JP2009535781A - Electrode active material with improved safety and electrochemical device using the same - Google Patents
Electrode active material with improved safety and electrochemical device using the same Download PDFInfo
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
本発明は、表面の一部又は全部に酸点を含むことを特徴とする電極活物質、前記電極活物質を含んだり、酸点を有する化合物で表面処理された電極、及び前記電極を備える電気化学素子を提供する。
本発明による電極活物質は、表面に形成された無機物又は有機−無機複合体により酸点が形成されるだけでなく、表面酸点強度を適切に調節できるため、電解液との副反応性の減少及び電極活物質の構造的安全性の確保により電池の性能を向上させることができる。The present invention provides an electrode active material containing acid sites on part or all of the surface, an electrode containing the electrode active material or surface-treated with a compound having acid sites, and an electric device comprising the electrode A chemical element is provided.
In the electrode active material according to the present invention, not only the acid sites are formed by the inorganic material or the organic-inorganic composite formed on the surface, but also the surface acid site strength can be appropriately adjusted. The performance of the battery can be improved by reducing and ensuring the structural safety of the electrode active material.
Description
本発明は、電極活物質の表面の酸点強度の調節により安全性が向上した電極活物質、前記電極活物質を含んだり、酸点を有する化合物が電極表面にコートされたり電極材料と混合される電極、前記電極を備えて性能の向上を図る電気化学素子、好ましくはリチウム二次電池に関する。 The present invention relates to an electrode active material whose safety is improved by adjusting the acid point strength of the surface of the electrode active material, the electrode active material, a compound having an acid point being coated on the electrode surface or mixed with the electrode material. The present invention relates to an electrode, and an electrochemical device, preferably a lithium secondary battery, which is provided with the electrode to improve performance.
リチウム二次電池の商用化の以後、電池開発における第一の目標は、高用量及び長寿の電気化学的特性に優れた正極活物質の開発である。電気化学的特性の以外に、熱露出、燃焼又は過充電などのような非正常な条件下でも、電池システムの安全性及び信頼性を確保できる安全性に優れた正極活物質の開発も切実に要求されている。 Since the commercialization of lithium secondary batteries, the primary goal in battery development is the development of positive electrode active materials with high dose and long life and excellent electrochemical properties. In addition to electrochemical characteristics, we are eager to develop positive active cathode materials with excellent safety that can ensure the safety and reliability of battery systems even under abnormal conditions such as heat exposure, combustion or overcharge. It is requested.
リチウム二次電池の正極活物質として広く用いられているＬｉＭＯ２(Ｍ＝Ｎｉ、Ｍｎ、Ｃｏ等の遷移金属)等は、充電状態又は過充電状態で電解液と反応して副産物を生成したり、電極活物質の構造崩壊などにより電池性能の減少を招く。よって、殆どの研究者は、安定した酸化物で表面処理を行って活物質の性能を向上させる作業を進行してきたが、所望の電極活物質の安全性及び性能向上を同時に図るのに困難さがある。 LiMO 2 (transition metals such as M = Ni, Mn, Co, etc.) widely used as the positive electrode active material of lithium secondary batteries reacts with the electrolyte in the charged state or overcharged state to generate by-products. In addition, the battery performance is reduced due to the structural collapse of the electrode active material. Therefore, most researchers have been working to improve the performance of the active material by surface treatment with a stable oxide, but it is difficult to improve the safety and performance of the desired electrode active material at the same time. There is.
一方、本発明者らは、電極活物質粒子の表面上に反応性が低い化合物をコートする従来の表面改質法を用いる場合、電極活物質の安全性は確保されるが、必ず電池の性能が低下することを認識した。よって、前述した従来の表面改質法の代りに、電極活物質の表面上に酸点強度が調節された化合物をコートすることで、電極活物質の構造的安全性の向上及び物質変化の防止を図ることができ、電解液との反応性を有意的に減少させて電池の諸般性能を向上できる新規な表面改質法を採択して使用しようとする。 On the other hand, when using the conventional surface modification method in which the surface of the electrode active material particles is coated with a compound having low reactivity, the safety of the electrode active material is ensured, but the performance of the battery is always ensured. Recognized that the decline. Therefore, instead of the conventional surface modification method described above, the surface of the electrode active material is coated with a compound with adjusted acid point strength, thereby improving the structural safety of the electrode active material and preventing material changes. Therefore, it is intended to adopt and use a novel surface modification method that can significantly reduce the reactivity with the electrolyte and improve various performances of the battery.
本発明の目的は、表面の一部又は全部に酸点を含むことを特徴とする電極活物質、前記電極活物質を含む電極、及び前記電極を備える電気化学素子、好ましくはリチウム二次電池を提供することにある。 An object of the present invention is to provide an electrode active material containing acid sites on part or all of the surface, an electrode including the electrode active material, and an electrochemical device including the electrode, preferably a lithium secondary battery. It is to provide.
また、本発明の目的は、酸点を有する化合物が既に製造された電極表面にコートされたり、電極材料と混合されることを特徴とする電極、及び前記電極を備える電気化学素子、好ましくはリチウム二次電池を提供することにある。 Another object of the present invention is to provide an electrode characterized in that a compound having an acid site is coated on the surface of an already produced electrode or mixed with an electrode material, and an electrochemical device comprising the electrode, preferably lithium. It is to provide a secondary battery.
さらに、本発明の目的は、(i)(ａ)プロトン(又は電子対)供与、或いは、プロトン(又は電子対)受容を行う化合物と、(ｂ)酸点を有する化合物とを反応させる段階；及び、(ii)前記(ｉ)段階の結果物を電極活物質の表面にコートし、そのコーティング層を乾燥させる段階を含むことを特徴とする、酸点強度が調節されたコーティング層を有する電極活物質の製造方法を提供することにある。 Furthermore, the object of the present invention is to react (i) (a) a compound that provides a proton (or electron pair) or accepts a proton (or electron pair) and (b) a compound having an acid point; And (ii) coating the surface of the electrode active material with the resultant product of step (i) and drying the coating layer, and an electrode having a coating layer with adjusted acid point strength The object is to provide a method for producing an active material.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明では、リチウムのインターカレーション／デインターカレーションを行ったり、或いは、挿入及び放出を行う電極活物質粒子の表面の一部又は全部に酸点を形成させ、電極活物質の表面の電気化学的物性を改質することを特徴とする。 In the present invention, acid sites are formed on a part or all of the surface of the electrode active material particles for intercalation / deintercalation of lithium, or insertion and release, and the surface of the electrode active material is electrically charged. It is characterized by modifying chemical properties.
一般に、酸点は、ゼオライト等のような固体酸性触媒に存在して、化学反応、例えば分解反応等を起こす反応活性点として知られている。これに対し、本発明では、新規な表面改質法により、活物質の表面の一部又は全部に形成される表面改質部における特定の酸点強度を示す活性点を称する。 In general, an acid site is known as a reaction active site that exists in a solid acidic catalyst such as zeolite and causes a chemical reaction such as a decomposition reaction. On the other hand, in this invention, the active point which shows the specific acid point intensity | strength in the surface modification part formed in a part or all of the surface of an active material with a novel surface modification method is called.
酸点強度は、プロトンをどれくらい容易に供与できるか、或いは、電子対をどれくらい容易に受容できるかにより決定されるものである。よって、このような酸点特性は、一般に、表面構造よりは表面を構成する原子間の電子的性質と連関性があると言える。 The acid point intensity is determined by how easily a proton can be donated or how easily an electron pair can be accepted. Therefore, it can be said that such acid point characteristics are generally related to the electronic properties between atoms constituting the surface rather than the surface structure.
このように、表面に酸点が形成された電極活物質は、正電荷を有したり、又は電気陰性度の差により部分的に正電荷を有する通常の酸性物質と類似に作用する。したがって、電池内部に存在する、プロトンを供与する酸性物質(ブレンステッド酸)と、電子対を受容する親電子性物質(ルイス酸)との反応性自体が有意的に減少して、電池の諸般性能を向上できる。これに対しては下記のように推定することができる。 Thus, the electrode active material having acid spots formed on the surface has a positive charge, or acts in a similar manner to a normal acidic substance having a positive charge partially due to a difference in electronegativity. Therefore, the reactivity itself between the acidic substance (Bronsted acid) that donates protons and the electrophilic substance (Lewis acid) that accepts an electron pair existing in the battery is significantly reduced, and various kinds of battery Performance can be improved. This can be estimated as follows.
１）従来の電極活物質の表面は、リチウム副産物又は親水性表面処理により弱塩基性を示す。よって、実際に酸点に対する認識が殆どなかった。 1) The surface of the conventional electrode active material is weakly basic due to lithium by-product or hydrophilic surface treatment. Therefore, there was practically no recognition of acid sites.
このような従来の電極活物質、好ましくは正極活物質を用いる電池は、電極又は電解液内に存在する水分及びリチウム塩(例えば、ＬｉＰＦ６)と反応して強酸であるＨＦを形成し、形成されたＨＦは、弱塩基性を示す電極活物質と自発的に反応して電極活物質成分を溶出させて退化させる。また、正極表面にＬｉＦを形成して、電極内の電気抵抗の増加及びガスの発生により電池の寿命を低下させる。特に、ＨＦによる電極の溶出速度は高温下で上昇するため、ＨＦは高温での電池サイクル寿命及び保存性に大きな問題点を有することになる。 A battery using such a conventional electrode active material, preferably a positive electrode active material, forms HF, which is a strong acid, by reacting with water and lithium salt (eg, LiPF 6 ) present in the electrode or the electrolyte solution. The generated HF reacts spontaneously with the electrode active material exhibiting weak basicity to elute the electrode active material component and degenerate. In addition, LiF is formed on the surface of the positive electrode to reduce the battery life by increasing the electrical resistance in the electrode and generating gas. In particular, since the elution rate of the electrode by HF increases at a high temperature, HF has a significant problem in battery cycle life and storage stability at a high temperature.
これに対し、本発明の電極活物質は、表面上に酸点を有することで、実質的に酸性物質として作用することになる。よって、強酸の一種であるＨＸ(Ｘ＝ハロゲン元素)との反応性自体が低下するため、前述の問題点を根本的に解消でき、電極活物質の構造的安全性の確保及び電池性能の向上を図ることができる。 On the other hand, the electrode active material of the present invention has an acid point on the surface, and thus acts substantially as an acidic substance. Therefore, since the reactivity with HX (X = halogen element) which is a kind of strong acid is lowered, the above-mentioned problems can be fundamentally solved, the structural safety of the electrode active material is ensured, and the battery performance is improved. Can be achieved.
２）従来の電池用電解液としてはカーボネート系非水溶媒を用いる。このようなカーボネート系電解液溶媒は、下記反応式１に表されるように、双極子モーメント上で相対的に正電荷(+)を有する炭素と、負電荷(-)を有する酸素とが存在するようになる。このとき、電極活物質の表面上に非共有電子対を供与できるルイス塩基が存在する場合、ルイス塩基が正電荷を表す炭素を攻撃して、電解液の親電子性分解反応がより活性化される。
2) A carbonate-based nonaqueous solvent is used as a conventional battery electrolyte. Such a carbonate-based electrolyte solvent includes carbon having a relatively positive charge (+) and oxygen having a negative charge (-) on the dipole moment as represented by the following
これに対し、酸点を有する本発明の電極活物質は、非共有電子対を供与するよりは非共有電子対を受容するルイス酸である。これにより、前述した電解液との副反応自体が有意的に減少して、電池性能の低下を最小化できる。
本発明により電極活物質の表面の一部又は全部に形成される酸点は、公知された通常の酸点を意味する。一例として、プロトンを供与できるブレンステッド酸点又は非共有電子対を受容できるルイス酸点であり得る。 The acid point formed on part or all of the surface of the electrode active material according to the present invention means a known ordinary acid point. As an example, it can be a Bronsted acid point that can donate a proton or a Lewis acid point that can accept an unshared electron pair.
酸点強度は、Ｈ０(Hammett indicator：ハメット インジケーター)で表され、公知された通常の範囲、例えば−２０〜２０内で調節可能である。酸点強度の調節により、電極活物質の退化防止及び電解液との副反応発生の抑制を図るために、Ｈ０が−１０〜１０であるのが好ましい。 The acid point intensity is represented by H 0 (Hammett indicator) and can be adjusted within a known normal range, for example, −20 to 20. It is preferable that H 0 is −10 to 10 in order to prevent degeneration of the electrode active material and suppression of side reaction with the electrolytic solution by adjusting the acid point strength.
電極活物質の表面上に酸点を形成する方法は、特別に制限されず、一例として下記の２種類の実施形態がある。 The method for forming acid sites on the surface of the electrode active material is not particularly limited, and there are the following two embodiments as an example.
１）第一の実施形態は、電極活物質を無機物で表面処理するものである。 1) In the first embodiment, the electrode active material is surface-treated with an inorganic substance.
このように、電極活物質の表面上に表面処理された無機物は、無機物の表面の一部又は全部に存在するプロトン供与体作用基、及び／又は異種金属原子の電気陰性度の差により、電極活物質の表面電子の分布を変化させて表面の電気化学的物性が変化するものであり、これにより電極活物質の表面上に酸点が形成されるものである。 As described above, the inorganic material surface-treated on the surface of the electrode active material has an electrode due to a difference in electronegativity of proton donor functional groups and / or different metal atoms present on a part or all of the surface of the inorganic material. By changing the distribution of surface electrons of the active material, the electrochemical properties of the surface are changed, whereby acid spots are formed on the surface of the electrode active material.
無機物は、公知された通常の無機物、例えばセラミック、金属又はこれらの混合物であって、電極活物質の表面に存在するとき、表面の電気化学的物性を変化させることができるものであれば特別に制限がない。特に、原子サイズが小さくて電極活物質の表面上に容易にドープされることで、Ｌｉのインターカレーションに従う電極の構造的安全性が図られる１３族元素、１４族元素、１５族元素、例えばＢ、Ａｌ、Ｇａ、Ｉｎ、Ｔｉ又はこれらの組合を含む化合物が好ましい。 The inorganic substance is a known normal inorganic substance such as ceramic, metal, or a mixture thereof, and specially provided that it can change the electrochemical properties of the surface when it is present on the surface of the electrode active material. There is no limit. In particular, a group 13 element, a group 14 element, a group 15 element, for example, having a small atomic size and being easily doped on the surface of the electrode active material, can achieve structural safety of the electrode according to Li intercalation. A compound containing B, Al, Ga, In, Ti or a combination thereof is preferred.
使用可能な無機物の非制限的な例としては、(ａ)１３族元素含有化合物；(ｂ)(ｉ)１３族元素；及び(ｉｉ)アルカリ土金属、アルカリ金属、１４族元素、１５族元素、遷移金属、ランタノイド金属及びアクチナイド金属からなる群より選ばれた１種以上の元素を含有する化合物などがある。一例として、無機物は、Ｍ１−ＸＳｉＸＯ２(Ｍ＝１３族及び遷移金属からなる群より選ばれた１種以上の元素；０≦ｘ＜１)であり得る。 Non-limiting examples of usable inorganic materials include: (a) Group 13 element-containing compounds; (b) (i) Group 13 elements; and (ii) Alkaline earth metals, alkali metals, Group 14 elements, Group 15 elements And compounds containing one or more elements selected from the group consisting of transition metals, lanthanoid metals and actinide metals. As an example, the inorganic substance may be M 1-X Si X O 2 (one or more elements selected from the group consisting of M = 13 groups and transition metals; 0 ≦ x <1).
酸点を有する無機物は、電極活物質の表面改質の後、熱処理により形成され得る。このとき、熱処理温度は、酸点を形成する温度以上であれば特別に制限がない。表面にヒドロキシル基が相変らず存在する場合、強いルイス酸点を形成できないため、可能であればヒドロキシル基を除去できる４００℃以上が好ましい。 The inorganic substance having an acid point can be formed by heat treatment after the surface modification of the electrode active material. At this time, the heat treatment temperature is not particularly limited as long as it is higher than the temperature at which acid sites are formed. When a hydroxyl group is present on the surface as it is, a strong Lewis acid point cannot be formed. Therefore, if possible, the temperature is preferably 400 ° C. or higher so that the hydroxyl group can be removed.
前述した無機物の粒径及び含量は特別に制限されず、公知された通常の範囲内で適切に調節可能である。 The particle size and content of the inorganic substance described above are not particularly limited, and can be appropriately adjusted within a known normal range.
２）第二の実施形態は、電極活物質の表面を、有機(半)金属化合物及び無機物の複合体で表面処理するものである。 2) In the second embodiment, the surface of the electrode active material is surface-treated with a composite of an organic (semi) metal compound and an inorganic substance.
このような電極活物質の表面上に形成される有機(半)金属化合物及び無機物の複合体は、互いに結合された有機(半)金属化合物と無機物との間の電気陰性度の差及び／又は有機金属化合物に結合された有機物質により、表面の電気化学的物性が変化して酸点を形成し得る。 The organic (semi) metal compound and inorganic composite formed on the surface of the electrode active material may have a difference in electronegativity between the organic (semi) metal compound and the inorganic combined with each other and / or The organic substance bonded to the organometallic compound can change the electrochemical properties of the surface to form acid spots.
このとき、複合体のうち、有機(半)金属化合物及び無機物は、互いに化学結合により連結しており、このような化学結合の形態及び種類は特別に制限されない。例えば、共有結合、配位結合であり得る。 At this time, in the composite, the organic (semi) metal compound and the inorganic substance are connected to each other through a chemical bond, and the form and type of such a chemical bond are not particularly limited. For example, it may be a covalent bond or a coordinate bond.
このように、電極活物質又は電極の表面改質剤として有機(半)金属化合物及び無機物の複合体を並用する場合、有機−無機複合体に含まれた有機物成分により無機物成分、例えば無機アルコキシド化合物の加水分解速度を減少させることができる。従って、より均一な表面を生成できると共に、生成された表面を持続的に維持できるため、充放電の進行による電極活物質の構造的安全性の低下及び構造崩壊、これによる電池性能の低下を最小化できる。合せて、有機−無機複合体に含まれた無機成分により、表面改質層の導入に従う電極活物質の電気伝導性の低下を効率よく向上できる。 As described above, when an organic (semi) metal compound and an inorganic composite are commonly used as an electrode active material or an electrode surface modifier, an inorganic component such as an inorganic alkoxide compound is added depending on the organic component contained in the organic-inorganic composite. The hydrolysis rate of can be reduced. Therefore, since a more uniform surface can be generated and the generated surface can be maintained continuously, the structural safety and structural collapse of the electrode active material due to the progress of charging and discharging are minimized, and the deterioration of the battery performance due to this is minimized. Can be In addition, the decrease in the electrical conductivity of the electrode active material according to the introduction of the surface modification layer can be efficiently improved by the inorganic component contained in the organic-inorganic composite.
また、電極活物質の表面に導入された有機−無機複合体は、空気中の水分又は二酸化炭素と反応してＬｉ−副産物を生成し、これにより副反応を発生させる経時変化を防止できる。したがって外部要人による電極活物質の物質変化防止をはかることができる。特に、水分により変化が激しく発生するニッケル系正極活物質などがより効果的である。 In addition, the organic-inorganic composite introduced on the surface of the electrode active material reacts with moisture or carbon dioxide in the air to generate a Li-byproduct, thereby preventing a change over time causing a side reaction. Therefore, it is possible to prevent the material change of the electrode active material by an external person. In particular, a nickel-based positive electrode active material that changes drastically due to moisture is more effective.
さらに、従来の表面改質されない電極活物質からなる電池での正極及び電解液間の副反応性接触面を減少させることで、電池の安全性を向上させることができる。 Furthermore, the safety of the battery can be improved by reducing the side-reactive contact surface between the positive electrode and the electrolyte in a battery made of an electrode active material that has not been surface-modified.
前述したように、電極活物質の粒子の表面の一部又は全部に酸点を形成できる有機−無機複合体成分の一つは、公知された通常の有機(半)金属化合物であれば特別に制限がない。酸点強度の調節効果及び経時変化の防止効果を高めるために、ブレンステッド酸点を増加できる電子供与基を含むことが好ましい。電子供与基は、構造式、置換基又は炭素数の範囲などに特別に制限がなく、例えば水素又は炭化水素などがある。 As described above, one of the organic-inorganic composite components capable of forming acid sites on part or all of the surface of the electrode active material particles is specially known as long as it is a known ordinary organic (semi) metal compound. There is no limit. In order to enhance the effect of adjusting the acid point strength and the effect of preventing change over time, it is preferable to include an electron donating group capable of increasing the Bronsted acid point. The electron-donating group is not particularly limited in the structural formula, substituent, or carbon number range, and includes, for example, hydrogen or hydrocarbon.
有機(半)金属化合物は、(ａ)１４族元素含有化合物；又は(ｂ)(ｉ)１４族元素；及び(ｉｉ)アルカリ土金属、アルカリ金属、１３族元素、１５族元素、遷移金属、ランタノイド金属及びアクチナイド金属からなる群より選ばれた１種以上の元素を含有する化合物などがあるが、これに制限されるものではない。有機(半)金属化合物としてはシリコン含有化合物が好ましいが、その具体例としては、シラン、シリル化剤、シランカップリング剤、水素化珪素、モノシラン、シランポリマー又はこれらの混合物などがある。 The organic (semi) metal compound includes (a) a group 14 element-containing compound; or (b) (i) a group 14 element; and (ii) an alkaline earth metal, an alkali metal, a group 13 element, a group 15 element, a transition metal, Although there is a compound containing one or more elements selected from the group consisting of lanthanoid metals and actinide metals, it is not limited thereto. As the organic (semi) metal compound, a silicon-containing compound is preferable, and specific examples thereof include silane, silylating agent, silane coupling agent, silicon hydride, monosilane, silane polymer, or a mixture thereof.
有機(半)金属化合物は、下記化学式１〜化学式７で表されるが、これに制限されるものではない。
［化１］
ＳｉＨ４
［化２］
Ｓｉ(ＯＲ)４−ｘＲｘ(０.１≦ｘ≦３)
［化３］
Ｓｉ(ＯＲ)４−(ｘ＋ｙ)ＲｘＺｙ(０.１≦ｘ＋ｙ≦３.９)
［化４］
Ｓｉ(ＯＲ)４−ｘＲｘ Ｓｉ(０.１≦ｘ≦３)
［化５］
Ｓｉ(ＯＲ)４−(ｘ＋ｙ)ＲｘＺｙＳｉ(０.１≦ｘ＋ｙ≦３.９)
［化６］
ＲｘＭ(ＯＲ)４−ｘ(１≦ｘ≦３)
［化７］
ＲｘＭＺｙ(ＯＲ)４−(ｘ＋ｙ)(０.１≦ｘ＋ｙ≦３.９)
上記式中、
Ｚは、ハロゲン元素であり、
Ｍは、アルカリ土金属、アルカリ金属、遷移金属、ランタノイド金属及びアクチナイド金属からなる群より選ばれた１種以上の元素であり、
Ｒは、ハロゲン元素に置換されたり、又は非置換されたＣ１〜Ｃ２０のアルキル基、アルケニル基、アルキニル基、ビニル基、アミノ基及びメルカプト基からなる群より選ばれた置換基である。
The organic (semi) metal compound is represented by the following
[Chemical 1]
SiH 4
[Chemical 2]
Si (OR) 4-x R x (0.1 ≦ x ≦ 3)
[Chemical formula 3]
Si (OR) 4− (x + y) R x Z y (0.1 ≦ x + y ≦ 3.9)
[Chemical formula 4]
Si (OR) 4-x R x Si (0.1 ≦ x ≦ 3)
[Chemical formula 5]
Si (OR) 4− (x + y) R x Z y Si (0.1 ≦ x + y ≦ 3.9)
[Chemical 6]
R x M (OR) 4-x (1 ≦ x ≦ 3)
[Chemical 7]
R x MZ y (OR) 4- (x + y) (0.1 ≦ x + y ≦ 3.9)
In the above formula,
Z is a halogen element,
M is one or more elements selected from the group consisting of alkaline earth metals, alkali metals, transition metals, lanthanoid metals and actinide metals,
R is a substituent selected from the group consisting of a C1-C20 alkyl group, an alkenyl group, an alkynyl group, a vinyl group, an amino group, and a mercapto group, which are substituted or unsubstituted by a halogen element.
本発明の電極活物質粒子の表面の一部又は全部に酸点を形成できる有機−無機複合体成分のもう一つは、前述した有機(半)金属化合物と化学結合数の差が発生して酸点を形成できる通常の無機物であれば、特別に制限がない。一例として前述した無機物成分が用いられる。このとき、有機−無機複合体の導入による電極活物質の伝導性の低下を防止するために、可能であれば伝導性を有する金属、金属含有酸化物、金属含有水酸化物、又はこれらの混合形態などを用いることが好ましい。 Another of the organic-inorganic composite components that can form acid sites on part or all of the surface of the electrode active material particles of the present invention is the difference in the number of chemical bonds with the organic (semi) metal compound described above. If it is a normal inorganic substance which can form an acid point, there will be no restriction | limiting in particular. As an example, the inorganic component described above is used. At this time, in order to prevent a decrease in conductivity of the electrode active material due to the introduction of the organic-inorganic composite, if possible, a conductive metal, a metal-containing oxide, a metal-containing hydroxide, or a mixture thereof It is preferable to use a form or the like.
前述した有機(半)金属化合物及び無機物からなる有機−無機複合体は、有機物及び無機物の単純混合形態でなく、これらが化学的に互いに結合された形態を示す。一例として、(ａ)金属−有機(半)金属化合物が結合された形態、金属酸化物−有機(半)金属化合物が結合された形態(Ａｌ２Ｏ３−Ｓｉ−ＣＨ３)、或いは金属水酸化物−有機(半)金属化合物が結合された形態(ＡｌＯＯＨ−Ｓｉ−ＣＨ３)を示す。 The organic-inorganic composite composed of an organic (semi) metal compound and an inorganic material described above is not a simple mixed form of an organic substance and an inorganic substance but a form in which they are chemically bonded to each other. As an example, (a) a form in which a metal-organic (semi) metal compound is bonded, a form in which a metal oxide-organic (semi) metal compound is bonded (Al 2 O 3 —Si—CH 3 ), or metal water oxide - an organic form (semi) metal compound is bonded (AlOOH-Si-CH 3) .
酸点を形成する化合物のうち、有機(半)金属化合物：無機物の成分比率は、特別に制限ないが、可能であれば０ｗｔ％〜９５ｗｔ％：５ｗｔ％〜１００ｗｔ％の範囲が好ましい。 Among the compounds that form acid sites, the ratio of the organic (semi) metal compound: inorganic component is not particularly limited, but is preferably in the range of 0 wt% to 95 wt%: 5 wt% to 100 wt% if possible.
また、本発明の有機−無機複合体は、前述した成分の以外に、公知された通常の成分、例えば添加剤成分などをさらに含むことができる。 Moreover, the organic-inorganic composite of the present invention can further contain known ordinary components such as additive components in addition to the components described above.
本発明による電極活物質は、電極活物質の表面の一部又は全部を酸点を有する化合物で表面処理することにより製造可能である。 The electrode active material according to the present invention can be produced by surface-treating part or all of the surface of the electrode active material with a compound having an acid site.
その好ましい実施形態によれば、(ａ)無機物含有化合物又は無機物含有化合物と有機(半)金属化合物を混合したり、或いは溶媒に分散させる段階；及び、(ｂ)前記混合物又は分散液に電極活物質を添加及び撹はんした後、乾燥する段階を含むことができる。 According to the preferred embodiment, (a) a step of mixing an inorganic substance-containing compound or an inorganic substance-containing compound and an organic (semi) metal compound, or dispersing in a solvent; and (b) electrode activity in the mixture or dispersion. A step of drying after adding and stirring the substance may be included.
前記無機物含有化合物としては、前述した元素を１種以上含む通常の水溶性又は非水溶性化合物が用いられる。例えば、前述した無機物を含むアルコキシド、硝酸、アセテートなどがある。 As said inorganic substance containing compound, the normal water-soluble or water-insoluble compound containing 1 or more types of the element mentioned above is used. For example, there are alkoxides, nitric acid, acetate, etc. containing the inorganic substances described above.
溶媒としては、公知された通常の溶媒が用いられるが、その非制限的な例としては、水、アルコールなどの有機溶媒又はこれらの混合物などがある。 As the solvent, a known ordinary solvent is used, and non-limiting examples include water, organic solvents such as alcohol, and mixtures thereof.
前述した混合物又は分散媒に添加、混合及び撹はんしてコートされる電極活物質は、公知された通常の正極活物質、負極活物質を制限なく使用することができる。 As the electrode active material to be added, mixed and stirred to the mixture or dispersion medium described above, known normal positive electrode active materials and negative electrode active materials can be used without limitation.
このとき、電極活物質の表面を無機物と有機(半)金属化合物との混合溶液でコートする方法は、公知された通常の方法、例えば、溶媒蒸発法、共沈法、沈殿法、ゾルゲル(sol-gel)法、吸着後フィルター法、スパッタ(sputtering)法、ＣＶＤなどが用いられる。中でもスプレーコート法が好ましい。 At this time, a method of coating the surface of the electrode active material with a mixed solution of an inorganic substance and an organic (semi) metal compound is a known ordinary method, for example, a solvent evaporation method, a coprecipitation method, a precipitation method, a sol-gel (sol -gel) method, post-adsorption filter method, sputtering method, CVD, etc. are used. Of these, the spray coating method is preferred.
無機物含有化合物又は無機物と有機(半)金属化合物との混合溶液(又は分散液)を電極活物質に添加するとき、電極活物質１００重量部当り０.０５〜２０重量部の範囲で添加するのが好ましい。しかしながら、これに限定されるものではない。前記混合溶液が多過ぎる場合、活物質の表面に多量の表面処理層が存在して電極活物質へのリチウム移動及び 伝達が円滑ではなくて、電気化学的特性が減少し得る。また、前記混合溶液が少な過ぎる場合、所望の酸点効果を発揮し難い。以後、コートされた電極活物質は、公知された通常の方法により乾燥し得る。 When an inorganic substance-containing compound or a mixed solution (or dispersion) of an inorganic substance and an organic (semi) metal compound is added to the electrode active material, it is added in the range of 0.05 to 20 parts by weight per 100 parts by weight of the electrode active material. Is preferred. However, the present invention is not limited to this. When the amount of the mixed solution is too large, a large amount of a surface treatment layer is present on the surface of the active material, so that lithium transfer and transmission to the electrode active material is not smooth, and electrochemical characteristics may be reduced. Moreover, when there is too little said mixed solution, it is difficult to exhibit a desired acid point effect. Thereafter, the coated electrode active material can be dried by a known ordinary method.
必要に応じて、乾燥された電極活物質を熱処理する段階を追加できる。このとき、熱処理温度は１００℃以上であれば、特別に制限がなく、好ましくは１００〜６００℃の範囲である。また、熱処理は空気中又は非活性条件下で実施しても良い。 If necessary, a step of heat treating the dried electrode active material can be added. At this time, if heat processing temperature is 100 degreeC or more, there will be no restriction | limiting in particular, Preferably it is the range of 100-600 degreeC. The heat treatment may be performed in air or under inactive conditions.
従来には、高温焼成時、有機物が熱的に不安定であり、有機物が一部消耗されるため、所望の効果を発揮し難い。これにより焼成温度に制約が発生することになる。これに対し、本発明では、有機物の熱的不安定が無機物成分により補償されて熱的安全性を示すことができる。また、通常の乾燥段階又は低温焼成により製造可能であるため、製造方法の単純化に従う経済性の向上及び量産性を図ることができる。 Conventionally, during high-temperature firing, the organic matter is thermally unstable, and a portion of the organic matter is consumed, so that it is difficult to exert a desired effect. This places restrictions on the firing temperature. On the other hand, in the present invention, the thermal instability of the organic substance can be compensated for by the inorganic component, thereby showing thermal safety. Moreover, since it can manufacture by a normal drying step or low temperature baking, the improvement of economical efficiency and mass productivity which follow simplification of a manufacturing method can be aimed at.
このように製造された電極活物質は、表面上に無機物又は有機−無機複合体層が形成されるが、形成された無機物又は有機−無機複合体は、前述したように酸点を形成することになる。 In the electrode active material thus manufactured, an inorganic or organic-inorganic composite layer is formed on the surface, but the formed inorganic or organic-inorganic composite forms acid spots as described above. become.
本発明では、無機物又は有機−無機複合体で表面改質された電極活物質の表面物性が酸点を有することを、本願の実験例を通して確認できた(図９参照)。特に、有機−無機複合体は、有機物及び無機物が互いに結合された形態を示すだけでなく(図７参照)、複合体内の有機物に存在する電子を供与する作用基により無機物のブレンステッド酸点が相対的に増加することで、一層酸点強度が増加したことを確認できた(図９参照)。 In the present invention, it was confirmed through the experimental example of the present application that the surface properties of the electrode active material surface-modified with an inorganic substance or an organic-inorganic composite have acid sites (see FIG. 9). In particular, the organic-inorganic composite not only shows a form in which the organic substance and the inorganic substance are bonded to each other (see FIG. 7), but also has a Bronsted acid point of the inorganic substance due to the functional group that donates electrons present in the organic substance in the composite. It was confirmed that the acid point strength was further increased by the relative increase (see FIG. 9).
本発明は、前記のような電極活物質を含む電極を提供する。このとき、前記電極は、ＨＦや水分による変化が激しい正極である場合が好ましい。 The present invention provides an electrode including the electrode active material as described above. In this case, it is preferable that the electrode is a positive electrode that is greatly changed by HF or moisture.
これと同時に、本発明は、酸点を有する化合物が電極の表面にコートされたり、或いは電極材料と混合される電極を提供する。 At the same time, the present invention provides an electrode in which a compound having an acid site is coated on the surface of the electrode or mixed with an electrode material.
本発明により酸点を有する化合物を電極の構成成分として含む電極を製造する方法は、特別に制限されず、通常の方法により製造可能である。その好ましい実施例によれば、無機物含有化合物又は無機物含有化合物と有機(半)金属化合物とを混合したり溶媒に分散させて製造された混合物又は分散液を、電極活物質と混合して電極スラリーを製造した後、製造されたスラリーを集電体に塗布して電極を製造してから、乾燥することで完了できる。 The method for producing an electrode containing a compound having an acid point as a constituent component of the electrode according to the present invention is not particularly limited, and can be produced by a usual method. According to the preferred embodiment, an inorganic substance-containing compound or a mixture or dispersion prepared by mixing an inorganic substance-containing compound and an organic (semi) metal compound or dispersing it in a solvent is mixed with an electrode active material to form an electrode slurry. Can be completed by applying the produced slurry to a current collector to produce an electrode and then drying.
このとき、前記段階(ｂ)のうち、混合過程の例としては、前記混合物又は分散液と電極活物質を混合して電極スラリーを製造した後、製造されたスラリーを集電体に塗布するものである。 At this time, in the step (b), as an example of a mixing process, an electrode slurry is manufactured by mixing the mixture or dispersion and an electrode active material, and then the manufactured slurry is applied to a current collector. It is.
また、本発明により有機−無機複合体を電極のコーティング成分として使用して電極を製造する方法も、公知された通常の方法により製造可能である。その一実施例によれば、無機物含有化合物又は無機物含有化合物と有機(半)金属化合物とを混合したり溶媒に分散させた後、これを既に製造された電極表面にコート及び乾燥すればよい。このとき、既に製造された電極は、公知された通常の方法により製造可能である。 In addition, a method for producing an electrode using an organic-inorganic composite as an electrode coating component according to the present invention can also be produced by a known ordinary method. According to one embodiment, the inorganic substance-containing compound or the inorganic substance-containing compound and the organic (semi) metal compound may be mixed or dispersed in a solvent, and then coated and dried on the surface of the electrode already produced. At this time, the already manufactured electrode can be manufactured by a known ordinary method.
また、本発明は、正極、負極、分離膜及び電解液を含む電気化学素子において、前記正極、負極又は両電極が前述した電極活物質を含んだり電極であることを特徴とする電気化学素子を提供する。 Further, the present invention provides an electrochemical element comprising a positive electrode, a negative electrode, a separation membrane, and an electrolyte solution, wherein the positive electrode, the negative electrode, or both electrodes include the electrode active material described above or are electrodes. provide.
電気化学素子は、電気化学反応を行う全ての素子を含み、具体例としては、全ての種類の一次・二次電池、燃料電池、太陽電池又はキャパシターなどがある。特に、二次電池の中、リチウム金属二次電池、リチウムイオン二次電池、リチウムポリマー二次電池又はリチウムイオンポリマー二次電池などを含むリチウム二次電池が好ましい。 The electrochemical element includes all elements that perform an electrochemical reaction, and specific examples include all types of primary and secondary batteries, fuel cells, solar cells, and capacitors. In particular, among secondary batteries, lithium secondary batteries including lithium metal secondary batteries, lithium ion secondary batteries, lithium polymer secondary batteries, or lithium ion polymer secondary batteries are preferable.
本発明の電気化学素子は、公知された通常の方法により、正極及び負極間に多孔性の分離膜を入れ、前記電解液を投入して製造できる。 The electrochemical device of the present invention can be produced by inserting a porous separation membrane between a positive electrode and a negative electrode and introducing the electrolytic solution by a known ordinary method.
前記電極と共に適用される電解液及び分離膜は、特別に制限されず、従来の電気化学素子に用いられる通常のものを使用することができる。 The electrolyte solution and the separation membrane applied together with the electrode are not particularly limited, and usual ones used for conventional electrochemical devices can be used.
本発明で提示された方法により製作された電気化学素子、好ましくはリチウム二次電池の外形は、特別に制限がないが、缶からなる円筒形、コイン形、角形又はパウチ形が可能である。 The outer shape of the electrochemical device, preferably a lithium secondary battery, manufactured by the method presented in the present invention is not particularly limited, but can be cylindrical, coin-shaped, rectangular, or pouch-shaped.
さらに、本発明は、表面の酸点強度が調節された電極活物質の製造方法を提供する。このような製造方法の一実施例によれば、(ａ)酸点を有する化合物；及び、(ｂ)プロトン(又は電子対)供与、或いは、プロトン(又は電子対)受容を行う化合物を反応させた後、電極活物質の表面の一部又は全部に表面処理することによりなされるが、これに制限されるものではない。 Furthermore, this invention provides the manufacturing method of the electrode active material by which the acid point intensity | strength of the surface was adjusted. According to one embodiment of such a production method, (a) a compound having an acid point; and (b) a compound that provides a proton (or electron pair) or accepts a proton (or electron pair) is reacted. Thereafter, a part or all of the surface of the electrode active material is subjected to a surface treatment, but is not limited thereto.
プロトン(又は電子対)供与、或いは、プロトン(又は電子対)受容を行う化合物は、従来の化合物の酸点強度を特定範囲に調節できる影響因子として使用するものである。このとき、化合物の含量、化合物内に存在する作用基、成分比の調節により、酸点強度を所望の範囲に調節できる。 A compound that provides a proton (or electron pair) or accepts a proton (or electron pair) is used as an influencing factor that can adjust the acid point intensity of a conventional compound to a specific range. At this time, the acid point strength can be adjusted to a desired range by adjusting the content of the compound, the functional group present in the compound, and the component ratio.
このとき、プロトン(又は電子対)供与、或いは、プロトン(又は電子対)受容を行う化合物は、前述した作用が行われるものであれば、特別に制限がない。調節された活物質の表面の酸点強度は、Ｈ０が−１０〜１０範囲であるのが好ましいが、これに制限されるものではない。その他、同一の作用によりＨ０を−２０〜２０範囲に調節することも、本発明の範囲に属している。 At this time, the compound that provides proton (or electron pair) or accepts proton (or electron pair) is not particularly limited as long as the above-described action is performed. The acid point strength on the surface of the adjusted active material is preferably H 0 in the range of −10 to 10 but is not limited thereto. In addition, it is also within the scope of the present invention to adjust H 0 to the -20 to 20 range by the same action.
本発明によれば、電極活物質の表面の酸点強度を調節することで、電解液との副反応性の減少及び電極活物質の構造的安全性の確保により、電池の性能を向上できる。 According to the present invention, by adjusting the acid point strength of the surface of the electrode active material, the performance of the battery can be improved by reducing the side reactivity with the electrolytic solution and ensuring the structural safety of the electrode active material.
以下、本発明の理解を容易にするために好適な実施例を提示するが、下記の実施例は、本発明を例示するものに過ぎず、本発明を限定するものではない。 Hereinafter, preferred examples will be presented in order to facilitate understanding of the present invention. However, the following examples are merely illustrative of the present invention and do not limit the present invention.
実施例１
１−１ 正極活物質の製造
アルミニウムイソプロポキシド(Al-isopropoxide)及びＣＨ３Ｓｉ(ＯＣＨ３)３を、それぞれ活物質に対し０.８ｍｏｌ％になるように、２００ｍｌの無水アルコールに入れ、１８時間撹はんした。以後、ＬｉＣｏ２ １００ｇを投入して１時間２０分間再撹はんした後、減圧フィルターを用いてフィルターリングした。得られた活物質を１３０℃の真空オーブンで乾燥した後、表面処理された活物質を得た。
Example 1
1-1 Production of Positive Electrode Active Material Aluminum isopropoxide (Al-isopropoxide) and CH 3 Si (OCH 3 ) 3 were each placed in 200 ml of anhydrous alcohol so as to be 0.8 mol% with respect to the active material. Stir for hours. Thereafter, 100 g of LiCo 2 was added and the mixture was re-stirred for 1 hour and 20 minutes, and then filtered using a vacuum filter. The obtained active material was dried in a vacuum oven at 130 ° C. to obtain a surface-treated active material.
１−２ 正極の製造
前記製造された正極活物質：導電剤：バインダーの比率が９５：２.５：２.５になるように、ＮＭＰ溶媒に入れてスラリーを生成した後、製造された正極スラリーを２０μｍのアルミ箔上に塗布した後、１３０℃のオーブンで乾燥して正極を得た。
1-2 Production of Positive Electrode A positive electrode produced after a slurry was produced in an NMP solvent so that the ratio of the produced positive electrode active material: conductive agent: binder was 95: 2.5: 2.5. The slurry was applied on a 20 μm aluminum foil and then dried in an oven at 130 ° C. to obtain a positive electrode.
１−３ リチウム二次半電池の製造
得られた電極の気孔率が２５％になるように圧延した後、コイン状に穿孔してコイン状電池を製造した。このとき、対向電極としてはＬｉ−金属を用い、電解液としてはＥＣ：ＥＭＣが１：２で混合された溶媒にＬｉＰＦ６が１Ｍ溶解された電解液を用いた。
1-3 Production of Lithium Secondary Half Battery After rolling the obtained electrode to have a porosity of 25%, a coin-like battery was produced by punching into a coin shape. At this time, Li-metal was used as the counter electrode, and an electrolytic solution in which 1M LiPF 6 was dissolved in a 1: 2 mixture of EC: EMC was used as the electrolytic solution.
実施例２
乾燥した活物質を３００℃でさらに熱処理した以外は、前記実施例１と同様な方法により、正極活物質、前記正極活物質を用いた正極及び前記正極を備えるコイン状電池を製造した。
Example 2
A coin-shaped battery including a positive electrode active material, a positive electrode using the positive electrode active material, and the positive electrode was manufactured in the same manner as in Example 1 except that the dried active material was further heat-treated at 300 ° C.
実施例３
アルミニウムイソプロポキシドを単独で使用して得られた正極活物質を４００℃で熱処理した以外は、前記実施例１と同様な方法により、正極活物質、前記正極活物質を用いた正極及び前記正極を備えるコイン状電池を製造した。
Example 3
A positive electrode active material, a positive electrode using the positive electrode active material, and the positive electrode were obtained in the same manner as in Example 1 except that the positive electrode active material obtained by using aluminum isopropoxide alone was heat-treated at 400 ° C. A coin-shaped battery comprising
比較例１
表面処理されない通常のＬｉＣｏＯ２を正極活物質として用いた以外は、前記実施例１と同様な方法により、正極及び前記正極を備えるコイン状電池を製造した。
Comparative Example 1
A coin-shaped battery including a positive electrode and the positive electrode was manufactured in the same manner as in Example 1 except that normal LiCoO 2 that was not surface-treated was used as the positive electrode active material.
比較例２
ＣＨ３Ｓｉ(ＯＣＨ３)３を使用することなく、アルミニウムイソプロポキシドを単独で使用した以外は、前記実施例１と同様な方法により、正極活物質、前記正極活物質を用いた正極及び前記正極を備えるコイン状電池を製造した。
Comparative Example 2
A positive electrode active material, a positive electrode using the positive electrode active material, and the positive electrode were prepared in the same manner as in Example 1 except that aluminum isopropoxide was used alone without using CH 3 Si (OCH 3 ) 3. A coin-shaped battery including a positive electrode was manufactured.
比較例３
アルミニウムイソプロポキシドをを使用することなく、ＣＨ３Ｓｉ(ＯＣＨ３)３を単独で使用した以外は、前記実施例１と同様な方法により、正極活物質、前記正極活物質を用いた正極及び前記正極を備えるコイン状電池を製造した。
Comparative Example 3
Except for using CH 3 Si (OCH 3 ) 3 alone without using aluminum isopropoxide, the positive electrode active material, the positive electrode using the positive electrode active material, and A coin-shaped battery including the positive electrode was manufactured.
実験例１ 電極活物質の表面物性の分析
本発明により表面改質された電極活物質の物性を評価するために、下記のような実験を行った。
Experimental Example 1 Analysis of Surface Properties of Electrode Active Material In order to evaluate the physical properties of the electrode active material whose surface was modified according to the present invention, the following experiment was conducted.
試料としては、実施例１において有機−無機複合体で表面改質された正極活物質を用い、その対照群としては、通常の正極活物質(ＬｉＣｏＯ２)を用いた。 As the sample, the positive electrode active material surface-modified with the organic-inorganic composite in Example 1 was used, and as the control group, a normal positive electrode active material (LiCoO 2 ) was used.
前述した正極活物質を用いて常温大気中、常温真空、５０℃真空、１００℃真空、２００℃真空、３００℃真空状態において、それぞれＩＲスペクトル装置で分析した。その結果、２８００〜３０００ｃｍ−１近傍で現れるアルキル基(−ＣＨ２ＣＨ３)が、比較例１及び比較例２の正極活物質では現れないのに対し(図８参照)、本発明の正極活物質は有機物に含まれたアルキル基の存在を確認できた(図７参照)。よって、本発明の電極活物質上に存在する表面改質物質は、有機物及び無機物が互いに複合体を形成して存在することを確認できた。 Using the positive electrode active material described above, analysis was performed with an IR spectrum device in normal temperature air, normal temperature vacuum, 50 ° C. vacuum, 100 ° C. vacuum, 200 ° C. vacuum, and 300 ° C. vacuum. As a result, the alkyl group (—CH 2 CH 3 ) that appears in the vicinity of 2800 to 3000 cm −1 does not appear in the positive electrode active materials of Comparative Example 1 and Comparative Example 2 (see FIG. 8), whereas the positive electrode active of the present invention. The substance was confirmed to have an alkyl group contained in the organic substance (see FIG. 7). Therefore, it was confirmed that the surface modifying material present on the electrode active material of the present invention was present by forming a complex between the organic material and the inorganic material.
実験例２ 電極活物質の酸点の分析
本発明による電極活物質の表面の物性を評価するために、下記のような実験を行った。
Experimental Example 2 Analysis of Acid Site of Electrode Active Material In order to evaluate the physical properties of the surface of the electrode active material according to the present invention, the following experiment was conducted.
試料としては、実施例１において有機−無機複合体で表面改質された正極活物質と、実施例３において酸点を有する無機物で表面改質された正極活物質とを用いた。その対照群としては、比較例１の通常の正極活物質(ＬｉＣｏＯ２)と、無機物及び有機物でそれぞれ単独表面処理された比較例２並びに比較例３の正極活物質とを用いた。 As a sample, a positive electrode active material surface-modified with an organic-inorganic composite in Example 1 and a positive electrode active material surface-modified with an inorganic substance having an acid point in Example 3 were used. As the control group, the normal positive electrode active material (LiCoO 2 ) of Comparative Example 1 and the positive electrode active materials of Comparative Example 2 and Comparative Example 3 that were respectively surface-treated with an inorganic material and an organic material were used.
前述した正極活物質にＣＨ３ＣＮ化合物を吸着させて、ＩＲスペクトル装置の分析により酸点強度を測定した。参考として、ＣＨ３ＣＮ化合物は、非共有電子対を有する塩基性化合物であるから、酸点を有する化合物と中和反応による表面吸着を発生させることで、ＩＲスペクトル上でピーク変化を示すことができる。したがって、酸点を有する化合物の酸点強度を測定できる。 The CH 3 CN compound was adsorbed on the positive electrode active material described above, and the acid point intensity was measured by analysis with an IR spectrum apparatus. For reference, a CH 3 CN compound is a basic compound having an unshared electron pair, and therefore, by generating surface adsorption by a neutralization reaction with a compound having an acid point, it may show a peak change on the IR spectrum. it can. Therefore, the acid point strength of a compound having an acid point can be measured.
実験の結果、通常の正極活物質を用いた比較例１の正極活物質と、無機物で単独表面処理された比較例２の正極活物質と、有機物で単独表面処理された比較例３の正極活物質とは、ＩＲデータ上で特別な変化が現れなかった。これに対し、酸点を有する無機物で単独表面処理された実施例３の正極活物質と、有機物及び無機物の複合体で表面処理された実施例１の正極活物質とは、２２００〜２４００ｃｍ−１近傍でニトリル基(−ＣＮ)に対するピークが現れることで、表面に酸点が存在することを確認できた(図９参照)。 As a result of the experiment, the positive electrode active material of Comparative Example 1 using a normal positive electrode active material, the positive electrode active material of Comparative Example 2 treated with an inorganic material alone, and the positive electrode active material of Comparative Example 3 treated with an organic material alone. With substance, no special change appeared on IR data. In contrast, the positive electrode active material of Example 3 that was surface-treated alone with an inorganic substance having an acid point and the positive electrode active material of Example 1 that was surface-treated with a composite of an organic material and an inorganic material were 2200 to 2400 cm −1. A peak for the nitrile group (—CN) appeared in the vicinity, confirming the presence of acid sites on the surface (see FIG. 9).
特に、同一の成分の無機物で単独表面処理された実施例３の正極活物質と、比較例２の正極活物質とを比較した結果、比較例２の正極活物質は、無機物の表面処理により電解液との副反応性を止めるとしても、酸点が形成されないため、電池の性能が著しく減少したのに対し(図５参照)、酸点が形成された実施例３の正極活物質を用いた電池は、性能が向上したことが分かった(図３参照)。よって、酸点形成が電池の諸般性能に関連付ける因子であることを確認できた。 In particular, as a result of comparing the positive electrode active material of Example 3 that was surface-treated alone with the same inorganic material and the positive electrode active material of Comparative Example 2, the positive electrode active material of Comparative Example 2 was electrolyzed by the inorganic surface treatment. Even if the side reactivity with the liquid was stopped, acid sites were not formed, so the performance of the battery was significantly reduced (see FIG. 5), whereas the positive electrode active material of Example 3 in which acid sites were formed was used. The battery was found to have improved performance (see FIG. 3). Therefore, it was confirmed that acid spot formation is a factor relating to various performances of the battery.
実験例３ リチウム二次電池の性能の評価
本発明により表面上に酸点を有する電極活物質を用いて製造されたリチウム二次電池の性能評価を下記のように行った。
Experimental Example 3 Evaluation of Performance of Lithium Secondary Battery Performance evaluation of a lithium secondary battery manufactured using an electrode active material having acid sites on the surface according to the present invention was performed as follows.
酸点を有する正極活物質を用いて製造された実施例１〜実施例３のコイン状電池を用い、その対照群として表面改質されなかったり、無機物及び有機物でそれぞれ単独表面処理された比較例１〜比較例３のコイン状電池を用いた。 Comparative examples in which the coin-shaped batteries of Examples 1 to 3 manufactured using a positive electrode active material having acid sites were not surface-modified as a control group, or were individually surface-treated with an inorganic material and an organic material, respectively. The coin-shaped battery of 1 to Comparative Example 3 was used.
各電池を５０℃で３〜４.５Ｖまで０.５ＣにＣＣ／ＣＶ充放電を行い、得られた結果を各サイクル別に充放電グラフで図１〜図６に示した。 Each battery was subjected to CC / CV charge / discharge at 50 ° C. to 3 to 4.5 V to 0.5 C, and the obtained results are shown in FIG. 1 to FIG.
実験の結果、表面に酸点を有する電極活物質を用いて製造された実施例１〜実施例３の電池は、サイクルの進行により優れた充放電の効率が維持されることで、サイクル特性が著しく向上することを確認できた(図１〜図３参照)。これに対し、表面上に酸点が存在しない正極活物質を用いて製造された比較例１〜比較例３の電池は、充放電の特性が低下することを確認できた(図３〜図５参照)。 As a result of the experiment, the batteries of Examples 1 to 3 manufactured using an electrode active material having an acid point on the surface maintained cycle characteristics by maintaining excellent charge / discharge efficiency as the cycle progressed. It was confirmed that it was remarkably improved (see FIGS. 1 to 3). On the other hand, the batteries of Comparative Examples 1 to 3 manufactured using the positive electrode active material having no acid sites on the surface could confirm that the charge / discharge characteristics were degraded (FIGS. 3 to 5). reference).
Claims (23)
(ａ)１３族元素含有化合物、又は
(ｂ)(ｉ)１３族元素、及び(ｉｉ)アルカリ土金属、アルカリ金属、１４族元素、１５族元素、遷移金属、ランタノイド金属及びアクチナイド金属からなる群より選ばれた１種以上の元素を含有する化合物であることを特徴とする、請求項４に記載の電極活物質。 The inorganic substance is
(a) a group 13 element-containing compound, or
(b) one or more elements selected from the group consisting of (i) group 13 elements and (ii) alkaline earth metals, alkali metals, group 14 elements, group 15 elements, transition metals, lanthanoid metals and actinide metals The electrode active material according to claim 4, which is a compound to be contained.
(ａ)１４族元素含有化合物、又は
(ｂ)１４族元素、及び、アルカリ土金属、アルカリ金属、１３族元素、１５族元素、遷移金属、ランタノイド金属及びアクチナイド金属からなる群より選ばれた１種以上の元素を含有する化合物であることを特徴とする、請求項４に記載の電極活物質。 The organic (semi) metal compound is
(a) a group 14 element-containing compound, or
(b) A compound containing a group 14 element and one or more elements selected from the group consisting of alkaline earth metals, alkali metals, group 13 elements, group 15 elements, transition metals, lanthanoid metals, and actinide metals. The electrode active material according to claim 4, wherein
［化１］
ＳｉＨ４
［化２］
Ｓｉ(ＯＲ)４−ｘＲｘ(０.１≦ｘ≦３)
［化３］
Ｓｉ(ＯＲ)４−(ｘ＋ｙ)ＲｘＺｙ(０.１≦ｘ＋ｙ≦３.９)
［化４］
Ｓｉ(ＯＲ)４−ｘＲｘＳｉ(０.１≦ｘ≦３)
［化５］
Ｓｉ(ＯＲ)４−(ｘ＋ｙ)ＲｘＺｙＳｉ(０.１≦ｘ＋ｙ≦３.９)
［化６］
ＲｘＭ(ＯＲ)４−ｘ(１≦ｘ≦３)
［化７］
ＲｘＭＺｙ(ＯＲ)４−(ｘ＋ｙ)(０.１≦ｘ＋ｙ≦３.９)
［上記式中、
Ｚは、ハロゲン元素であり、
Ｍは、アルカリ土金属、アルカリ金属、遷移金属、ランタノイド金属及びアクチナイド金属からなる群より選ばれた１種以上の元素であり、
Ｒは、ハロゲン元素に置換又は非置換の、Ｃ１〜Ｃ２０のアルキル基、アルケニル基、アルキニル基、ビニル基、アミノ基及びメルカプト基からなる群より選ばれた置換基である。］ The electrode active material according to claim 4, wherein the organic (semi) metal compound is represented by any one of the following chemical formulas 1 to 7.
[Chemical 1]
SiH 4
[Chemical 2]
Si (OR) 4-x R x (0.1 ≦ x ≦ 3)
[Chemical formula 3]
Si (OR) 4− (x + y) R x Z y (0.1 ≦ x + y ≦ 3.9)
[Chemical formula 4]
Si (OR) 4-x R x Si (0.1 ≦ x ≦ 3)
[Chemical formula 5]
Si (OR) 4− (x + y) R x Z y Si (0.1 ≦ x + y ≦ 3.9)
[Chemical 6]
R x M (OR) 4-x (1 ≦ x ≦ 3)
[Chemical 7]
R x MZ y (OR) 4- (x + y) (0.1 ≦ x + y ≦ 3.9)
[In the above formula,
Z is a halogen element,
M is one or more elements selected from the group consisting of alkaline earth metals, alkali metals, transition metals, lanthanoid metals and actinide metals,
R is a substituent selected from the group consisting of a C1-C20 alkyl group, an alkenyl group, an alkynyl group, a vinyl group, an amino group, and a mercapto group, which is substituted or unsubstituted with a halogen element. ]
前記正極、前記負極又は両電極が、請求項１〜請求項１５の何れか一つの電極活物質を含んでなる電極或いは請求項１９に記載の電極であることを特徴とする、電気化学素子。 An electrochemical device comprising a positive electrode, a negative electrode, a separation membrane, and an electrolyte solution,
An electrochemical element, wherein the positive electrode, the negative electrode, or both electrodes are electrodes comprising the electrode active material according to any one of claims 1 to 15, or the electrode according to claim 19.
(ii)前記(ｉ)段階の結果物を電極活物質の表面にコートし、そのコーティング層を乾燥させる段階を含むことを特徴とする、酸点強度が調節されたコーティング層を有する電極活物質の製造方法。 (i) (a) reacting a compound that provides a proton (or electron pair) or accepts a proton (or electron pair) and (b) a compound having an acid point; and
(ii) An electrode active material having a coating layer with adjusted acid point strength, comprising the step of coating the surface of the electrode active material with the resultant product of step (i) and drying the coating layer Manufacturing method.
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| US10978704B2 (en) | 2015-11-16 | 2021-04-13 | HHeLI, LLC | Synthesized, surface-functionalized, acidified metal oxide materials for energy storage, catalytic, photovoltaic and sensor applications |
| JP2018536272A (en) * | 2015-11-16 | 2018-12-06 | ヒーリー，エルエルシー | Synthetic surface functionalized and acidified metal oxide materials for energy storage, catalyst, photovoltaic and sensor applications |
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| JP2020521281A (en) * | 2017-05-17 | 2020-07-16 | ヒーリー，エルエルシー | Battery cell with new structure |
| JP7340460B2 (en) | 2017-05-17 | 2023-09-07 | ヒーリー，エルエルシー | Battery cell with new structure |
| JP7429321B2 (en) | 2017-05-17 | 2024-02-07 | ヒーリー，エルエルシー | Battery cell with new structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5450057B2 (en) | 2014-03-26 |
| JP5761725B2 (en) | 2015-08-12 |
| JP2014013770A (en) | 2014-01-23 |
| CN102916163A (en) | 2013-02-06 |
| CN101438434A (en) | 2009-05-20 |
| DE112007001087T5 (en) | 2009-02-19 |
| KR20090013841A (en) | 2009-02-05 |
| CA2651235C (en) | 2014-12-09 |
| CA2651235A1 (en) | 2007-11-15 |
| KR20070108086A (en) | 2007-11-08 |
| CN101438434B (en) | 2017-09-15 |
| KR100984591B1 (en) | 2010-09-30 |
| WO2007129842A1 (en) | 2007-11-15 |
| DE112007001087B4 (en) | 2019-11-28 |
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