosphere at 600.
Calcination for 6 hours at ℃, lithium transition metal composite nitride (Li
5 CuN 2 ) powder was obtained. 1 g of the lithium-transition metal composite nitride powder was dispersed in a solution prepared by dissolving 1 g of the compound 1 in 3 g of THF, and diluted with a mixed solvent of 2.5 g of THF / 2.5 g of hexane. Then, this solution was added dropwise to 10 g of hexane to obtain a precipitate of the lithium-transition metal composite nitride having Compound 1 deposited on the surface. After recovering the precipitate and removing the solvent, the precipitate is placed in a copper crucible and kept in a nitrogen gas atmosphere at 500 ° C. for 1 hour.
Firing was performed for a time to obtain a powder of the lithium-containing electrode material of the present invention. The average particle size of the obtained powder was about 20 μm.
【００７３】（実施例９）実施例８と同様の方法で、リ
チウム遷移金属複合窒化物の粉末を得た。次に、得られ
た粉末をペルヒドロポリシラザン２０％含有キシレン溶
液に分散し、しばらく攪拌した後に沈降させることで、
表面にペルヒドロポリシラザンを付着させたリチウム遷
移金属複合窒化物を得た。これを窒素９５体積％、酸素
５体積％の混合ガス雰囲気下５００℃で１時間焼成し、
本発明のリチウム含有電極材料の粉末を得た。得られた
粉末の平均粒径は約２０μｍであった。Example 9 By the same method as in Example 8, powder of lithium transition metal composite nitride was obtained. Next, the obtained powder is dispersed in a xylene solution containing 20% of perhydropolysilazane, stirred for a while, and then allowed to settle,
A lithium transition metal composite nitride having perhydropolysilazane attached to the surface was obtained. This is fired at 500 ° C. for 1 hour in a mixed gas atmosphere of 95% by volume of nitrogen and 5% by volume of oxygen,
A powder of the lithium-containing electrode material of the present invention was obtained. The average particle size of the obtained powder was about 20 μm.
【００７４】（実施例１０）ぺルヒドロポリシラザンを
付着させたリチウム遷移金属複合窒化物の焼成条件が、
窒素ガス雰囲気下５００℃で１時間焼成したこと以外は
実施例６と同様の方法で、本発明のリチウム含有電極材
料の粉末を得た。得られた粉末の平均粒径は約１０μｍ
であり、ケイ素の含有量は１２％であった。(Example 10) The firing conditions for the lithium-transition metal composite nitride having perhydropolysilazane attached were as follows:
A lithium-containing electrode material powder of the present invention was obtained in the same manner as in Example 6, except that the powder was fired at 500 ° C. for 1 hour in a nitrogen gas atmosphere. The average particle size of the obtained powder is about 10 μm.
And the silicon content was 12%.
【００７５】次に、上記実施例１〜１０で製造したリチ
ウム含有電極材料の粒子の表層部の組成分析を行った。
分析方法はＸ線光電子分光法（ＸＰＳ）を用い、分析装
置はＵＬＶＡＣ ＰＨＩ（アルバック ファイ）製のＥ
ＳＣＡ ５５００ＭＣを用いた。その結果を図１〜図４
に示す。図１〜図４は、実施例１で製造したリチウム含
有電極材料の粒子の表面から１０００ｎｍまでの酸素、
ケイ素、コバルト及びリチウムのそれぞれの含有量を任
意単位でプロットした図である。図１〜図４から明らか
なように、前記リチウム遷移金属複合窒化物の粒子に含
有された酸素及びケイ素の含有量は、粒子の表面近傍か
ら内部に向かって減少し、一方、コバルトの含有量は、
粒子の表面近傍から内部に向かって増加し、傾斜材料を
形成していることがわかる。更に、リチウムの含有量
は、深さ方向にほぼ一様に分布していることもわかる。
また、実施例２〜１０で製造したリチウム含有電極材料
も全て同様に傾斜材料を形成していた。Next, composition analysis of the surface layer portion of the particles of the lithium-containing electrode material produced in the above Examples 1 to 10 was conducted.
The analysis method uses X-ray photoelectron spectroscopy (XPS), and the analyzer is E manufactured by ULVAC PHI (ULVAC-PHI).
SCA 5500MC was used. The results are shown in FIGS.
Shown in. 1 to 4 show oxygen up to 1000 nm from the surface of the particles of the lithium-containing electrode material produced in Example 1,
It is the figure which plotted each content of silicon, cobalt, and lithium in arbitrary units. As is clear from FIGS. 1 to 4, the contents of oxygen and silicon contained in the particles of the lithium transition metal composite nitride decrease from the vicinity of the surface of the particles toward the inside, while the contents of cobalt are Is
It can be seen that the grain size increases from the vicinity of the surface toward the inside to form a graded material. Furthermore, it can be seen that the lithium content is distributed almost uniformly in the depth direction.
In addition, all the lithium-containing electrode materials manufactured in Examples 2 to 10 also formed gradient materials.
【００７６】（比較例１）実施例１と同様の方法で、リ
チウム遷移金属複合窒化物の粉末を得た。得られた粉末
に酸素、及びリチウムと合金を形成することができる元
素の導入は行わなかった。得られた粉末の平均粒径は約
１５μｍであった。Comparative Example 1 In the same manner as in Example 1, a lithium-transition metal composite nitride powder was obtained. Oxygen and an element capable of forming an alloy with lithium were not introduced into the obtained powder. The average particle size of the obtained powder was about 15 μm.
【００７７】（比較例２）実施例８と同様の方法で、リ
チウム遷移金属複合窒化物の粉末を得た。得られた粉末
に酸素、及びリチウムと合金を形成することができる元
素の導入は行わなかった。得られた粉末の平均粒径は約
１５μｍであった。(Comparative Example 2) In the same manner as in Example 8, a lithium-transition metal composite nitride powder was obtained. Oxygen and an element capable of forming an alloy with lithium were not introduced into the obtained powder. The average particle size of the obtained powder was about 15 μm.
【００７８】（比較例３）実施例１と同様の方法で、リ
チウム遷移金属複合窒化物の粉末を得た。得られた粉末
に一酸化ケイ素（ＳｉＯ）粉末を混合した後、その混合
物を銅製のるつぼに入れ、窒素ガス雰囲気下５００℃で
１時間焼成し、リチウム含有電極材料の粉末を得た。得
られた粉末の平均粒径は約２０μｍであった。(Comparative Example 3) In the same manner as in Example 1, a lithium transition metal composite nitride powder was obtained. After mixing silicon monoxide (SiO) powder with the obtained powder, the mixture was put into a copper crucible and baked at 500 ° C. for 1 hour in a nitrogen gas atmosphere to obtain a lithium-containing electrode material powder. The average particle size of the obtained powder was about 20 μm.
【００７９】次に、比較例３で製造したリチウム含有電
極材料の粒子の表層部の組成分析を行った。分析は前記
実施例１〜１０と同様に行った。その結果、比較例３に
おいてはリチウム遷移金属複合窒化物の粒子の表層部に
は、リチウムと合金を形成することができるケイ素は含
有されていなかった。Next, the composition of the surface layer of the particles of the lithium-containing electrode material produced in Comparative Example 3 was analyzed. The analysis was performed in the same manner as in Examples 1 to 10 above. As a result, in Comparative Example 3, silicon capable of forming an alloy with lithium was not contained in the surface layer part of the particles of the lithium transition metal composite nitride.
【００８０】次に、上記のようにして得られた実施例１
〜１０及び比較例１〜３のリチウム含有電極材料の大気
下での安定性を評価した。評価は、温度２５℃、湿度６
０％の大気中に上記リチウム含有電極材料を放置し、放
置開始からＸ線回折プロファイルに変化が生じるまでの
経過時間を測定して行った。即ち、製造直後のリチウム
含有電極材料のＸ線回折プロファイルと、大気中に放置
した後のＸ線回折プロファイルを比較して、図５に示す
ようなＬｉＯＨやＬｉ2ＣＯ3等の分解生成物のピークを
確認することにより、大気中での安定性を評価した。な
お、図５は、比較例１のリチウム含有電極材料の放置開
始前及び放置開始から４時間後のＸ線回折プロファイ
ル、並びに実施例１０のリチウム含有電極材料の放置開
始から４時間後のＸ線回折プロファイルをそれぞれ示し
たものである。また、測定は０．５時間ごとに行った。
その結果を表１に示す。Next, Example 1 obtained as described above
-10 and the stability of the lithium-containing electrode materials of Comparative Examples 1 to 3 in the atmosphere were evaluated. Evaluation is temperature 25 ℃, humidity 6
The lithium-containing electrode material was allowed to stand in 0% air and the elapsed time from the start of standing until the change in the X-ray diffraction profile was measured. That is, by comparing the X-ray diffraction profile of the lithium-containing electrode material immediately after production with the X-ray diffraction profile after leaving it in the air, decomposition products such as LiOH and Li 2 CO 3 as shown in FIG. By confirming the peak, stability in the atmosphere was evaluated. In addition, FIG. 5 shows the X-ray diffraction profiles of the lithium-containing electrode material of Comparative Example 1 before and 4 hours after the start of leaving, and the X-rays of the lithium-containing electrode material of Example 10 after 4 hours after the start of leaving. The respective diffraction profiles are shown. The measurement was performed every 0.5 hours.
The results are shown in Table 1.
【００８１】[0081]
【表１】 [Table 1]
【００８２】表１に示すように、酸素、及びリチウムと
合金を形成することができる元素を導入しなかった比較
例１及び比較例２のリチウム含有電極材料では大気下で
の安定性が低いのに対し、酸素、及びリチウムと合金を
形成することができる元素を表層部に含む実施例１〜９
のリチウム含有電極材料の大気下での安定性は高かっ
た。また、表層部にリチウムと合金を形成することがで
きる元素のみを含有させた実施例１０のリチウム含有電
極材料は、同じ条件で酸素をも含有させた実施例６のリ
チウム含有電極材料に比べて大気下での安定性が多少劣
っていた。As shown in Table 1, the lithium-containing electrode materials of Comparative Example 1 and Comparative Example 2 in which oxygen and an element capable of forming an alloy with lithium were not introduced have low stability in the atmosphere. On the other hand, Examples 1 to 9 containing oxygen and an element capable of forming an alloy with lithium in the surface layer portion
The stability of the lithium-containing electrode material of No. 1 in the atmosphere was high. Further, the lithium-containing electrode material of Example 10 in which only the element capable of forming an alloy with lithium was contained in the surface layer portion compared to the lithium-containing electrode material of Example 6 in which oxygen was also included under the same conditions. The stability in the atmosphere was somewhat inferior.
【００８３】また、リチウム含有電極材料の製造方法と
して、リチウムと合金を形成することができる元素を含
む単一の化合物を予め合成した後、その化合物をリチウ
ム遷移金属複合窒化物の粒子の表面に付着させて焼成す
る手法を採用した実施例１〜１０のリチウム含有電極材
料は、酸素、及びリチウムと合金を形成することができ
る元素を含む化合物と、リチウム遷移金属複合窒化物と
を混合したのみで、表面に付着させる処理を行わずに焼
成した比較例３のリチウム含有電極材料に比べ、大気下
でも高い安定性を示した。In addition, as a method for producing a lithium-containing electrode material, a single compound containing an element capable of forming an alloy with lithium is previously synthesized and then the compound is formed on the surface of particles of the lithium-transition metal composite nitride. The lithium-containing electrode materials of Examples 1 to 10, which adopted the technique of depositing and firing, were obtained by mixing only a compound containing oxygen and an element capable of forming an alloy with lithium, and a lithium transition metal composite nitride. In comparison with the lithium-containing electrode material of Comparative Example 3 which was fired without the treatment of adhering to the surface, it showed higher stability in the atmosphere.
【００８４】次に、上記実施例１〜１０で製造したリチ
ウム含有電極材料を用いてリチウム二次電池を試作し
た。なお、リチウム含有電極材料は、温度２５℃、湿度
６０％の大気中での放置時間が１時間以内のものを用い
た。Next, a lithium secondary battery was experimentally produced using the lithium-containing electrode materials produced in Examples 1 to 10 above. The lithium-containing electrode material used had a standing time of 1 hour or less in the atmosphere at a temperature of 25 ° C. and a humidity of 60%.
【００８５】先ず、負極材料として前記リチウム含有電
極材料１０ｍｇ、導電助剤として人造黒鉛９ｍｇ、結着
剤としてＰＴＦＥ１ｍｇを混合して調製した負極合剤を
金型内に充填し、９８ＭＰａの圧力で直径１０ｍｍの円
盤状に加圧成形して負極を作製した。また、正極材料と
してコバルト酸リチウム（ＬｉＣｏＯ2）６７ｍｇ、導
電助剤としてアセチレンブラック３．７ｍｇ、結着剤と
してＰＴＦＥ３．７ｍｇを混合して調製した正極合剤を
金型内に充填し、９８ＭＰａの圧力で直径１０ｍｍの円
盤状に加圧成形して正極を作製した。これらの正極、負
極の間にポリエチレン製のセパレータを配置し、非水電
解質としてはエチレンカーボネートとメチルエチルカー
ボネートとの体積比１：２の混合溶媒にＬｉＰＦ6を
１．２ｍｏｌ／ｄｍ3溶解したものを用いて、直径２０
ｍｍ、厚さ１．６ｍｍのコイン型リチウム二次電池を作
製した。これらの９種類の電池について、電流値０．５
ｍＡ／ｃｍ2、室温で０．０１〜１．４Ｖの電圧範囲で
充放電特性を調べた。その結果を表２に示す。First, a negative electrode mixture prepared by mixing 10 mg of the above-mentioned lithium-containing electrode material as a negative electrode material, 9 mg of artificial graphite as a conduction aid, and 1 mg of PTFE as a binder was filled in a mold, and the diameter was increased at a pressure of 98 MPa. A negative electrode was produced by pressure molding into a disk shape of 10 mm. In addition, a positive electrode mixture prepared by mixing lithium cobalt oxide (LiCoO 2 ) 67 mg as a positive electrode material, acetylene black 3.7 mg as a conduction aid, and PTFE 3.7 mg as a binder was filled in a mold, and 98 MPa of A positive electrode was produced by pressure molding into a disk shape having a diameter of 10 mm. A polyethylene separator is placed between the positive electrode and the negative electrode, and 1.2 mol / dm 3 of LiPF 6 is dissolved in a mixed solvent of ethylene carbonate and methyl ethyl carbonate in a volume ratio of 1: 2 as the non-aqueous electrolyte. With a diameter of 20
mm, and a thickness of 1.6 mm, a coin-type lithium secondary battery was produced. The current value of these 9 types of batteries is 0.5
The charge / discharge characteristics were examined in the voltage range of 0.01 to 1.4 V at mA / cm 2 and room temperature. The results are shown in Table 2.
【００８６】[0086]
【表２】 [Table 2]
【００８７】表２から明らかなように、初期放電容量は
いずれも８００ｍＡｈ／ｇ以上と高容量であった。ま
た、すべての電池で３０サイクル後の放電容量は、初期
放電容量の８０％以上を維持しており、サイクル特性も
良好であった。As is clear from Table 2, the initial discharge capacities were all high at 800 mAh / g or more. In addition, the discharge capacity after 30 cycles of all the batteries was maintained at 80% or more of the initial discharge capacity, and the cycle characteristics were good.
【００８８】[0088]
【発明の効果】以上のように、本発明によれば、高容量
で且つサイクル特性に優れた電気化学素子を構成するこ
とのできる電極材料として、大気中での安定性に優れた
リチウム含有電極材料を提供することができる。INDUSTRIAL APPLICABILITY As described above, according to the present invention, a lithium-containing electrode excellent in stability in the air is used as an electrode material capable of forming an electrochemical device having a high capacity and excellent cycle characteristics. Material can be provided.
【図１】実施例１で製造したリチウム含有電極材料の粒
子の表面から１０００ｎｍまでの酸素の含有量（任意単
位）をプロットした図である。FIG. 1 is a diagram in which the oxygen content (arbitrary unit) up to 1000 nm from the surface of particles of the lithium-containing electrode material produced in Example 1 is plotted.
【図２】実施例１で製造したリチウム含有電極材料の粒
子の表面から１０００ｎｍまでのケイ素の含有量（任意
単位）をプロットした図である。FIG. 2 is a diagram in which the content (arbitrary unit) of silicon up to 1000 nm from the surface of particles of the lithium-containing electrode material manufactured in Example 1 is plotted.
【図３】実施例１で製造したリチウム含有電極材料の粒
子の表面から１０００ｎｍまでのコバルトの含有量（任
意単位）をプロットした図である。FIG. 3 is a diagram in which the content (arbitrary unit) of cobalt up to 1000 nm from the surface of the particles of the lithium-containing electrode material manufactured in Example 1 is plotted.
【図４】実施例１で製造したリチウム含有電極材料の粒
子の表面から１０００ｎｍまでのリチウムの含有量（任
意単位）をプロットした図である。FIG. 4 is a diagram in which the lithium content (arbitrary unit) from the surface of the particles of the lithium-containing electrode material produced in Example 1 to 1000 nm is plotted.
【図５】実施例１０で製造したリチウム含有電極材料の
大気中放置４時間後、及び比較例１で製造したリチウム
含有電極材料の大気中放置前及び放置４時間後のＸ線回
折プロファイルを示した図である。FIG. 5 shows X-ray diffraction profiles of the lithium-containing electrode material manufactured in Example 10 after being left in the air for 4 hours, and the lithium-containing electrode material manufactured in Comparative Example 1 before being left in the air and after being left for 4 hours. It is a figure.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西原 昭二 大阪府茨木市丑寅１丁目１番88号 日立マ クセル株式会社内 (72)発明者 上田 篤司 大阪府茨木市丑寅１丁目１番88号 日立マ クセル株式会社内 (72)発明者 青山 茂夫 大阪府茨木市丑寅１丁目１番88号 日立マ クセル株式会社内 Ｆターム(参考） 4G048 AA01 AB01 AB04 AB05 AC06 AE05 5H029 AJ03 AJ05 AK03 AK05 AL00 AL12 AL18 AM03 AM04 AM05 AM07 CJ02 CJ22 CJ28 DJ12 HJ00 HJ01 5H050 AA07 AA08 BA16 BA17 CA07 CA11 CB00 CB12 CB30 FA12 FA14 FA18 GA02 GA17 GA22 GA27 HA00 HA01 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Shoji Nishihara Hitachi Ma, 1-88, Torora, Ibaraki City, Osaka Prefecture Within Kucsel Co., Ltd. (72) Inventor Atsushi Ueda Hitachi Ma, 1-88, Torora, Ibaraki City, Osaka Prefecture Within Kucsel Co., Ltd. (72) Inventor Shigeo Aoyama Hitachi Ma, 1-88, Torora, Ibaraki City, Osaka Prefecture Within Kucsel Co., Ltd. F-term (reference) 4G048 AA01 AB01 AB04 AB05 AC06 AE05 5H029 AJ03 AJ05 AK03 AK05 AL00 AL12 AL18 AM03 AM04 AM05 AM07 CJ02 CJ22 CJ28 DJ12 HJ00 HJ01 5H050 AA07 AA08 BA16 BA17 CA07 CA11 CB00 CB12 CB30 FA12 FA14 FA18 GA02 GA17 GA22 GA27 HA00 HA01
Claims (11)
なくとも表層部に、リチウムと合金を形成することがで
きる元素を含有させたことを特徴とするリチウム含有電
極材料。1. A lithium-containing electrode material, characterized in that at least a surface layer portion of particles of a lithium transition metal composite nitride contains an element capable of forming an alloy with lithium.
なくとも表層部に、酸素と、リチウムと合金を形成する
ことができる元素とを含有させたことを特徴とするリチ
ウム含有電極材料。2. A lithium-containing electrode material, wherein oxygen and an element capable of forming an alloy with lithium are contained in at least the surface layer portion of the particles of the lithium-transition metal composite nitride.
面に、少なくともリチウムと合金を形成することができ
る元素を含む化合物を付着させた後、これを焼成するこ
とにより形成することができるリチウム含有電極材料。3. A lithium-containing compound which can be formed by depositing a compound containing at least an element capable of forming an alloy with lithium on the surface of particles of a lithium-transition metal composite nitride, followed by firing. Electrode material.
する遷移金属元素が、コバルト、銅、鉄及びニッケルよ
りなる群から選ばれた少なくとも１種の元素である請求
項１、２又は３に記載のリチウム含有電極材料。4. The transition metal element constituting the lithium transition metal composite nitride is at least one element selected from the group consisting of cobalt, copper, iron and nickel. Lithium containing electrode material.
きる元素が、ケイ素、錫及びアルミニウムよりなる群か
ら選ばれた少なくとも１種の元素である請求項１〜４の
いずれかに記載のリチウム含有電極材料。5. The lithium-containing element according to claim 1, wherein the element capable of forming an alloy with lithium is at least one element selected from the group consisting of silicon, tin and aluminum. Electrode material.
に含有されたリチウムと合金を形成することができる元
素の含有量が、前記リチウム遷移金属複合窒化物の粒子
の表面近傍から内部に向かって減少している請求項１〜
５のいずれかに記載のリチウム含有電極材料。6. The content of an element capable of forming an alloy with lithium contained in the particles of the lithium-transition metal composite nitride increases from the vicinity of the surface of the particles of the lithium-transition metal composite nitride toward the inside. Claim 1 which is decreasing
5. The lithium-containing electrode material according to any one of 5 above.
に含有された酸素の含有量が、前記リチウム遷移金属複
合窒化物の粒子の表面近傍から内部に向かって減少して
いる請求項２〜５のいずれかに記載のリチウム含有電極
材料。7. The content of oxygen contained in the particles of the lithium transition metal composite nitride decreases from the vicinity of the surface of the particles of the lithium transition metal composite nitride toward the inside. The lithium-containing electrode material according to any one of 1.
ともリチウムと合金を形成することができる元素を含む
化合物とを混合し、前記リチウム遷移金属複合窒化物の
粒子の表面に、前記少なくともリチウムと合金を形成す
ることができる元素を含む化合物を付着させた後、これ
を焼成することを特徴とするリチウム含有電極材料の製
造方法。8. A lithium-transition metal composite nitride is mixed with a compound containing an element capable of forming an alloy with at least lithium, and the surface of the particles of the lithium-transition metal composite nitride is alloyed with at least the lithium. A method for producing a lithium-containing electrode material, comprising: depositing a compound containing an element capable of forming a lithium-containing electrode material;
する遷移金属元素が、コバルト、銅、鉄及びニッケルよ
りなる群から選ばれた少なくとも１種の元素である請求
項８に記載のリチウム含有電極材料の製造方法。9. The lithium-containing electrode according to claim 8, wherein the transition metal element constituting the lithium-transition metal composite nitride is at least one element selected from the group consisting of cobalt, copper, iron and nickel. Material manufacturing method.
できる元素が、ケイ素、錫及びアルミニウムよりなる群
から選ばれた少なくとも１種の元素である請求項８又は
９に記載のリチウム含有電極材料の製造方法。10. The lithium-containing electrode material according to claim 8, wherein the element capable of forming an alloy with lithium is at least one element selected from the group consisting of silicon, tin and aluminum. Production method.
ウム含有電極材料を負極に用いたことを特徴とする電気
化学素子。11. An electrochemical device using the lithium-containing electrode material according to claim 1 as a negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001279494A JP3568499B2 (en) | 2000-09-19 | 2001-09-14 | Lithium-containing electrode material, method for producing the same, and electrochemical element using lithium-containing electrode material |
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000-283130 | 2000-09-19 | ||
| JP2000283130 | 2000-09-19 | ||
| JP2001197109 | 2001-06-28 | ||
| JP2001-197109 | 2001-06-28 | ||
| JP2001230196 | 2001-07-30 | ||
| JP2001-230196 | 2001-07-30 | ||
| JP2001279494A JP3568499B2 (en) | 2000-09-19 | 2001-09-14 | Lithium-containing electrode material, method for producing the same, and electrochemical element using lithium-containing electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003115296A true JP2003115296A (en) | 2003-04-18 |
| JP3568499B2 JP3568499B2 (en) | 2004-09-22 |
Family
ID=27481621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001279494A Expired - Fee Related JP3568499B2 (en) | 2000-09-19 | 2001-09-14 | Lithium-containing electrode material, method for producing the same, and electrochemical element using lithium-containing electrode material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3568499B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009153664A1 (en) * | 2008-06-18 | 2009-12-23 | Centre National De La Recherce Scientifique | Method for the manufacturing of sputtering targets using an inorganic polymer |
| WO2013129376A1 (en) * | 2012-02-29 | 2013-09-06 | 三洋電機株式会社 | Active material for non-aqueous electrolyte secondary cell, electrode for non-aqueous electrolyte secondary cell, non-aqueous electrolyte secondary cell, and method for producing active material for non-aqueous electrolyte secondary cell |
| JP2014112534A (en) * | 2012-11-02 | 2014-06-19 | Semiconductor Energy Lab Co Ltd | Electrode for electricity storage device and method for manufacturing the same, electricity storage device, and electrical device |
-
2001
- 2001-09-14 JP JP2001279494A patent/JP3568499B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009153664A1 (en) * | 2008-06-18 | 2009-12-23 | Centre National De La Recherce Scientifique | Method for the manufacturing of sputtering targets using an inorganic polymer |
| US20110147207A1 (en) * | 2008-06-18 | 2011-06-23 | Alain Levasseur | Method for Manufacturing of Sputtering Targets Using an Inorganic Polymer |
| US8652305B2 (en) | 2008-06-18 | 2014-02-18 | Centre National De La Recherche Scientifique | Method for manufacturing of sputtering targets using an inorganic polymer |
| WO2013129376A1 (en) * | 2012-02-29 | 2013-09-06 | 三洋電機株式会社 | Active material for non-aqueous electrolyte secondary cell, electrode for non-aqueous electrolyte secondary cell, non-aqueous electrolyte secondary cell, and method for producing active material for non-aqueous electrolyte secondary cell |
| JP2014112534A (en) * | 2012-11-02 | 2014-06-19 | Semiconductor Energy Lab Co Ltd | Electrode for electricity storage device and method for manufacturing the same, electricity storage device, and electrical device |
| US9806334B2 (en) | 2012-11-02 | 2017-10-31 | Semiconductor Energy Laboratory Co., Ltd. | Power storage device electrode, method for forming the same, power storage device, and electrical device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3568499B2 (en) | 2004-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10950363B2 (en) | Active material for negative electrodes of nonaqueous secondary batteries, and nonaqueous secondary battery | |
| CN107403910A (en) | For forming the polymerization technique of polymer ultra-thin conforma coating on electrode material | |
| JP5329858B2 (en) | Method for producing negative electrode active material for nonaqueous electrolyte secondary battery and negative electrode active material for nonaqueous electrolyte battery obtained thereby | |
| US7674554B2 (en) | Anode active material, method of preparing the same, and anode and lithium battery containing the anode active material | |
| JP4467926B2 (en) | Electrochemical element | |
| US20090239148A1 (en) | High voltage cathode compositions | |
| WO2006061948A1 (en) | Process for producing polyradical compound and battery | |
| JP2006092969A (en) | Anode active material for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery | |
| JP2003303588A (en) | Electrode material and method of manufacturing the same, and negative electrode for nonaqueous secondary battery and nonaqueous secondary battery | |
| KR20060091486A (en) | Cathode active material, method of preparing the same, and cathode and lithium battery containing the material | |
| KR20030047037A (en) | Electrode, lithium battery adopting the same, and method for manufacturing the same | |
| CN104334496A (en) | Hollow silicon-based particles, preparation method therefor, and anode active material for lithium secondary battery, containing same | |
| TWI766129B (en) | Negative electrode active material and method for producing the same | |
| KR100975875B1 (en) | Cathode active material, method of preparing the same, and cathode and lithium battery containing the material | |
| JPH1074520A (en) | Electrode for lithium ion battery using polycarbosilane | |
| WO2013125761A1 (en) | Germanium nanoparticle/carbon composite anode material using no binder for lithium-polymer battery having high capacity and high rapid charge/discharge characteristics | |
| CN113707883B (en) | Organic coating layer, electrode active material containing organic coating layer and lithium ion battery | |
| JP2004281055A (en) | Binder resin composition for battery, mix slurry, electrode and battery using resin containing carboxyl group | |
| JP3633557B2 (en) | Negative electrode active material for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery | |
| JP2012151129A (en) | Manufacturing method of negative electrode active material for nonaqueous electrolyte secondary battery, and negative electrode active material for nonaqueous electrolyte battery provided thereby | |
| US6306541B1 (en) | Electrodes for lithium ion batteries using polysilanes | |
| JP2018106830A (en) | Method for manufacturing active material for non-aqueous secondary battery negative electrode, active material for non-aqueous secondary battery negative electrode, and method for manufacturing non-aqueous secondary battery negative electrode | |
| JP2017088437A (en) | Method for producing graphite-covered silicon composite body | |
| US11063261B2 (en) | Electrode for electrochemical device, method for manufacturing the same, and electrochemical device including the same | |
| JP3568499B2 (en) | Lithium-containing electrode material, method for producing the same, and electrochemical element using lithium-containing electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040119 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20040217 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040414 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20040428 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20040518 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040615 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080625 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090625 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100625 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100625 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100625 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110625 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120625 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120625 Year of fee payment: 8 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120625 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120625 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120625 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120625 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130625 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130625 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140625 Year of fee payment: 10 |
|
| R255 | Notification that request for automated payment was rejected |
Free format text: JAPANESE INTERMEDIATE CODE: R2525 |
|
| LAPS | Cancellation because of no payment of annual fees |