JP6357195B2 - Method for producing positive electrode for lithium ion secondary battery, and positive electrode for lithium ion secondary battery obtained therefrom - Google Patents
Method for producing positive electrode for lithium ion secondary battery, and positive electrode for lithium ion secondary battery obtained therefrom Download PDFInfo
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- JP6357195B2 JP6357195B2 JP2016140237A JP2016140237A JP6357195B2 JP 6357195 B2 JP6357195 B2 JP 6357195B2 JP 2016140237 A JP2016140237 A JP 2016140237A JP 2016140237 A JP2016140237 A JP 2016140237A JP 6357195 B2 JP6357195 B2 JP 6357195B2
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- positive electrode
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- acid
- ion secondary
- lithium ion
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- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、優れたサイクル特性を発現するリチウムイオン二次電池を得ることのできるリチウムイオン二次電池用正極の製造方法及びそれから得られるリチウムイオン二次電池用正極に関する。 The present invention relates to a method for producing a positive electrode for a lithium ion secondary battery capable of obtaining a lithium ion secondary battery exhibiting excellent cycle characteristics, and a positive electrode for a lithium ion secondary battery obtained therefrom.
携帯電子機器、ハイブリッド自動車、電気自動車等に用いられる二次電池の開発が行われており、特にリチウムイオン二次電池は広く知られている。こうしたなか、オリビン型構造を有するＬｉ（Ｆｅ，Ｍｎ）ＰＯ4等のリチウム遷移金属リン酸塩化合物やＬｉ2（Ｆｅ，Ｍｎ）ＳｉＯ4等のリチウム遷移金属ケイ酸塩化合物は、資源的な制約に大きく左右されることがなく、しかも高い安全性を発揮することができるため、高出力で大容量のリチウムイオン二次電池を形成する正極の材料として最適である。そして、さらなる改善を図るべく、従来より種々の開発がなされている。 Secondary batteries used for portable electronic devices, hybrid cars, electric cars, and the like have been developed. In particular, lithium ion secondary batteries are widely known. Under these circumstances, lithium transition metal phosphate compounds such as Li (Fe, Mn) PO 4 having an olivine structure and lithium transition metal silicate compounds such as Li 2 (Fe, Mn) SiO 4 are resource constraints. Therefore, it is optimal as a material for a positive electrode for forming a high-power, large-capacity lithium ion secondary battery. Various developments have been made in the past for further improvement.
例えば、特許文献１では、超微粒子化した一次結晶粒子から得られるリチウム遷移金属リン酸塩の活物質に炭素を被覆した電極が開示されており、これによってリチウムイオン拡散距離の短縮化を図り、得られる電池の性能向上を試みている。また、特許文献２では、リチウム及び遷移金属のホスフェート類やシリケート類等の酸化物の粒子表面に伝導性炭質材料を均一に堆積させ、かかる粒子表面で規則的な電場分布を得ることにより、得られる電池の高出力化を図っている。 For example, Patent Document 1 discloses an electrode in which carbon is coated on an active material of a lithium transition metal phosphate obtained from ultrafine primary crystal particles, thereby shortening a lithium ion diffusion distance, We are trying to improve the performance of the battery. In Patent Document 2, a conductive carbonaceous material is uniformly deposited on the surface of oxide particles such as phosphates and silicates of lithium and transition metals, and a regular electric field distribution is obtained on the surface of the particles. To increase the output of the battery.
一方、特許文献３には、導電性金属箔の表面上に、リチウム遷移金属酸化物を含む正極活物質とポリイミド樹脂とを含む正極合剤層が形成された正極が開示されており、高電位の充放電条件での正極活物質の劣化を抑制しようと試みている。 On the other hand, Patent Document 3 discloses a positive electrode in which a positive electrode mixture layer including a positive electrode active material containing a lithium transition metal oxide and a polyimide resin is formed on the surface of a conductive metal foil, and has a high potential. An attempt is made to suppress the deterioration of the positive electrode active material under the charge / discharge conditions.
しかしながら、正極の劣化を抑制してサイクル特性を高めようとするにあたり、ポリイミド樹脂のような材料を用いることは有効ではあるものの、正極活物質としてリチウム遷移金属ケイ酸塩を用いようとする場合、上記文献に記載の技術では、いずれもリチウム遷移金属ケイ酸塩固有の事情を加味するものではないため、充分にサイクル特性を発現できず、依然として改善の余地がある。 However, in order to suppress the deterioration of the positive electrode and improve the cycle characteristics, it is effective to use a material such as a polyimide resin, but when using lithium transition metal silicate as the positive electrode active material, None of the techniques described in the above documents take into consideration the circumstances peculiar to lithium transition metal silicates, so that the cycle characteristics cannot be sufficiently exhibited, and there is still room for improvement.
したがって、本発明の課題は、正極活物質としてリチウム遷移金属ケイ酸塩化合物を用いつつ、正極の劣化を有効に抑制して、優れたサイクル特性を発現するリチウムイオン二次電池を得ることのできるリチウムイオン二次電池用正極の製造方法及びそれから得られるリチウムイオン二次電池用正極を提供することにある。 Therefore, the subject of this invention can obtain the lithium ion secondary battery which expresses the outstanding cycling characteristics, suppressing the deterioration of a positive electrode effectively, using a lithium transition metal silicate compound as a positive electrode active material. It is providing the manufacturing method of the positive electrode for lithium ion secondary batteries, and the positive electrode for lithium ion secondary batteries obtained from it.
そこで本発明者らは、種々検討したところ、正極活物質としてリチウム遷移金属ケイ酸塩化合物とともにポリイミド樹脂等の特定の結着剤を用いつつ、ホウ酸等の特定の酸と導電助剤を含む正極活物質層を正極用集電体表面に形成することにより、良好なサイクル特性の発現に有効な正極が得られることを見出し、本発明を完成させるに至った。 Therefore, the present inventors have made various studies, and include a specific acid such as boric acid and a conductive additive while using a specific binder such as a polyimide resin together with a lithium transition metal silicate compound as a positive electrode active material. It has been found that by forming the positive electrode active material layer on the surface of the current collector for positive electrode, a positive electrode effective for developing good cycle characteristics can be obtained, and the present invention has been completed.
すなわち、本発明は、次の成分（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）、並びに（Ｅ）：
（Ａ）リチウム遷移金属ケイ酸塩化合物、
（Ｂ）ポリイミド樹脂、ポリアミドイミド樹脂、及びポリアミド樹脂から選ばれる結着剤、
（Ｃ）ホウ酸、及びリン酸二水素アンモニウムから選ばれる無機酸（ｃ−１）、並びに酢酸、ギ酸、及びプロピオン酸から選ばれる有機酸（ｃ−２）を含む酸、
（Ｄ）導電助剤、並びに
（Ｅ）有機溶媒
を用いる、リチウムイオン二次電池用正極の製造方法であって、
成分（Ｂ）、成分（Ｃ）、及び成分（Ｅ）を含む混合物Ｘを調製する工程（Ｉ）、
得られた混合物Ｘに、成分（Ａ）、及び成分（Ｄ）を添加して混合し、ペースト組成物Ｙを得る工程（II）、並びに
得られたペースト組成物Ｙを正極用集電体上に塗布した後、乾燥して加熱し、正極活物質層を形成する工程（III）
を備えるリチウムイオン二次電池用正極の製造方法に関する。
That is, the present invention includes the following components (A), (B), (C), (D), and (E):
(A) a lithium transition metal silicate compound,
(B) a binder selected from polyimide resin, polyamideimide resin, and polyamide resin,
(C) An acid containing an inorganic acid (c-1) selected from boric acid and ammonium dihydrogen phosphate, and an organic acid (c-2) selected from acetic acid, formic acid, and propionic acid,
(D) a conductive assistant, and (E) a method for producing a positive electrode for a lithium ion secondary battery using an organic solvent,
Preparing a mixture X comprising component (B), component (C), and component (E) (I),
Step (II) to obtain the paste composition Y by adding and mixing the component (A) and the component (D) to the obtained mixture X, and the obtained paste composition Y on the positive electrode current collector Step (III) of forming a positive electrode active material layer by drying and heating after coating
The manufacturing method of the positive electrode for lithium ion secondary batteries provided with this.
また、本発明は、正極用集電体表面に、次の成分（Ａ）、（Ｂ）、（ｃ−１）、並びに（Ｄ）：
（Ａ）リチウム遷移金属ケイ酸塩化合物、
（Ｂ）ポリイミド樹脂、ポリアミドイミド樹脂、及びポリアミド樹脂から選ばれる結着剤、
（ｃ−１）ホウ酸、及びリン酸二水素アンモニウムから選ばれる無機酸、並びに
（Ｄ）導電助剤
を含む正極活物質層が形成されてなる、リチウムイオン二次電池用正極に関する。
Further, the present invention provides the following components (A), (B), (c-1), and (D) on the surface of the positive electrode current collector:
(A) a lithium transition metal silicate compound,
(B) a binder selected from polyimide resin, polyamideimide resin, and polyamide resin,
(C-1) It is related with the positive electrode for lithium ion secondary batteries in which the inorganic acid chosen from boric acid and ammonium dihydrogen phosphate, and (D) the positive electrode active material layer containing a conductive support agent are formed.
本発明のリチウムイオン二次電池用正極によれば、正極活物質であるリチウム遷移金属ケイ酸塩化合物固有の事情を加味しながら、良好な強度や耐久性を付与することのできるポリイミド樹脂等の結着剤を用いることができるので、繰り返される充放電処理にも充分な耐久性を示し、良好なサイクル特性を発現するリチウムイオン二次電池を実現することができる。 According to the positive electrode for a lithium ion secondary battery of the present invention, while taking into consideration the circumstances unique to the lithium transition metal silicate compound that is a positive electrode active material, such as a polyimide resin that can impart good strength and durability Since the binder can be used, it is possible to realize a lithium ion secondary battery that exhibits sufficient durability for repeated charge / discharge treatments and exhibits good cycle characteristics.
以下、本発明について詳細に説明する。
本発明のリチウムイオン二次電池用正極の製造方法は、次の成分（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）、並びに（Ｅ）：
（Ａ）リチウム遷移金属ケイ酸塩化合物、
（Ｂ）ポリイミド樹脂、ポリアミドイミド樹脂、及びポリアミド樹脂から選ばれる結着剤、
（Ｃ）ホウ酸、及びリン酸二水素アンモニウムから選ばれる無機酸（ｃ−１）、並びに酢酸、ギ酸、及びプロピオン酸から選ばれる有機酸（ｃ−２）を含む酸、
（Ｄ）導電助剤、並びに
（Ｅ）有機溶媒
を用いる、リチウムイオン二次電池用正極の製造方法であって、
成分（Ｂ）、成分（Ｃ）、及び成分（Ｅ）を含む混合物Ｘを調製する工程（Ｉ）、
得られた混合物Ｘに、成分（Ａ）、及び成分（Ｄ）を添加して混合し、ペースト組成物Ｙを得る工程（II）、並びに
得られたペースト組成物Ｙを正極用集電体上に塗布した後、乾燥して加熱し、正極活物質層を形成する工程（III）
を備える。
Hereinafter, the present invention will be described in detail.
The method for producing a positive electrode for a lithium ion secondary battery of the present invention comprises the following components (A), (B), (C), (D), and (E):
(A) a lithium transition metal silicate compound,
(B) a binder selected from polyimide resin, polyamideimide resin, and polyamide resin,
(C) An acid containing an inorganic acid (c-1) selected from boric acid and ammonium dihydrogen phosphate, and an organic acid (c-2) selected from acetic acid, formic acid, and propionic acid,
(D) a conductive assistant, and (E) a method for producing a positive electrode for a lithium ion secondary battery using an organic solvent,
Preparing a mixture X comprising component (B), component (C), and component (E) (I),
Step (II) to obtain the paste composition Y by adding and mixing the component (A) and the component (D) to the obtained mixture X, and the obtained paste composition Y on the positive electrode current collector Step (III) of forming a positive electrode active material layer by drying and heating after coating
Is provided.
本発明では、成分（Ａ）として、リチウム遷移金属ケイ酸塩化合物を用いる。リチウム遷移金属ケイ酸塩化合物は、高い電池物性を付与することができ、具体的には、（ｏ）遷移金属化合物、（ｐ）ケイ酸化合物、（ｑ）リチウム化合物、及び（ｒ）水、さらに必要に応じて（ｓ）遷移金属以外の金属化合物を含有する混合物スラリーを耐圧容器内で水熱反応させる方法により製造することができる。 In the present invention, a lithium transition metal silicate compound is used as the component (A). Lithium transition metal silicate compounds can impart high battery physical properties, specifically: (o) transition metal compounds, (p) silicate compounds, (q) lithium compounds, and (r) water, Furthermore, if necessary, it can be produced by a method in which a mixture slurry containing a metal compound other than (s) a transition metal is subjected to a hydrothermal reaction in a pressure vessel.
成分（ｏ）の遷移金属化合物を構成する遷移金属（Ｍ）としては、例えば、Ｆｅ、Ｎｉ、Ｃｏ、Ｍｎ、Ｖ、Ｚｒ、Ｙ、Ｍｏ、Ｌａ、Ｃｅ及びＮｄ等が挙げられ、これらを含む遷移金属化合物を１種単独で用いてもよく、２種以上組み合わせて用いてもよい。かかる遷移金属化合物（Ｍ）としては、例えばフッ化物、塩化物、ヨウ化物等のハロゲン化遷移金属塩、硫酸遷移金属塩の他、有機酸遷移金属塩、並びにこれらの水和物等が挙げられる。このうち、有機酸遷移金属塩を構成する有機酸としては、炭素数１〜２０の有機酸、さらに炭素数２〜１２の有機酸が好ましい。さらに好ましくは、シュウ酸、フマル酸等のジカルボン酸、乳酸等のヒドロキシカルボン酸、酢酸等の脂肪酸が挙げられる。 Examples of the transition metal (M) constituting the component (o) transition metal compound include Fe, Ni, Co, Mn, V, Zr, Y, Mo, La, Ce, and Nd, and these are included. A transition metal compound may be used individually by 1 type, and may be used in combination of 2 or more type. Examples of the transition metal compound (M) include halogenated transition metal salts such as fluoride, chloride and iodide, transition metal salts of sulfuric acid, organic acid transition metal salts, and hydrates thereof. . Among these, the organic acid constituting the organic acid transition metal salt is preferably an organic acid having 1 to 20 carbon atoms, and more preferably an organic acid having 2 to 12 carbon atoms. More preferred are dicarboxylic acids such as oxalic acid and fumaric acid, hydroxycarboxylic acids such as lactic acid, and fatty acids such as acetic acid.
成分（ｐ）のケイ酸化合物としては、反応性のあるシリカ化合物であれば特に限定されず、非晶質シリカ、Ｎａ4ＳｉＯ4（例えばＮａ4ＳｉＯ4・Ｈ2Ｏ）等が用いられる。 The silicic acid compound of the component (p) is not particularly limited as long as it is a reactive silica compound, and amorphous silica, Na 4 SiO 4 (for example, Na 4 SiO 4 .H 2 O), etc. are used.
成分（ｑ）のリチウム化合物としては、フッ化リチウム、塩化リチウム、臭化リチウム、ヨウ化リチウム等のリチウム金属塩、水酸化リチウム、炭酸リチウム等が挙げられ、安価である点で炭酸リチウムを使用するのが好ましい。 Examples of the lithium compound of component (q) include lithium metal salts such as lithium fluoride, lithium chloride, lithium bromide and lithium iodide, lithium hydroxide, lithium carbonate and the like, and lithium carbonate is used because it is inexpensive. It is preferable to do this.
成分（ｓ）の遷移金属以外の金属化合物を構成する金属（Ｒ）としては、例えば、Ａｌ、Ｚｎ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｐｂ、及びＢｉ等が挙げられ、これらを含む金属化合物を１種単独で用いてもよく、２種以上組み合わせて用いてもよい。かかる金属化合物（Ｒ）としては、例えばフッ化物、塩化物、ヨウ化物等のハロゲン化金属塩、硫酸金属塩の他、有機酸金属塩、並びにこれらの水和物等が挙げられる。このうち、有機酸金属塩を構成する有機酸としては、炭素数１〜２０の有機酸、さらに炭素数２〜１２の有機酸が好ましい。さらに好ましくは、シュウ酸、フマル酸等のジカルボン酸、乳酸等のヒドロキシカルボン酸、酢酸等の脂肪酸が挙げられる。 Examples of the metal (R) constituting the metal compound other than the transition metal of the component (s) include Al, Zn, Mg, Ca, Sr, Ba, Pb, Bi, and the like. You may use individually by 1 type and may be used in combination of 2 or more type. Examples of the metal compound (R) include metal halides such as fluorides, chlorides and iodides, sulfate metal salts, organic acid metal salts, and hydrates thereof. Among these, the organic acid constituting the organic acid metal salt is preferably an organic acid having 1 to 20 carbon atoms, and more preferably an organic acid having 2 to 12 carbon atoms. More preferred are dicarboxylic acids such as oxalic acid and fumaric acid, hydroxycarboxylic acids such as lactic acid, and fatty acids such as acetic acid.
かかる成分（Ａ）のリチウム遷移金属ケイ酸塩化合物としては、具体的には、例えば以下のような態様が含まれる。
Ｌｉ2ＦｅｘＭｎｙＺｒｚＳｉＯ4 ・・・（１）
（式中、ｘ、ｙ及びｚは、０≦ｘ＜１、０≦ｙ＜１、０＜ｚ＜０．５、２ｘ＋２ｙ＋４ｚ＝２、及びｘ＋ｙ≠０を満たす数を示す。）
Ｌｉ2Ｆｅｘ1Ｍｎｙ1Ｚｒｚ1Ｍ2 c2Ｒd2ＳｉＯ4 ・・・（２）
（式中、Ｍ2はＮｉ、Ｃｏ、Ａｌ、Ｚｎ、Ｖ、Ｙ、Ｍｏ、Ｌａ、Ｃｅ及びＮｄから選ばれる１種又は２種以上を、ＲはＭｇ、Ｃａ、Ｓｒ、Ｂａ、Ｐｂ、及びＢｉから選ばれる１種又は２種以上を示す。ｘ1、ｙ1、ｚ1、ｃ2、ｄ2は、０≦ｘ1＜１、０≦ｙ1＜１、０＜ｚ1＜０．５、及び０＜（ｃ2＋ｄ2）≦０．２を満たし、かつ２ｘ1＋２ｙ1＋４ｚ1＋（Ｍ2の価数）×ｃ2＋（Ｒの価数）×ｄ2＝２、及びｘ1＋ｙ1≠０を満たす数を示す。）
Specific examples of the component (A) lithium transition metal silicate compound include the following embodiments.
Li 2 Fe x Mn y Zr z SiO 4 ··· (1)
(In the formula, x, y, and z represent numbers satisfying 0 ≦ x <1, 0 ≦ y <1, 0 <z <0.5, 2x + 2y + 4z = 2, and x + y ≠ 0.)
Li 2 Fe x1 Mn y1 Zr z1 M 2 c2 R d2 SiO 4 ··· (2)
(Wherein M 2 is one or more selected from Ni, Co, Al, Zn, V, Y, Mo, La, Ce and Nd, R is Mg, Ca, Sr, Ba, Pb, and 1 or 2 or more types selected from Bi are shown, and x 1 , y 1 , z 1 , c 2 , and d 2 are 0 ≦ x 1 <1, 0 ≦ y 1 <1, 0 <z 1 <0. 5 and 0 <(c 2 + d 2 ) ≦ 0.2, and 2x 1 + 2y 1 + 4z 1 + (valence of M 2 ) × c 2 + (valence of R) × d 2 = 2, and Indicates a number satisfying x 1 + y 1 ≠ 0.)
（ｏ）遷移金属化合物と、（ｐ）ケイ酸化合物、（ｑ）リチウム化合物、及び（ｓ）遷移金属以外の金属化合物の使用量は、目的物によって異なる。例えば、目的物がケイ酸鉄リチウム（Ｌｉ2ＦｅＳｉＯ4）の場合には、（ｏ）遷移金属（鉄）化合物及び（ｓ）遷移金属以外の金属化合物の合計使用量と、（ｑ）リチウム化合物の使用量とのモル比は、鉄イオンとリチウムイオン換算で１：２〜１：３が好ましく、１：２〜１：２．５とするのがより好ましい。また、（ｑ）リチウム化合物の使用量と（ｐ）ケイ酸化合物の使用量とのモル比は、リチウムイオン及びケイ酸イオン換算で２：１〜３：１が好ましい。 The amount of (o) the transition metal compound, (p) the silicate compound, (q) the lithium compound, and (s) the metal compound other than the transition metal varies depending on the target product. For example, when the object is lithium iron silicate (Li 2 FeSiO 4 ), (o) the total amount of the transition metal (iron) compound and (s) the metal compound other than the transition metal, and (q) the lithium compound The molar ratio with the use amount of is preferably 1: 2 to 1: 3, more preferably 1: 2 to 1: 2.5 in terms of iron ions and lithium ions. In addition, the molar ratio between the amount of (q) the lithium compound used and the amount of the (p) silicate compound used is preferably 2: 1 to 3: 1 in terms of lithium ions and silicate ions.
成分（ｒ）の水の使用量は、原料化合物の溶解性、撹拌の容易性、合成の効率等の点から、ケイ酸化合物のケイ酸イオン１モルに対して１０〜５０モルが好ましく、さらに１３〜３０モルが好ましい。 The amount of the component (r) water used is preferably 10 to 50 moles per mole of silicate ions of the silicate compound, from the viewpoints of solubility of the raw material compound, ease of stirring, synthesis efficiency, and the like. 13-30 mol is preferable.
これらの原料の添加順序は特に限定されない。また、混合物スラリー中には、必要により酸化防止剤を添加してもよく、酸化防止剤としては、ハイドロサルファイトナトリウム（Ｎａ2Ｓ2Ｏ4）、アンモニア水、亜硫酸ナトリウム等を用いることができる。水分散液中の酸化防止剤の含有量は、多量に添加するリチウム遷移金属ケイ酸塩化合物の生成を抑制してしまうため、遷移金属に対して等モル量以下が好ましい。 The order of adding these raw materials is not particularly limited. In addition, an antioxidant may be added to the mixture slurry as necessary. As the antioxidant, sodium hydrosulfite (Na 2 S 2 O 4 ), aqueous ammonia, sodium sulfite, and the like can be used. . The content of the antioxidant in the aqueous dispersion is preferably equal to or less than the equimolar amount with respect to the transition metal because it suppresses the generation of a lithium transition metal silicate compound to be added in a large amount.
これらの成分の混合物スラリーは、塩基性とするのが副反応を防止し、ケイ酸化合物を溶解するうえで好ましい。混合物スラリーのｐＨは、塩基性であればよいが、１２．０〜１３．５であるのが副反応の防止、ケイ酸化合物の溶解性及び反応の進行の点で特に好ましい。該混合物スラリーのｐＨの調整は、塩基、例えば、水酸化ナトリウムを添加することにより行ってもよいが、ケイ酸化合物としてＮａ4ＳｉＯ4を用いるのが特に好ましい。 It is preferable that the mixture slurry of these components is basic in order to prevent side reactions and dissolve the silicate compound. The pH of the mixture slurry may be basic, but 12.0 to 13.5 is particularly preferable in terms of prevention of side reactions, solubility of silicic acid compounds, and progress of the reaction. The pH of the mixture slurry may be adjusted by adding a base such as sodium hydroxide, but it is particularly preferable to use Na 4 SiO 4 as the silicate compound.
水熱反応は、１００℃以上であればよく、１３０〜１８０℃が好ましい。水熱反応は耐圧容器中で行うのが好ましく、１３０〜１８０℃で反応を行う場合、この時の圧力は０．３〜０．９ＭＰａであるのが好ましく、１４０〜１６０℃で反応を行う場合の圧力は０．３〜０．６ＭＰａであるのが好ましい。水熱反応時間は０．５〜２４時間が好ましく、さらに１〜１２時間が好ましい。
得られたリチウム遷移金属ケイ酸塩化合物は、ろ過後、乾燥することにより単離できる。乾燥手段は、凍結乾燥、真空乾燥が用いられる。
Hydrothermal reaction should just be 100 degreeC or more, and 130-180 degreeC is preferable. The hydrothermal reaction is preferably carried out in a pressure vessel, and when the reaction is carried out at 130 to 180 ° C, the pressure at this time is preferably 0.3 to 0.9 MPa, and the reaction is carried out at 140 to 160 ° C. The pressure is preferably 0.3 to 0.6 MPa. The hydrothermal reaction time is preferably 0.5 to 24 hours, more preferably 1 to 12 hours.
The obtained lithium transition metal silicate compound can be isolated by filtration and then drying. As the drying means, freeze drying or vacuum drying is used.
本発明では、成分（Ｂ）として、ポリイミド樹脂、ポリアミドイミド樹脂、及びポリアミド樹脂から選ばれる結着剤を用いる。これら成分（Ｂ）の結着剤は、いずれも後述する成分（Ｄ）の導電助剤との親和性が良好であるとともに、形成される正極活物質層に剛直性を付与して高い寸法安定性をもたらすことも可能であることから、得られる正極に良好な強度や耐久性を付与することができ、充放電処理を繰り返した後に発現し得る電池物性の劣化を効果的に抑制して、優れたサイクル特性を発現するリチウムイオン二次電池を得ることができる。 In the present invention, as the component (B), a binder selected from a polyimide resin, a polyamideimide resin, and a polyamide resin is used. These component (B) binders all have good affinity with the conductive aid of component (D) described later, and impart high rigidity to the positive electrode active material layer to be formed, resulting in high dimensional stability. Since it is also possible to provide good strength and durability to the positive electrode obtained, it is possible to effectively suppress deterioration of battery physical properties that can be manifested after repeated charge and discharge treatments, A lithium ion secondary battery that exhibits excellent cycle characteristics can be obtained.
ポリイミド樹脂は、主鎖にイミド結合を有する樹脂であり、縮合反応により得られる半芳香族ポリイミドや、付加反応により得られる全芳香族ポリイミド等が挙げられる。
ポリアミドイミド樹脂は、分子内にイミド基とアミド基を交互に共重合させたものであり、酸クロライド法やイソシアネート法、又は直接重合法により得られる樹脂である。
ポリアミド樹脂は、ナイロンとも総称されるアミド結合の繰り返し単位が主鎖を構成する樹脂であり、ＰＡ６６やＰＡ１１等の脂肪族ポリアミド、アラミド等の芳香族ポリアミド等が挙げられる。
なかでも、電池物性の劣化を有効に抑制する観点から、ポリイミド樹脂が好ましい。
The polyimide resin is a resin having an imide bond in the main chain, and examples thereof include semi-aromatic polyimide obtained by condensation reaction, wholly aromatic polyimide obtained by addition reaction, and the like.
The polyamide-imide resin is obtained by alternately copolymerizing imide groups and amide groups in the molecule, and is a resin obtained by an acid chloride method, an isocyanate method, or a direct polymerization method.
The polyamide resin is a resin in which a repeating unit of an amide bond, also referred to as nylon, constitutes a main chain, and examples thereof include aliphatic polyamides such as PA66 and PA11, aromatic polyamides such as aramid, and the like.
Among these, a polyimide resin is preferable from the viewpoint of effectively suppressing deterioration of battery physical properties.
本発明では、成分（Ｃ）として、ホウ酸、及びリン酸二水素アンモニウムから選ばれる無機酸（ｃ−１）、並びに酢酸、ギ酸、及びプロピオン酸から選ばれる有機酸（ｃ−２）からなる群より選ばれる１種以上の酸を用いる。かかる成分（Ｃ）の酸を用いることにより、後述する工程（II）において、正極活物質層を形成するためのペースト組成物を調製する際、成分（Ａ）のリチウム遷移金属ケイ酸塩化合物の存在によって、かかるペースト組成物のｐＨがアルカリ領域へ偏向して成分（Ｂ）の結着剤が分解等してしまうのを有効に抑制することができる。
なかでも、成分（Ａ）のリチウム遷移金属ケイ酸塩化合物の分解等をも有効に抑制する観点、及び適切なｐＨ領域に調整しやすい観点から、成分（ｃ−１）の無機酸が好ましく、ホウ酸がより好ましい。
In the present invention, the component (C) comprises an inorganic acid (c-1) selected from boric acid and ammonium dihydrogen phosphate, and an organic acid (c-2) selected from acetic acid, formic acid, and propionic acid. One or more acids selected from the group are used. In preparing the paste composition for forming the positive electrode active material layer in the step (II) described later by using the acid of the component (C), the lithium transition metal silicate compound of the component (A) is prepared. The presence of the paste composition can effectively prevent the pH of the paste composition from deviating to the alkaline region and the component (B) binder from being decomposed.
Among these, from the viewpoint of effectively suppressing the decomposition of the lithium transition metal silicate compound of the component (A) and the viewpoint of easy adjustment to an appropriate pH region, the inorganic acid of the component (c-1) is preferable. Boric acid is more preferred.
なお、これら成分（Ｃ）のうち、成分（ｃ−１）は、後述する工程（III）において形成される正極活物質層中に残存する一方、成分（ｃ−２）は加熱等の処理を経ることによって揮発してしまうため、正極活物質層中に残存しない。しかしながら、ともにペースト組成物のｐＨがアルカリ領域へ偏向して成分（Ｂ）の結着剤が分解等してしまうのを有効に抑制する効果を有するため、得られるリチウムイオン二次電池用正極においては、繰り返される充放電処理に対する優れた耐久性や、二次電池における良好なサイクル特性の発現効果については、同等の優れた効果を発揮することができる。 Of these components (C), component (c-1) remains in the positive electrode active material layer formed in step (III) described later, while component (c-2) is subjected to a treatment such as heating. Since it volatilizes by passing, it does not remain in the positive electrode active material layer. However, since both have the effect of effectively suppressing the pH of the paste composition from deviating to the alkaline region and decomposing the binder of component (B), the resulting positive electrode for a lithium ion secondary battery Can exhibit the same excellent effect with respect to the excellent durability against repeated charge / discharge treatment and the effect of developing good cycle characteristics in the secondary battery.
本発明では、成分（Ｄ）として、導電助剤を用いる。かかる成分（Ｄ）を用いることによって、これを正極活物質層に含まれる成分（Ａ）や成分（Ｂ）の粒子間間隙に介在させ、正極活物質層の導電性を高めることができる。かかる導電助剤としては、得られる電池物性を効果的に高めつつ発塵量を有効に低減する観点から、水不溶性導電性炭素材料、及び水溶性炭素材料の炭化物のほか、セルロースナノファイバーの炭化物が挙げられる。 In this invention, a conductive support agent is used as a component (D). By using such a component (D), this can be interposed in the interparticle gaps of the component (A) and the component (B) contained in the positive electrode active material layer, and the conductivity of the positive electrode active material layer can be increased. As such a conductive assistant, from the viewpoint of effectively reducing the amount of dust generated while effectively enhancing the physical properties of the obtained battery, in addition to the water-insoluble conductive carbon material and the carbide of the water-soluble carbon material, the carbide of cellulose nanofibers Is mentioned.
上記水不溶性導電性炭素材料とは、セルロースナノファイバー以外の炭素源であり、２５℃の水１００ｇに対する溶解量が、水不溶性導電性炭素材料の炭素原子換算量で０．４ｇ未満である水不溶性の炭素材料であって、焼成等せずともそのもの自体が導電性を有する導電助剤である。かかる水不溶性導電性炭素材料としては、グラファイト、アセチレンブラック、ケッチェンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、及びサーマルブラックから選ばれる１種又は２種以上が挙げられる。なかでも、特定の無機化合物と相まって、ポリアニオン材料の粒子表面に効果的に担持させる観点から、グラファイトが好ましい。グラファイトとしては、人造グラファイト（鱗片状、塊状、土状、グラフェン）、天然グラファイトのいずれであってもよい。 The water-insoluble conductive carbon material is a carbon source other than cellulose nanofiber, and the water-insoluble conductive carbon material has a solubility in 100 g of water at 25 ° C. of less than 0.4 g in terms of carbon atom of the water-insoluble conductive carbon material. The carbon material itself is a conductive auxiliary agent having conductivity without firing. Examples of the water-insoluble conductive carbon material include one or more selected from graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black. Among these, graphite is preferable from the viewpoint of being effectively supported on the particle surface of the polyanion material in combination with a specific inorganic compound. The graphite may be any of artificial graphite (scaly, massive, earthy, graphene) or natural graphite.
水不溶性導電性炭素材料のＢＥＴ比表面積は、高温環境下におけるサイクル特性を効果的に高める観点から、好ましくは１〜７５０ｍ2／ｇであり、より好ましくは３〜５００ｍ2／ｇである。また、かかる水不溶性導電性炭素材料の平均粒子径は、同様の観点から、好ましくは０．５〜２０μｍであり、より好ましくは１．０〜１５μｍである。 The BET specific surface area of the water-insoluble conductive carbon material is preferably 1 to 750 m 2 / g, more preferably 3 to 500 m 2 / g, from the viewpoint of effectively enhancing cycle characteristics in a high temperature environment. Moreover, from the same viewpoint, the average particle size of the water-insoluble conductive carbon material is preferably 0.5 to 20 μm, more preferably 1.0 to 15 μm.
上記水溶性炭素材料とは、２５℃の水１００ｇに、水溶性炭素材料の炭素原子換算量で０．４ｇ以上、好ましくは１．０ｇ以上溶解する炭素材料を意味し、炭化されることで炭素として上記ポリアニオン材料の粒子表面に存在する導電助剤である。かかる水溶性炭素材料としては、例えば、糖類、ポリオール、ポリエーテル、及び有機酸から選ばれる１種又は２種以上が挙げられる。より具体的には、例えば、グルコース、フルクトース、ガラクトース、マンノース等の単糖類；マルトース、スクロース、セロビオース等の二糖類；デンプン、デキストリン等の多糖類；エチレングリコール、プロピレングリコール、ジエチレングリコール、ポリエチレングリコール、ブタンジオール、プロパンジオール、ポリビニルアルコール、グリセリン等のポリオールやポリエーテル；クエン酸、酒石酸、アスコルビン酸等の有機酸が挙げられる。なかでも、溶媒への溶解性及び分散性を高めて導電助剤として効果的に機能させる観点から、グルコース、フルクトース、スクロース、デキストリンが好ましく、グルコースがより好ましい。 The water-soluble carbon material means a carbon material that dissolves in 100 g of water at 25 ° C. in terms of carbon atom of the water-soluble carbon material in an amount of 0.4 g or more, preferably 1.0 g or more. As a conductive aid present on the particle surface of the polyanion material. Examples of the water-soluble carbon material include one or more selected from saccharides, polyols, polyethers, and organic acids. More specifically, for example, monosaccharides such as glucose, fructose, galactose and mannose; disaccharides such as maltose, sucrose and cellobiose; polysaccharides such as starch and dextrin; ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol and butane Examples include polyols and polyethers such as diol, propanediol, polyvinyl alcohol, and glycerin; and organic acids such as citric acid, tartaric acid, and ascorbic acid. Among these, glucose, fructose, sucrose, and dextrin are preferable, and glucose is more preferable from the viewpoint of enhancing solubility and dispersibility in a solvent and effectively functioning as a conductive additive.
上記セルロースナノファイバーとは、全ての植物細胞壁の約５割を占める骨格成分であって、かかる細胞壁を構成する植物繊維をナノサイズまで解繊等することにより得ることができる軽量高強度繊維であり、セルロースナノファイバーが炭化されてなる炭素（セルロースナノファイバー由来の炭素）は、周期的構造を有する。かかるセルロースナノファイバーの繊維径は、１ｎｍ〜５００μｍであり、水への良好な分散性も有している。また、セルロースナノファイバーを構成するセルロース分子鎖では、炭素による周期的構造が形成されていることから、これが炭化されて正極活物質層中おいて上記成分（Ａ）や成分（Ｂ）の粒子間間隙に介在し、優れた電池物性を有する正極を得ることができる。 The cellulose nanofiber is a skeletal component that occupies about 50% of all plant cell walls, and is a lightweight high-strength fiber that can be obtained by defibrating the plant fibers constituting such cell walls to nano size. Carbon obtained by carbonizing cellulose nanofibers (carbon derived from cellulose nanofibers) has a periodic structure. The fiber diameter of the cellulose nanofiber is 1 nm to 500 μm, and has good dispersibility in water. In the cellulose molecular chain constituting the cellulose nanofiber, since a periodic structure of carbon is formed, this is carbonized, and between the particles of the component (A) and the component (B) in the positive electrode active material layer. A positive electrode that is interposed in the gap and has excellent battery properties can be obtained.
これら成分（Ｄ）の導電助剤のなかでも、上記成分（Ａ）及び（Ｂ）とも相まって、良好な電池特性を確保する観点から、ケッチェンブラック、セルロースナノファイバーの炭化物が好ましい。 Among these conductive assistants of component (D), ketjen black and carbides of cellulose nanofibers are preferable from the viewpoint of ensuring good battery characteristics in combination with the components (A) and (B).
本発明の製造方法が備える工程（Ｉ）は、成分（Ｂ）、成分（Ｃ）、及び有機溶媒（Ｅ）を含む混合物Ｘを調製する工程である。
成分（Ｂ）は、上記と同義である。混合物Ｘにおける成分（Ｂ）の含有量は、成分（Ｅ）の有機溶媒１００質量部に対し、好ましくは０．１〜２０質量部であり、より好ましくは０．５〜１０質量部である。
Step (I) included in the production method of the present invention is a step of preparing a mixture X containing component (B), component (C), and organic solvent (E).
Component (B) is as defined above. The content of the component (B) in the mixture X is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the organic solvent of the component (E).
成分（Ｃ）は、上記と同義であり、後述する工程（II）で得られるペースト組成物ＹのｐＨがアルカリ領域に偏向するのを有効に抑制し、成分（Ａ）や成分（Ｂ）の分解等を効果的に抑制することができる。なかでも、ホウ酸が好ましい。混合物Ｘにおける成分（Ｃ）の含有量は、成分（Ｅ）の有機溶媒１００質量部に対し、好ましくは０．００５〜２．５質量部であり、より好ましくは０．０３〜１．５質量部である。 Component (C) has the same meaning as described above, and effectively suppresses the pH of the paste composition Y obtained in the step (II) to be described later from being deflected to the alkaline region, and the components (A) and (B) Decomposition etc. can be controlled effectively. Of these, boric acid is preferred. The content of the component (C) in the mixture X is preferably 0.005 to 2.5 parts by mass, more preferably 0.03 to 1.5 parts by mass with respect to 100 parts by mass of the organic solvent of the component (E). Part.
成分（Ｅ）の有機溶媒としては、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド、１，３−ジメチル−２−イミダゾリジノン等が挙げられる。なかでも、後述する工程（II）で得られるペースト組成物Ｙに適度な粘性を付与する観点から、Ｎ−メチル−２−ピロリドン（ＮＭＰ）が好ましい。 As the organic solvent of component (E), N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, 1,3-dimethyl-2-amide Examples include imidazolidinone. Among these, N-methyl-2-pyrrolidone (NMP) is preferable from the viewpoint of imparting an appropriate viscosity to the paste composition Y obtained in the step (II) described later.
混合物Ｘを調製する際、成分（Ｂ）、成分（Ｃ）、及び有機溶媒（Ｅ）を添加した後、混合するのが好ましく、混合時の温度は、好ましくは１〜４５℃、より好ましくは５〜３５℃であり、混合時間は、好ましくは１〜６０分、より好ましくは３〜３０分である。 When preparing the mixture X, it is preferable to mix after adding a component (B), a component (C), and an organic solvent (E), and the temperature at the time of mixing becomes like this. Preferably it is 1-45 degreeC, More preferably The mixing time is preferably 1 to 60 minutes, more preferably 3 to 30 minutes.
本発明の製造方法が備える工程（II）は、上記工程（Ｉ）で得られた混合物Ｘに、成分（Ａ）、及び成分（Ｄ）を添加して混合し、ペースト組成物Ｙを得る工程である。
成分（Ａ）は、上記と同義である。かかる成分（Ａ）の添加量は、混合物Ｘ中における成分（Ｂ）１００質量部に対し、好ましくは１１０〜１９８００質量部であり、より好ましくは１７０〜９８００質量部である。また、ペースト組成物Ｙ中における成分（Ａ）の含有量は、ペースト組成物Ｙ１００質量％中に、好ましくは１０〜３０質量％であり、より好ましくは１２〜２８質量％である。
Step (II) with which the production method of the present invention is provided is a step in which component (A) and component (D) are added to and mixed with mixture X obtained in step (I) to obtain paste composition Y. It is.
Component (A) is as defined above. The addition amount of the component (A) is preferably 110 to 19800 parts by mass, more preferably 170 to 9800 parts by mass with respect to 100 parts by mass of the component (B) in the mixture X. Further, the content of the component (A) in the paste composition Y is preferably 10 to 30% by mass and more preferably 12 to 28% by mass in 100% by mass of the paste composition Y.
成分（Ｄ）は、上記と同義であり、成分（Ａ）とともに添加してもよく、成分（Ａ）を添加する前、或いは成分（Ａ）を添加した後に添加してもよい。成分（Ｄ）の添加量は、混合物Ｘ中における成分（Ｂ）１００質量部に対し、好ましくは１０〜９００質量部であり、より好ましくは１５〜７００質量部である。また、ペースト組成物Ｙ中における成分（Ｄ）の含有量は、ペースト組成物Ｙ１００質量％中に、好ましくは０．０５〜２７質量％であり、より好ましくは０．０６〜２５質量％である。 Component (D) has the same meaning as described above, and may be added together with component (A), or may be added before component (A) is added or after component (A) is added. The amount of component (D) added is preferably 10 to 900 parts by weight, more preferably 15 to 700 parts by weight, with respect to 100 parts by weight of component (B) in mixture X. Further, the content of the component (D) in the paste composition Y is preferably 0.05 to 27% by mass, more preferably 0.06 to 25% by mass in 100% by mass of the paste composition Y. .
なお、ペースト組成物Ｙ中における成分（Ｂ）の含有量は、ペースト組成物Ｙ１００質量％中に、好ましくは０．１〜１５質量％であり、より好ましくは０．２〜１２質量％である。またペースト組成物Ｙ中における成分（Ｃ）の含有量は、ペースト組成物Ｙ１００質量％中に、好ましくは０．００２〜１．５質量％であり、より好ましくは０．０１〜１．０質量％質量％である。 The content of the component (B) in the paste composition Y is preferably 0.1 to 15% by mass and more preferably 0.2 to 12% by mass in 100% by mass of the paste composition Y. . The content of the component (C) in the paste composition Y is preferably 0.002 to 1.5% by mass, more preferably 0.01 to 1.0% by mass in 100% by mass of the paste composition Y. % Mass%.
成分（Ａ）、及び成分（Ｄ）を添加した後、混合する際の温度は、好ましくは１〜４５℃、より好ましくは５〜３５℃であり、混合時間は、好ましくは１〜６０分、より好ましくは３〜３０分である。 After adding component (A) and component (D), the temperature during mixing is preferably 1 to 45 ° C, more preferably 5 to 35 ° C, and the mixing time is preferably 1 to 60 minutes, More preferably, it is 3 to 30 minutes.
工程（II）において得られるペースト組成物Ｙは、成分（Ａ）や成分（Ｂ）の分解を有効に抑制する観点から、水の含有を制限するのが好ましい。具体的には、水の含有量は、ペースト組成物Ｙ中に、好ましくは１質量％以下であり、より好ましくは０．５質量％以下であり、或いはペースト組成物Ｙは水を含有しないのが好ましい。 The paste composition Y obtained in the step (II) preferably restricts the water content from the viewpoint of effectively suppressing the decomposition of the component (A) and the component (B). Specifically, the content of water is preferably 1% by mass or less, more preferably 0.5% by mass or less in the paste composition Y, or the paste composition Y does not contain water. Is preferred.
工程（II）において得られるペースト組成物Ｙの２５℃における粘度は、好ましくは１〜５０００ｍＰａ・ｓであり、より好ましくは１００〜３０００ｍＰａ・ｓである。なお、かかる粘度は、東機産業社製ＢＩＩ形粘度計を用い、２５℃にて測定される値を意味する。 The viscosity at 25 ° C. of the paste composition Y obtained in the step (II) is preferably 1 to 5000 mPa · s, more preferably 100 to 3000 mPa · s. The viscosity means a value measured at 25 ° C. using a BII viscometer manufactured by Toki Sangyo Co., Ltd.
本発明の製造方法が備える工程（III）は、上記工程（II）で得られたペースト組成物Ｙを正極用集電体上に塗布した後、乾燥し、正極活物質層を形成する工程である。
正極用集電体の材質としては、アルミニウム、ステンレス、チタン、カーボン等が挙げられる。なかでも、アルミニウムが好ましい。正極用集電体の厚みは、電池のサイズにも左右され得ることから特に制限されないが、好ましくは５〜５０μｍであり、より好ましくは１０〜３０μｍである。
Step (III) included in the production method of the present invention is a step of forming the positive electrode active material layer by applying the paste composition Y obtained in the above step (II) onto the positive electrode current collector and then drying it. is there.
Examples of the material for the positive electrode current collector include aluminum, stainless steel, titanium, and carbon. Of these, aluminum is preferable. The thickness of the positive electrode current collector is not particularly limited because it can be influenced by the size of the battery, but is preferably 5 to 50 μm, more preferably 10 to 30 μm.
ペースト組成物Ｙの正極用集電体上への塗布には、スクリーン印刷、ロールコート等の方法を用いることができる。 For the application of the paste composition Y onto the positive electrode current collector, methods such as screen printing and roll coating can be used.
ペースト組成物Ｙを正極用集電体上に塗布した後の乾燥には、真空乾燥、温風乾燥、凍結乾燥のいずれかの方法を用いることができる。
かかる乾燥の後、加熱処理を施すのが好ましい。これにより、成分（Ｂ）を硬化させて剛直性等が付与された正極活物質層を有効に形成することができる。かかる加熱処理には、雰囲気の制御が可能な電気炉を用いることができ、加熱処理の温度は、好ましくは１００〜３００℃、より好ましくは１２０〜２５０℃である。
For drying after applying the paste composition Y on the positive electrode current collector, any of vacuum drying, hot air drying, and freeze drying can be used.
It is preferable to perform heat treatment after such drying. Thereby, the positive electrode active material layer to which rigidity etc. were provided by hardening a component (B) can be formed effectively. An electric furnace capable of controlling the atmosphere can be used for such heat treatment, and the temperature of the heat treatment is preferably 100 to 300 ° C, more preferably 120 to 250 ° C.
正極活物質層の厚みは、例えば電気自動車用の急速な充放電が必要な電池の場合には、好ましくは５〜２００μｍであり、より好ましくは７〜１５０μｍであり、例えば定置用の緩やかな速度での充放電のみ求められる電池の場合には、好ましくは２０〜４００μｍであり、より好ましくは３０〜３００μｍである。 The thickness of the positive electrode active material layer is preferably 5 to 200 μm, more preferably 7 to 150 μm, for example, in the case of a battery that requires rapid charge / discharge for an electric vehicle, for example, a moderate speed for stationary use. In the case of a battery in which only charging / discharging is required, the thickness is preferably 20 to 400 μm, more preferably 30 to 300 μm.
本発明の製造方法において、成分（Ｃ）として成分（ｃ−１）の無機酸を用いた場合、得られるリチウムイオン二次電池用正極は、正極用集電体表面に、次の成分（Ａ）、（Ｂ）、（ｃ−１）、並びに（Ｄ）：
（Ａ）リチウム遷移金属ケイ酸塩化合物、
（Ｂ）ポリイミド樹脂、ポリアミドイミド樹脂、及びポリアミド樹脂から選ばれる結着剤、
（ｃ−１）ホウ酸、及びリン酸二水素アンモニウムから選ばれる無機酸、並びに
（Ｄ）導電助剤
を含む正極活物質層が形成されてなる。
In the production method of the present invention, when the inorganic acid of component (c-1) is used as component (C), the resulting positive electrode for a lithium ion secondary battery has the following components (A ), (B), (c-1), and (D):
(A) a lithium transition metal silicate compound,
(B) a binder selected from polyimide resin, polyamideimide resin, and polyamide resin,
(C-1) A positive electrode active material layer containing an inorganic acid selected from boric acid and ammonium dihydrogen phosphate, and (D) a conductive auxiliary agent is formed.
成分（Ａ）のリチウム遷移金属ケイ酸塩化合物の含有量は、形成される正極活物質層中に、好ましくは５０〜９９質量％であり、より好ましくは６０〜９８質量％であり、さらに好ましくは７０〜９５質量％である。 The content of the lithium transition metal silicate compound as the component (A) is preferably 50 to 99% by mass, more preferably 60 to 98% by mass, and still more preferably in the positive electrode active material layer to be formed. Is 70-95 mass%.
成分（Ｂ）の結着剤の含有量は、正極活物質層中に、好ましくは０．４９〜４５質量％であり、より好ましくは０．９５〜３５質量％であり、さらに好ましくは２．４〜２５質量％である。 The content of the binder of component (B) is preferably 0.49 to 45% by mass, more preferably 0.95 to 35% by mass in the positive electrode active material layer, and still more preferably 2. 4 to 25% by mass.
成分（ｃ−１）の酸の含有量は、正極活物質層中に、好ましくは０．０１〜５質量％であり、より好ましくは０．０５〜３質量％であり、さらに好ましくは０．１〜２質量％である。 The content of the component (c-1) acid is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and still more preferably 0.005% by mass in the positive electrode active material layer. 1-2% by mass.
成分（Ｄ）の導電助剤の含有量は、正極活物質層中に、炭素原子換算量で、好ましくは０．５〜４５質量％であり、より好ましくは１〜３５質量％であり、さらに好ましくは２．５〜２５質量％である。
なお、正極活物質層中に存在する成分（Ｄ）の導電助剤の炭素原子換算量は、炭素・硫黄分析装置を用いて測定した炭素量として、確認することができる。
In the positive electrode active material layer, the content of the conductive assistant of component (D) is preferably 0.5 to 45% by mass, more preferably 1 to 35% by mass, and more preferably 1 to 35% by mass. Preferably it is 2.5-25 mass%.
In addition, the carbon atom conversion amount of the conductive support agent of the component (D) present in the positive electrode active material layer can be confirmed as a carbon amount measured using a carbon / sulfur analyzer.
本発明のリチウムイオン二次電池用正極を適用できるリチウムイオン二次電池としては、かかる本発明のリチウムイオン二次電池用正極に加え、さらに負極と電解液とセパレータを必須構成とするものであれば特に限定されない。 As a lithium ion secondary battery to which the positive electrode for lithium ion secondary battery of the present invention can be applied, in addition to the positive electrode for lithium ion secondary battery of the present invention, a negative electrode, an electrolyte and a separator are essential components. If it does not specifically limit.
ここで、負極については、リチウムイオンを充電時には吸蔵し、かつ放電時には放出することができれば、その材料構成で特に限定されるものではなく、公知の材料構成のものを用いることができる。たとえば、リチウム金属、グラファイト又は非晶質炭素等の炭素材料等である。そしてリチウムを電気化学的に吸蔵・放出し得るインターカレート材料で形成された電極、特に炭素材料を用いることが好ましい。 Here, as long as lithium ions can be occluded at the time of charging and released at the time of discharging, the material structure is not particularly limited, and a known material structure can be used. For example, a carbon material such as lithium metal, graphite, or amorphous carbon. It is preferable to use an electrode formed of an intercalating material capable of electrochemically inserting and extracting lithium, particularly a carbon material.
電解液は、有機溶媒に支持塩を溶解させたものである。有機溶媒は、通常リチウムイオン二次電池の電解液に用いられる有機溶媒であれば特に限定されるものではなく、例えば、カーボネート類、ハロゲン化炭化水素、エーテル類、ケトン類、ニトリル類、ラクトン類、オキソラン化合物等を用いることができる。 The electrolytic solution is obtained by dissolving a supporting salt in an organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent usually used for an electrolyte solution of a lithium ion secondary battery. For example, carbonates, halogenated hydrocarbons, ethers, ketones, nitriles, lactones An oxolane compound or the like can be used.
支持塩は、その種類が特に限定されるものではないが、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣｌＯ4及びＬｉＡｓＦ6から選ばれる無機塩、該無機塩の誘導体、ＬｉＳＯ3ＣＦ3、ＬｉＣ（ＳＯ3ＣＦ3）2及びＬｉＮ（ＳＯ3ＣＦ3）2、ＬｉＮ（ＳＯ2Ｃ2Ｆ5）2及びＬｉＮ（ＳＯ2ＣＦ3）（ＳＯ2Ｃ4Ｆ9）から選ばれる有機塩、並びに該有機塩の誘導体の少なくとも１種であることが好ましい。 The type of the supporting salt is not particularly limited, but an inorganic salt selected from LiPF 6 , LiBF 4 , LiClO 4 and LiAsF 6 , a derivative of the inorganic salt, LiSO 3 CF 3 , LiC (SO 3 CF 3 ) 2 and LiN (SO 3 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 and LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ), and organic salt derivatives It is preferable that it is at least 1 type of these.
セパレータは、正極及び負極を電気的に絶縁し、電解液を保持する役割を果たすものである。たとえば、多孔性合成樹脂膜、特にポリオレフィン系高分子（ポリエチレン、ポリプロピレン）の多孔膜を用いればよい。 The separator plays a role of electrically insulating the positive electrode and the negative electrode and holding the electrolytic solution. For example, a porous synthetic resin film, particularly a polyolefin polymer (polyethylene, polypropylene) porous film may be used.
以下、本発明について、実施例に基づき具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
［製造例１：正極活物質Ａの製造］
ＬｉＯＨ・Ｈ2Ｏ ４．２０ｇ（１００ｍｍｏｌ）、Ｎａ4ＳｉＯ4・ｎＨ2Ｏ １３．９８ｇ（５０ｍｍｏｌ）に超純水３０ｃｍ3 を加えて混合した（この時のｐＨは約１３）。この水分散液にＦｅＳＯ4・７Ｈ2Ｏ ８．９４ｇ（３２．２ｍｏｌ）、ＭｎＳＯ4・５Ｈ2Ｏ３．８２ｇ（１５．８ｍｏｌ）及びＺｒＳＯ4・４Ｈ2Ｏ０．２８ｇ（１ｍｍｏｌ）を添加し、混合した。得られた混合液をオートクレーブに投入し、１５０℃で１２ｈｒ水熱反応を行った。反応液をろ過後、凍結乾燥した。凍結乾燥（約１２時間）して得られた粉末８．４ｇにグルコース（炭素濃度として１０％）及び超純水１０ｃｍ3 を加え、還元雰囲気下で６００℃で１ｈｒ焼成して、正極活物質Ａを得た。
[Production Example 1: Production of positive electrode active material A]
30 cm 3 of ultrapure water was added to and mixed with 4.20 g (100 mmol) of LiOH.H 2 O and 13.98 g (50 mmol) of Na 4 SiO 4 .nH 2 O (pH at this time was about 13). This aqueous dispersion FeSO 4 · 7H 2 O 8.94g ( 32.2mol), was added MnSO 4 · 5H 2 O3.82g (15.8mol ) and ZrSO 4 · 4H 2 O0.28g (1mmol ), mixed did. The obtained mixed solution was put into an autoclave and subjected to a hydrothermal reaction at 150 ° C. for 12 hours. The reaction solution was filtered and then lyophilized. Glucose (carbon concentration: 10%) and ultrapure water (10 cm 3) were added to 8.4 g of the powder obtained by freeze-drying (about 12 hours), and calcined at 600 ° C. for 1 hr in a reducing atmosphere to produce positive electrode active material A Got.
［実施例１］
１０ｗｔ％ホウ酸エタノール溶液１００ｍｇ、ポリイミド（アイエスティ社製ドリームボンド）１００ｍｇ、及びＮ−メチル−２−ピロリドン１．６ｍｇを充分混練し、混合物Ｘを調製した。製造例１で得られた正極活物質Ａ７５０ｍｇとケッチェンブラック（導電剤）１５０ｍｇを混合物Ｘに加えて十分混練し、ペースト組成物Ｙを調製した。正極スラリーを厚さ２０μｍのアルミニウム箔からなる集電体に塗工機を用いて塗布し、８０℃で１２時間の真空乾燥を行った。その後、φ１４ｍｍの円盤状に打ち抜いてハンドプレスを用いて１６ＭＰａで２分間プレスし、Ｎ２雰囲気下で１５０℃の加熱処理を行い正極とした。
形成された正極活物質層中におけるポリイミドの含有量は９．９質量％、ホウ酸の含有量は１質量％であった。
[Example 1]
A mixture X was prepared by sufficiently kneading 100 mg of a 10 wt% boric acid ethanol solution, 100 mg of polyimide (dream bond manufactured by ISTI) and 1.6 mg of N-methyl-2-pyrrolidone. A paste composition Y was prepared by adding 750 mg of the positive electrode active material A obtained in Production Example 1 and 150 mg of ketjen black (conductive agent) to the mixture X and kneading sufficiently. The positive electrode slurry was applied to a current collector made of an aluminum foil having a thickness of 20 μm using a coating machine, and vacuum dried at 80 ° C. for 12 hours. Thereafter, it was punched into a disk shape with a diameter of 14 mm, pressed with a hand press at 16 MPa for 2 minutes, and heat-treated at 150 ° C. in an N 2 atmosphere to obtain a positive electrode.
The content of polyimide in the formed positive electrode active material layer was 9.9% by mass, and the content of boric acid was 1% by mass.
［実施例２］
ホウ酸の代わりにギ酸５ｍｇを用いた以外、実施例１と同様にして正極を作製した。形成された正極活物質層中におけるポリイミドの含有量は１０質量％、ギ酸の含有量は０質量％（熱処理時に揮発）であった。
[Example 2]
A positive electrode was produced in the same manner as in Example 1 except that 5 mg of formic acid was used instead of boric acid. The content of the polyimide in the formed positive electrode active material layer was 10% by mass, and the content of formic acid was 0% by mass (volatile during heat treatment).
［実施例３］
１０ｗｔ％ホウ酸エタノール溶液の代わりにプロピオン酸５ｍｇを用いた以外、実施例１と同様にして正極を作製した。
形成された正極活物質層中におけるポリイミドの含有量は１０質量％、プロピオン酸の含有量は０質量％（熱処理時に揮発）であった。
[Example 3]
A positive electrode was produced in the same manner as in Example 1 except that 5 mg of propionic acid was used instead of the 10 wt% boric acid ethanol solution.
In the formed positive electrode active material layer, the content of polyimide was 10% by mass, and the content of propionic acid was 0% by mass (volatile during heat treatment).
［実施例４］
１０ｗｔ％ホウ酸エタノール溶液の代わりに酢酸１０μｇを用いた以外、実施例１と同様にして正極を作製した。
形成された正極活物質層中におけるポリイミドの含有量は１０質量％、酢酸の含有量は０質量％（熱処理時に揮発）であった。
[Example 4]
A positive electrode was produced in the same manner as in Example 1 except that 10 μg of acetic acid was used instead of the 10 wt% boric acid ethanol solution.
In the formed positive electrode active material layer, the content of polyimide was 10% by mass, and the content of acetic acid was 0% by mass (volatile during heat treatment).
［実施例５］
１０ｗｔ％ホウ酸エタノール溶液の代わりに２０ｗｔ％リン酸二水素アンモニウム水溶液１５０ｍｇを用いた以外、実施例１と同様にして正極を作製した。
形成された正極活物質層中におけるポリイミドの含有量は９．７質量％、リン酸二水素アンモニウムの含有量は２．９質量％であった。
[Example 5]
A positive electrode was produced in the same manner as in Example 1, except that 150 mg of a 20 wt% ammonium dihydrogen phosphate aqueous solution was used instead of the 10 wt% borate ethanol solution.
The content of the polyimide in the formed positive electrode active material layer was 9.7% by mass, and the content of ammonium dihydrogen phosphate was 2.9% by mass.
［比較例１］
酸を添加しなかった以外、実施例１と同様にして正極を作製した。
[Comparative Example 1]
A positive electrode was produced in the same manner as in Example 1 except that no acid was added.
［比較例２］
ポリイミドの代わりにポリフッ化ビニリデン（ＰＶＤＦ、クレハ社製９３０５）を用いた以外、実施例１と同様にして正極を作製した。
[Comparative Example 2]
A positive electrode was produced in the same manner as in Example 1 except that polyvinylidene fluoride (PVDF, 9305 manufactured by Kureha Corporation) was used instead of polyimide.
［試験例］
実施例１〜５及び比較例１〜２の正極を用いてコイン型リチウムイオン二次電池を構築した。負極には、φ１５ｍｍに打ち抜いたリチウム箔を用いた。電解液には、エチレンカーボネート及びエチルメチルカーボネートを体積比１：１の割合で混合した混合溶媒に、ＬＩＰＦ6を１ｍｏｌ／Ｌの濃度で溶解したものを用いた。セパレータには、ポリプロピレンなどの高分子多孔フィルムなど、公知のものを用いた。これらの電池部品を露点が−５０℃以下の雰囲気で常法により組み込み収容し、コイン型リチウム二次電池（ＣＲ−２０３２）を製造した。
[Test example]
Coin-type lithium ion secondary batteries were constructed using the positive electrodes of Examples 1 to 5 and Comparative Examples 1 and 2. A lithium foil punched to φ15 mm was used for the negative electrode. As the electrolytic solution, a solution obtained by dissolving LIPF 6 at a concentration of 1 mol / L in a mixed solvent in which ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 1: 1 was used. As the separator, a known one such as a polymer porous film such as polypropylene was used. These battery components were assembled and housed in a conventional manner in an atmosphere with a dew point of −50 ° C. or lower to produce a coin-type lithium secondary battery (CR-2032).
製造したリチウムイオン二次電池を用いて定電流密度での充放電を行った。このときの充電条件は電流０．１ＣＡ（３３ｍＡ／ｇ）、電圧４．５Ｖの定電流定電圧充電とし、放電条件は電流０．１ＣＡ、終止電圧１．５Ｖの定電流放電とした。温度は全て３０℃とした。さらに、同様の充放電条件において、１００サイクル繰り返し試験を行い、下記式（１）により容量保持率（％）を求めた。
容量保持率（％）＝（１００サイクル後の放電容量）／（１サイクル後の放電容量）
×１００ ・・・（１）
容量保持率の結果を表１に示す。
Charging / discharging at a constant current density was performed using the manufactured lithium ion secondary battery. The charging conditions at this time were constant current and constant voltage charging with a current of 0.1 CA (33 mA / g) and a voltage of 4.5 V, and the discharging conditions were constant current discharging with a current of 0.1 CA and a final voltage of 1.5 V. All temperatures were 30 ° C. Furthermore, 100 cycles were repeatedly tested under the same charge / discharge conditions, and the capacity retention rate (%) was determined by the following formula (1).
Capacity retention (%) = (discharge capacity after 100 cycles) / (discharge capacity after 1 cycle)
× 100 (1)
Table 1 shows the results of capacity retention.
表１から明らかなように、結着剤として成分（Ｂ）ポリイミドを用い、かつ成分（Ｄ）酸を添加して正極活物質層を形成した実施例の正極は比較例と比べて高い容量保持率を有していた。 As is clear from Table 1, the positive electrode of the example using the component (B) polyimide as the binder and adding the component (D) acid to form the positive electrode active material layer has a higher capacity than the comparative example. Had a rate.
Claims (3)
（Ａ）リチウム遷移金属ケイ酸塩化合物、
（Ｂ）ポリイミド樹脂、ポリアミドイミド樹脂、及びポリアミド樹脂から選ばれる結着剤、
（Ｃ）ホウ酸、及びリン酸二水素アンモニウムから選ばれる無機酸（ｃ−１）、並びに酢酸、ギ酸、及びプロピオン酸から選ばれる有機酸（ｃ−２）からなる群より選ばれる１種以上の酸、
（Ｄ）導電助剤、並びに
（Ｅ）有機溶媒
を用いる、リチウムイオン二次電池用正極の製造方法であって、
成分（Ｂ）、成分（Ｃ）、及び成分（Ｅ）を含む混合物Ｘを調製する工程（Ｉ）、
得られた混合物Ｘに、成分（Ａ）、及び成分（Ｄ）を添加して混合し、成分（Ｂ）の含有量が０．１〜１５質量％のペースト組成物Ｙを得る工程（II）、並びに
得られたペースト組成物Ｙを正極用集電体上に塗布した後、乾燥して加熱し、正極活物質層を形成する工程（III）
を備えるリチウムイオン二次電池用正極の製造方法。 The following components (A), (B), (C), (D) and (E):
(A) a lithium transition metal silicate compound,
(B) a binder selected from polyimide resin, polyamideimide resin, and polyamide resin,
(C) One or more selected from the group consisting of an inorganic acid (c-1) selected from boric acid and ammonium dihydrogen phosphate, and an organic acid (c-2) selected from acetic acid, formic acid, and propionic acid Acid,
(D) a conductive assistant, and (E) a method for producing a positive electrode for a lithium ion secondary battery using an organic solvent,
Preparing a mixture X comprising component (B), component (C), and component (E) (I),
Step (II) of adding the component (A) and the component (D) to the obtained mixture X and mixing them to obtain a paste composition Y having a content of the component (B) of 0.1 to 15% by mass. And, after applying the obtained paste composition Y on the positive electrode current collector, drying and heating to form a positive electrode active material layer (III)
A method for producing a positive electrode for a lithium ion secondary battery.
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