JP2006331908A - Manufacturing method of iron lithium phosphate thin film electrode - Google Patents
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Abstract
Description
本発明はリン酸鉄リチウムから構成される薄膜電極の製造方法に関する。 The present invention relates to a method for producing a thin film electrode composed of lithium iron phosphate.
電子機器の小型化に伴い、その主電源やバックアップ電源として高エネルギー密度を有する電池が要望されている。中でもリチウムイオン二次電池は、従来の水溶液系電池に比べ、高電圧・高エネルギー密度を有しており注目を集めている。 With downsizing of electronic devices, a battery having high energy density is demanded as its main power source or backup power source. In particular, lithium ion secondary batteries are attracting attention because they have higher voltages and higher energy densities than conventional aqueous batteries.
リチウムイオン二次電池は、正極としてＬｉＣｏＯ2やＬｉＭｎ2Ｏ4、ＬｉＮｉＯ2などの酸化物、負極としてカーボンやＳｉなどの合金、Ｌｉ4/3Ｔｉ5/3Ｏ4などの酸化物、電解液には炭酸エステルやエーテル系の有機溶媒にＬｉ塩を溶解したものが用いられている。電解液は危険物の第四類に分類される可燃物が使用されており、漏液の可能性があるほか、誤使用時に発火・破裂の恐れがある。リチウムイオン二次電池の安全性及び信頼性を高めるために、安全性に優れるリン酸系活物質の研究開発が盛んに行われている。 Lithium ion secondary batteries are composed of oxides such as LiCoO 2 , LiMn 2 O 4 and LiNiO 2 as positive electrodes, alloys such as carbon and Si as negative electrodes, oxides such as Li 4/3 Ti 5/3 O 4 , electrolytes In this case, a solution obtained by dissolving a Li salt in a carbonic acid ester or an ether organic solvent is used. The electrolyte is a flammable material classified as Class 4 hazardous materials, which may cause leakage and may ignite or rupture when misused. In order to enhance the safety and reliability of lithium ion secondary batteries, research and development of phosphoric acid-based active materials that are excellent in safety are being actively conducted.
リン酸系活物質はその低い電子導電性のため、高率放電特性に課題があり、その導電性を改善するためにカーボンなどの電子導電助剤との混合方法や活物質の１次粒子径の低減などに関して種々の検討が行われてきた（特許文献１、特許文献２）。 Phosphoric acid-based active materials have problems with high-rate discharge characteristics due to their low electronic conductivity, and in order to improve their conductivity, the method of mixing with an electronic conductive aid such as carbon and the primary particle size of the active material Various studies have been made on the reduction of noise (Patent Document 1, Patent Document 2).
一方で、導電性の悪いリン酸系活物質を薄膜化することで高速充放電が可能であることが報告されている（非特許文献１）。レーザーアブレーション法を用いてＬｉＦｅＰＯ4ターゲットをアルゴン雰囲気にて白金板上へと薄膜形成させた後、５００℃にて３時間アニール処理すると、１Ｍ ＬｉＣｌＯ4／ＰＣ系電解液中で可逆性良く動作することが報告されている。このようにレーザーアブレーションなどの真空プロセスを用いると種々の活物質を種々の基板上に薄膜形成させることが可能であるが、一方でこのような真空プロセスはプロセスコストが高いため量産には不向きである、という課題があった。 On the other hand, it has been reported that high-speed charge / discharge is possible by thinning a phosphoric acid active material having poor conductivity (Non-patent Document 1). When a LiFePO 4 target is formed into a thin film on a platinum plate in an argon atmosphere using a laser ablation method and then annealed at 500 ° C. for 3 hours, it operates reversibly in a 1M LiClO 4 / PC electrolyte. It has been reported. As described above, when a vacuum process such as laser ablation is used, various active materials can be formed into thin films on various substrates. On the other hand, such a vacuum process is not suitable for mass production because of high process cost. There was a problem of being.
また、薄膜極板を作製するためのプロセスとして、ゾルーゲル法を用いたものが知られている。非特許文献２において、リチウムイソプロポキシド、酢酸コバルト、ポリビニルピロリドン、酢酸、イソプロパノール、水からなる前駆体を金基板上にスピンコートし、８００℃１時間空気雰囲気で焼成することでＬｉＣｏＯ2薄膜が形成されることが報告されている。また、酢酸コバルトに換えて酢酸マンガンを用いることでＬｉＭｎ2Ｏ4薄膜極板が得られることも報告されている。Ｃｏ（ＩＩＩ）またはＭｎ（ＩＶ）を有するこれらの活物質は空気などの酸化雰囲気での焼成が必須であり、また、有機溶媒を用いる系においては生成するカーボンを酸素により焼き飛ばす必要があるため、用いられる基板の材料としては高温・酸化雰囲気で安定に存在し得る金、白金、銀などの貴金属を用いる必要があった。このため、量産に際しては集電体材料コストが高くなるという課題があった。 Also, a process using a sol-gel method is known as a process for producing a thin film electrode plate. In Non-Patent Document 2, a precursor made of lithium isopropoxide, cobalt acetate, polyvinyl pyrrolidone, acetic acid, isopropanol, and water is spin-coated on a gold substrate and baked in an air atmosphere at 800 ° C. for 1 hour to obtain a LiCoO 2 thin film. It is reported to form. It has also been reported that a LiMn 2 O 4 thin film electrode plate can be obtained by using manganese acetate instead of cobalt acetate. These active materials having Co (III) or Mn (IV) must be baked in an oxidizing atmosphere such as air, and in a system using an organic solvent, it is necessary to burn off generated carbon with oxygen. As a substrate material to be used, it was necessary to use a noble metal such as gold, platinum or silver which can exist stably in a high temperature / oxidizing atmosphere. For this reason, in mass production, there existed a subject that the current collector material cost became high.
また、液相からＬｉＦｅＰＯ4を合成した例として非特許文献３がある。本報文によれば、酢酸リチウム、酢酸鉄、リン酸をエチレングリコールに溶解させてゲルを作製し、これを窒素雰囲気中にて７００℃１２時間の熱処理を施すことで表面がカーボンコートされたＬｉＦｅＰＯ4を得るというものである。しかしながら、その目的はＬｉＦｅＰＯ4粒子をカーボン被覆して粒子の電子導電性を向上させるためであり、カーボン被覆された粒子は緻密化が進行しないため、緻密な構造を有するＬｉＦｅＰＯ4薄膜極板を作製することは困難であった。
先述のように、薄膜電極においては電子導電性の低い活物質でも高速充放電が可能となるが、レーザーアブレーションなどの気相法を用いるとプロセスコストが高くなるという課題があった。一方、ゾルーゲル法を用いた場合、副成するカーボンなどを焼き飛ばすため、また遷移金属の酸化数を高く保持するために空気中での焼成が不可欠であり、このために集電体には貴金属を用いる必要があった。このため、集電体材料が高価になるという課題があった。本発明はこれらの課題を解決し、安価にリン酸系活物質の薄膜電極を提供することが可能となる製造方法に関するものである。 As described above, a thin film electrode can be charged and discharged at high speed even with an active material having low electronic conductivity. However, when a vapor phase method such as laser ablation is used, there is a problem that process cost increases. On the other hand, when using the sol-gel method, firing in air is indispensable in order to burn off by-product carbon, etc., and to maintain a high oxidation number of the transition metal. It was necessary to use. For this reason, there existed a subject that a collector material became expensive. The present invention relates to a production method capable of solving these problems and providing a thin film electrode of a phosphoric acid-based active material at a low cost.
本発明は、少なくともＬｉ、Ｆｅ、Ｐを含む溶液を金属基板上へ塗布し、熱処理を施して薄膜電極を作製する製造方法において、水蒸気を５〜９０体積％を含む低酸素分圧ガス雰囲気中、５００℃以上８００℃以下で加熱処理をほどこしてリン酸鉄リチウム薄膜電極を製造することを特徴とする。 The present invention relates to a manufacturing method for producing a thin film electrode by applying a solution containing at least Li, Fe, and P onto a metal substrate and performing a heat treatment in a low oxygen partial pressure gas atmosphere containing 5 to 90% by volume of water vapor. The lithium iron phosphate thin film electrode is manufactured by performing a heat treatment at 500 ° C. or more and 800 ° C. or less.
本発明によれば、リン酸系活物質であるオリビン型のＬｉＦｅＰＯ4の緻密な薄膜電極を安価に提供することができる。 According to the present invention, a dense thin film electrode of olivine type LiFePO 4 which is a phosphoric acid active material can be provided at low cost.
本発明は、少なくともＬｉ、Ｆｅ、Ｐを含む溶液を金属基板上へ塗布し、熱処理を施して薄膜電極を作製する製造方法において、水蒸気を５〜９０体積％を含む低酸素分圧ガス雰囲気中、８００℃以下で加熱処理することを特徴とするリン酸鉄リチウム薄膜電極の製造方法に関する。この水蒸気の添加により、有機物の熱分解が促進されるため、カーボン類の副成を抑制することができるため、合成されるＬｉＦｅＰＯ４を緻密化することが可能となる。また、有機化合物の熱分解は吸熱反応であるため、ＣＯ2やＨ2及びＮ2などと比べて比熱の大きいＨ2Ｏを用いることで分解に必要な熱が円滑に供給される効果もある。熱処理温度が５００℃を下回ると活物質であるＬｉＦｅＰＯ4の生成は困難であり、熱処理温度が８００℃を上回ると活物質の異常粒成長が起こり活物質層の平滑性が低下したり、集電体の熱変形が生じる恐れがある。 The present invention relates to a manufacturing method for producing a thin film electrode by applying a solution containing at least Li, Fe, and P onto a metal substrate and performing a heat treatment in a low oxygen partial pressure gas atmosphere containing 5 to 90% by volume of water vapor. The present invention relates to a method for producing a lithium iron phosphate thin film electrode, characterized by heat treatment at 800 ° C. or lower. Since the thermal decomposition of the organic matter is promoted by the addition of the water vapor, carbon by-products can be suppressed, so that the synthesized LiFePO4 can be densified. Moreover, since the thermal decomposition of the organic compound is an endothermic reaction, there is an effect that the heat necessary for the decomposition can be smoothly supplied by using H 2 O having a large specific heat compared with CO 2 , H 2 and N 2. . When the heat treatment temperature is lower than 500 ° C., it is difficult to produce LiFePO 4 as an active material. When the heat treatment temperature is higher than 800 ° C., abnormal grain growth of the active material occurs and the smoothness of the active material layer is reduced. There is a risk of thermal deformation of the body.
合成される活物質ＬｉＦｅＰＯ4中のＦｅの酸化数は２価であり、この２価のＦｅが安定な領域で熱処理を行う必要がある。そのため、熱処理する雰囲気の酸素分圧は下記一般式（１）の範囲内であることが望ましく、 The oxidation number of Fe in the synthesized active material LiFePO 4 is divalent, and it is necessary to perform heat treatment in a region where the divalent Fe is stable. Therefore, the oxygen partial pressure of the atmosphere to be heat-treated is preferably within the range of the following general formula (1),
酸素分圧が一般式（１）で規定される範囲を上回るとＦｅが酸化されたり、後述する金属基板が酸化される恐れがある。一方、酸素分圧が一般式（１）で規定される範囲未満にす
ると副成するカーボン類の除去が困難となる。
If the oxygen partial pressure exceeds the range defined by the general formula (1), Fe may be oxidized or a metal substrate described later may be oxidized. On the other hand, when the oxygen partial pressure is less than the range defined by the general formula (1), it is difficult to remove carbons generated as by-products.
金属基板としてＡｌ、Ｔｉ、Ｎｉ、ＳＵＳなどを用いることができる。ただし、Ａｌは融点が６６０℃であるため、熱処理温度は６００℃以下で行うことが必要である。 Al, Ti, Ni, SUS, or the like can be used as the metal substrate. However, since Al has a melting point of 660 ° C., the heat treatment temperature must be 600 ° C. or lower.
酸素分圧を一般式（１）で規定される範囲に安定して調整するために、二酸化炭素と水素及び窒素からなるガスを用いることができる。水素の体積含有率は安全のため、水素の爆発限界以下の４％以下にすることが望ましい。これらの気体から構成されるガスは平衡反応により、安定した酸素分圧を維持することが可能となる。 In order to stably adjust the oxygen partial pressure within the range defined by the general formula (1), a gas composed of carbon dioxide, hydrogen, and nitrogen can be used. For safety, the volume content of hydrogen is preferably 4% or less, which is below the explosion limit of hydrogen. A gas composed of these gases can maintain a stable oxygen partial pressure by an equilibrium reaction.
活物質を合成するための前駆体溶液を構成するＬｉ化合物として、酢酸リチウム二水和物、リチウムアルコキシドから選ばれる少なくとも１つを用いることができる。リチウムアルコキシドとしてはメトキシド、エトキシド、イソプロポキシド、ブトキシドが一般的に用いられる。これらの化合物は種々の溶媒に対して易溶であり、前駆体溶液の調整が容易である。Ｆｅ源としては、酢酸塩や硝酸塩ｎ水和物（ｎは０から１０までの正数）を用いることができる。特にフェロセン及びその誘導体を前駆体として用いると前駆体溶液の取り扱いが容易になる。Ｐ源としてはリン酸、リン酸エステル（ＰＯ（ＯＲ）3-n（ＯＨ）n： Ｒは炭素数１〜６の脂肪族炭化水素、ｎは０〜２の整数）から選ばれる少なくとも１つを用いることができる。リン酸エステルの炭素鎖は短い方がカーボンの副成が抑制できるため短時間での合成が可能であるが、リン酸エステルの揮発の恐れがあり化学両論比が狙いからずれる恐れがある。 As the Li compound constituting the precursor solution for synthesizing the active material, at least one selected from lithium acetate dihydrate and lithium alkoxide can be used. As lithium alkoxide, methoxide, ethoxide, isopropoxide and butoxide are generally used. These compounds are easily soluble in various solvents, and the preparation of the precursor solution is easy. As the Fe source, acetate or nitrate n-hydrate (n is a positive number from 0 to 10) can be used. In particular, when ferrocene and its derivatives are used as precursors, handling of the precursor solution becomes easy. The P source is at least one selected from phosphoric acid and phosphoric acid ester (PO (OR) 3-n (OH) n : R is an aliphatic hydrocarbon having 1 to 6 carbon atoms, and n is an integer of 0 to 2). Can be used. The shorter the carbon chain of the phosphate ester, the shorter the carbon by-product can be suppressed, so that the synthesis can be performed in a short time. However, the phosphate ester may volatilize and the stoichiometric ratio may not be aimed.
前駆体溶液を構成する溶媒としてはエタノール、イソプロパノール、酢酸、水、Ｎ−メチルピロリドン、エチレングリコール、アセトン、ＴＨＦから選ばれる少なくとも１つから構成することができる。溶解度が大きく、沸点の低いアセトンやＴＨＦを溶媒とした場合、カーボンの副成が少なくて望ましいが、金属基板への塗布時の溶媒の揮発が激しいため工程の管理が困難となる。反対に、Ｎ−メチルピロリドンを用いた場合、前駆体溶液は非常に安定して工程管理が容易であるが、熱分解によりカーボンが生成しやすく薄膜極板製造に長時間を要するという欠点がある。 The solvent constituting the precursor solution can be composed of at least one selected from ethanol, isopropanol, acetic acid, water, N-methylpyrrolidone, ethylene glycol, acetone, and THF. When acetone or THF having a high solubility and a low boiling point is used as a solvent, it is desirable because there are few carbon by-products, but the process is difficult to manage because the solvent is volatile during application to a metal substrate. On the contrary, when N-methylpyrrolidone is used, the precursor solution is very stable and process management is easy, but there is a disadvantage that carbon is easily generated by thermal decomposition and a long time is required for manufacturing a thin film electrode. .
本発明で形成される薄膜極板の活物質層厚みは活物質の前駆体溶液の粘度に大きく左右される。スピンコートなどで金属基板上に前駆体溶液を塗布する場合、ポリビニルピロリドンやポリビニルブチラール、ポリエチレンオキシドなどを添加して溶液の粘度を大きくすることで活物質層厚みを大きくすることができる。 The thickness of the active material layer of the thin film electrode plate formed in the present invention greatly depends on the viscosity of the precursor solution of the active material. When a precursor solution is applied onto a metal substrate by spin coating or the like, the active material layer thickness can be increased by increasing the viscosity of the solution by adding polyvinylpyrrolidone, polyvinyl butyral, polyethylene oxide, or the like.
以下に本発明を実施例に基づいて説明する。 The present invention will be described below based on examples.
（前駆体溶液の調製）
Ｆｅ（ＯＣＯＣＨ3）2 ８７０ｍｇ、ＬｉＯＣＯＣＨ3 ５１０ｍｇ、Ｈ3ＰＯ4 ４９０ｍｇをそれぞれ秤量し、エルレンマイヤーフラスコへ投入し、Ｎ−メチルピロリドン１５ｍＬへ溶解させた。
(Preparation of precursor solution)
Fe (OCOCH 3 ) 2 870 mg, LiOCOCH 3 510 mg, and H 3 PO 4 490 mg were weighed, put into an Erlenmeyer flask, and dissolved in 15 mL of N-methylpyrrolidone.
（金属基板への塗布）
表面を粗化処理した直径１５ｍｍ、厚さ１ｍｍのＳＵＳ基板上へ先述の前駆体溶液を３０００ｒｐｍにてスピンコートした。この前駆体溶液塗布後のＳＵＳ基板を１５０℃にて真空乾燥させた。
(Application to metal substrate)
The precursor solution described above was spin-coated at 3000 rpm on a SUS substrate having a diameter of 15 mm and a thickness of 1 mm whose surface had been roughened. The SUS substrate after the application of the precursor solution was vacuum-dried at 150 ° C.
（薄膜極板の作製）
上記前駆体溶液を塗布・乾燥させたＳＵＳ基板を雰囲気炉に入れ、昇温速度２００℃／
ｈ、最高温度７００℃、保持時間２ｈの温度スケジュールを用いて熱処理した。低酸素分圧ガスとしてＣＯ2／Ｈ2／Ｎ2 ＝ ４．９９／０．０１／９５の組成のガスを用い、水蒸気の体積が５、２０、３０、５０、９０％の５水準になるよう調整したガスを、それぞれ総ガス流量が温度７００℃、１気圧にて、１２Ｌ／ｍｉｎとなるように炉内温度が２００℃の時点から供給し、薄膜極板を作製した。
これを実施例１とする。
(Preparation of thin film electrode)
The SUS substrate coated with the precursor solution and dried is placed in an atmosphere furnace, and the temperature increase rate is 200 ° C. /
h, heat treatment was performed using a temperature schedule of a maximum temperature of 700 ° C. and a holding time of 2 h. A gas having a composition of CO 2 / H 2 / N 2 = 4.99 / 0.01 / 95 is used as the low oxygen partial pressure gas, and the volume of water vapor becomes five levels of 5, 20, 30, 50, and 90%. The gas thus adjusted was supplied from the time when the furnace temperature was 200 ° C. so that the total gas flow rate was 12 L / min at a total gas flow rate of 700 ° C. and 1 atm to produce a thin film electrode plate.
This is Example 1.
熱処理温度を５５０℃とし、水蒸気添加量を３０体積％としたこと以外は実施例１と同様にして薄膜極板を作製した。これを実施例２とする。 A thin-film electrode plate was produced in the same manner as in Example 1 except that the heat treatment temperature was 550 ° C. and the amount of water vapor was 30% by volume. This is Example 2.
熱処理温度を７５０℃とし、水蒸気添加量を３０体積％としたこと以外は実施例１と同様にして薄膜極板を作製した。これを実施例３とする。 A thin-film electrode plate was produced in the same manner as in Example 1 except that the heat treatment temperature was 750 ° C. and the amount of water vapor was 30% by volume. This is Example 3.
（比較例１）
水蒸気を添加しなかったこと以外は実施例１と同様にして薄膜極板を作製した。これを比較例１とする。
(Comparative Example 1)
A thin film electrode plate was prepared in the same manner as in Example 1 except that no water vapor was added. This is referred to as Comparative Example 1.
（比較例２）
熱処理温度を８５０℃とし、水蒸気添加量を３０体積％としたこと以外は実施例１と同様にして薄膜極板を作製した。これを比較例２とする。
(Comparative Example 2)
A thin-film electrode plate was produced in the same manner as in Example 1 except that the heat treatment temperature was 850 ° C. and the amount of water vapor was 30% by volume. This is referred to as Comparative Example 2.
（比較例３）
熱処理温度を４５０℃とし、水蒸気添加量を３０体積％としたこと以外は実施例１と同様にして薄膜極板を作製した。これを比較例３とする。
(Comparative Example 3)
A thin-film electrode plate was produced in the same manner as in Example 1 except that the heat treatment temperature was 450 ° C. and the amount of water vapor was 30% by volume. This is referred to as Comparative Example 3.
（比較例４）
ＣＯ2／Ｈ2／Ｎ2 ＝ ４．９９／０．０１／９５の組成の低酸素分圧ガスに替えて空気を用い、水蒸気添加量を３０体積％としたこと以外は実施例１と同様にして薄膜極板を作製した。これを比較例４とする。
(Comparative Example 4)
Example 1 except that air was used instead of the low oxygen partial pressure gas having a composition of CO 2 / H 2 / N 2 = 4.99 / 0.01 / 95 and the amount of water vapor was 30% by volume. Thus, a thin film electrode plate was produced. This is referred to as Comparative Example 4.
（電池の作製）
作製した薄膜極板にＡｌ製リードを取り付け、リードを取り付けた金属Ｌｉを対極としてＰＰ製セパレータを間に挟んで対向させ、電解液に１Ｍ ＬｉＣｌＯ4のエチレンカーボネート／プロピレンカーボネート（体積比１／１）溶液を用いてＡｌラミネートを用いて封止し、電池を構成した。
(Production of battery)
An Al lead is attached to the produced thin film electrode plate, and a metal Li to which the lead is attached is used as a counter electrode with a PP separator interposed therebetween, and 1M LiClO 4 ethylene carbonate / propylene carbonate (volume ratio 1/1) is used as the electrolyte. ) A battery was constructed by sealing with an Al laminate using the solution.
（電池の評価）
これらの電池を室温にて１００μＡ／ｃｍ2の電流密度で２．５から４．０Ｖの範囲で充放電を行った。なお、利用率は、各薄膜極板を全溶解させてＩＣＰ分析によりＬｉ量を算出し、Ｌｉが全てＬｉＦｅＰＯ4であったと仮定して算出した。表１に各電極の１サイクル目の放電利用率と１０サイクル目の放電利用率を示す。
(Battery evaluation)
These batteries were charged and discharged at a current density of 100 μA / cm 2 at room temperature in the range of 2.5 to 4.0 V. The utilization rate was calculated on the assumption that all the thin-film electrode plates were dissolved, the amount of Li was calculated by ICP analysis, and that all Li was LiFePO 4 . Table 1 shows the discharge utilization rate at the first cycle and the discharge utilization rate at the 10th cycle of each electrode.
ＬｉＦｅＰＯ4の理論容量１７０ｍＡｈ／ｇに対し、本発明による実施例１は１４５〜１５８ｍＡｈ／ｇの初期利用率を示し、１０サイクル目においてもほぼ同程度の利用率が維持された。また、５５０℃の熱処理を行った実施例２では１３０ｍＡｈ／ｇを越える利用率、７５０℃の熱処理を行った実施例３では１５０ｍＡｈ／ｇを越える利用率をそれぞれ示し、１０サイクル後も同程度の利用率が維持されていた。 In contrast to the theoretical capacity of 170 mAh / g of LiFePO 4 , Example 1 according to the present invention showed an initial utilization rate of 145 to 158 mAh / g, and the utilization rate was almost the same even at the 10th cycle. In Example 2 where the heat treatment at 550 ° C. was performed, the utilization rate exceeded 130 mAh / g, and in Example 3 where the heat treatment at 750 ° C. was performed, the utilization rate exceeded 150 mAh / g. The utilization rate was maintained.
一方、熱処理時に水蒸気を添加しなかった比較例１においては初期容量は１４４ｍＡｈ／ｇと良好であったが１０サイクル目には１３ｍＡｈ／ｇにまで利用率が低下した。これは副成したカーボンによりＬｉＦｅＰＯ4層が緻密化するのが妨げられ、充放電サイクルを重ねるに従って活物質層の崩壊が起こり活物質同士及び活物質／ＳＵＳ集電体間の電子電導パスが切断されたためであると考えられる。 On the other hand, in Comparative Example 1 in which water vapor was not added during the heat treatment, the initial capacity was as good as 144 mAh / g, but the utilization rate decreased to 13 mAh / g at the 10th cycle. This prevents the LiFePO 4 layer from being densified by the by-produced carbon, and the active material layer collapses as the charge / discharge cycle is repeated, and the electronic conductive path between the active materials and the active material / SUS current collector is disconnected. It is thought that it was because it was done.
また、熱処理温度を８５０℃とした比較例２では初期利用率が３５ｍＡｈ／ｇと低くなった。これは熱処理により活物質の粒成長が進行し、ＬｉＦｅＰＯ4の粒径が大きくなったため、活物質表面から活物質内部へのＬｉの拡散距離及び電子電導の距離が長くなったために利用率が低下したものと考えられる。また、熱処理温度を４５０℃とした比較例３では充放電が行われなかった。これは４５０℃の熱処理では活物質であるＬｉＦｅＰＯ4が生成しなかったためであると考えられる。 In Comparative Example 2 in which the heat treatment temperature was 850 ° C., the initial utilization rate was as low as 35 mAh / g. This is because the grain growth of the active material has progressed due to the heat treatment, and the particle size of LiFePO 4 has increased, so the diffusion rate of Li from the active material surface to the inside of the active material and the distance of electronic conduction have increased, and the utilization rate has decreased. It is thought that. Moreover, charging / discharging was not performed in the comparative example 3 which made heat processing temperature 450 degreeC. This is considered to be because LiFePO 4 which is an active material was not generated by the heat treatment at 450 ° C.
低酸素分圧ガスに替えて空気を用いた比較例４においては充放電は全く不可能であった。これは空気によりＦｅ（ＩＩ）が酸化されたためＬｉＦｅＰＯ4が生成しなかったためであると考えられる。
以上の結果から、本発明により製造されるリン酸鉄リチウム薄膜極板は初期の活物質利用率及び充放電サイクル寿命特性に優れることが示された。
In Comparative Example 4 in which air was used instead of the low oxygen partial pressure gas, charging / discharging was not possible at all. This is considered to be because LiFePO 4 was not generated because Fe (II) was oxidized by air.
From the above results, it was shown that the lithium iron phosphate thin-film electrode plate produced according to the present invention is excellent in the initial active material utilization and charge / discharge cycle life characteristics.
水蒸気添加量を３０体積％とし、ＣＯ2／Ｈ2／Ｎ2 ＝ ４．９９／０．０１／９５の組成の低酸素分圧ガスに替えて、純度４Ｎの高純度アルゴンガスを用いたこと以外は実施例１と同様に薄膜極板を作製した。これを実施例４とする。 A high purity argon gas having a purity of 4N was used instead of the low oxygen partial pressure gas having a composition of CO 2 / H 2 / N 2 = 4.99 / 0.01 / 95, with the amount of steam added being 30% by volume. A thin film electrode plate was produced in the same manner as in Example 1 except for the above. This is Example 4.
水蒸気添加量を３０体積％とし、ＣＯ2／Ｈ2／Ｎ2 ＝ ４．９９／０．０１／９５の組成の低酸素分圧ガスに替えて、純度４Ｎの高純度ＣＯ2ガスを用いたこと以外は実施例１と同様に薄膜極板を作製した。これを実施例５とする。 A high-purity CO 2 gas having a purity of 4N was used instead of the low oxygen partial pressure gas having a composition of CO 2 / H 2 / N 2 = 4.99 / 0.01 / 95 with the amount of steam added being 30% by volume. A thin film electrode plate was prepared in the same manner as in Example 1 except that. This is Example 5.
水蒸気添加量を３０体積％とし、ＣＯ2／Ｈ2／Ｎ2 ＝ ４．９９／０．０１／９５の組成の低酸素分圧ガスに替えて、純度４Ｎの高純度Ｈ2ガスを用いたこと以外は実施例１と同様に薄膜極板を作製した。これを実施例６とする。 A high-purity H 2 gas having a purity of 4N was used instead of the low oxygen partial pressure gas having a composition of CO 2 / H 2 / N 2 = 4.99 / 0.01 / 95 with the amount of steam added being 30% by volume. A thin film electrode plate was prepared in the same manner as in Example 1 except that. This is Example 6.
実施例４から６についても先述の方法で電池を構成し、評価を行った。結果を表２に示す。 Also in Examples 4 to 6, batteries were configured by the above-described method and evaluated. The results are shown in Table 2.
実施例４、５においては１２０ｍＡｈ／ｇを越える１サイクル目利用率が得られた。１０サイクル目利用率は実施例１と比較して若干、低下する傾向が見られた。これは実施例１で用いたＣＯ2／Ｈ2／Ｎ2 ＝ ４．９９／０．０１／９５の組成の低酸素分圧ガスが、 In Examples 4 and 5, the first cycle utilization rate exceeding 120 mAh / g was obtained. The 10th cycle utilization rate tended to decrease slightly compared to Example 1. This is because the low oxygen partial pressure gas having the composition of CO 2 / H 2 / N 2 = 4.99 / 0.01 / 95 used in Example 1 is used.
のような平衡反応により酸素分圧の緩衝作用があるため一定の酸素分圧が維持され、極板中に副成するカーボン類がこの酸素により除去されると考えられる。実施例１における７００℃における平衡酸素分圧は１０-16気圧程度と見積もられる。一方、実施例４の場合、高純度アルゴンにおいてはそのような緩衝作用はなく、また、７００℃においては式（４）の反応の平衡定数が約１０-11のオーダーであり、酸素分圧が１０-7気圧程度であると見積もられる。このため、Ｆｅ（ＩＩ）の一部がＦｅ（ＩＩＩ）へと酸化されたために利用率が低くなったものと考えられる。 It is considered that the oxygen partial pressure is buffered by the equilibrium reaction as described above, so that a constant oxygen partial pressure is maintained, and carbons by-produced in the electrode plate are removed by this oxygen. The equilibrium oxygen partial pressure at 700 ° C. in Example 1 is estimated to be about 10 −16 atm. On the other hand, in the case of Example 4, such a buffering action is not obtained in high-purity argon, and the equilibrium constant of the reaction of the formula (4) is on the order of about 10 −11 at 700 ° C., and the oxygen partial pressure is It is estimated to be about 10 −7 atm. For this reason, it is considered that the utilization rate was lowered because part of Fe (II) was oxidized to Fe (III).
実施例６においては、７００℃における平衡酸素分圧は１０-22気圧程度の極微量と見積もられるため、極板中に含まれるカーボン量が若干、実施例１よりも多く、ＬｉＦｅＰＯ4薄膜の緻密化が進行し難かったためであると考えられる。 In Example 6, since the equilibrium oxygen partial pressure at 700 ° C. is estimated to be a very small amount of about 10 −22 atm, the amount of carbon contained in the electrode plate is slightly larger than in Example 1 and the LiFePO 4 thin film is dense. This is thought to be because it was difficult to proceed.
一般式（１）から算出される７００℃における好ましい酸素分圧の値は１０-17.1気圧から１０-11.8気圧の範囲である。以上のように、低酸素分圧ガス雰囲気として、一般式（１）の範囲を満たすガスを用いることが好ましく、さらに低酸素分圧ガス雰囲気が、ＣＯ2などの酸素を放出可能なガスと、Ｈ2のように酸素と反応するガスの混合物から調整されることがより望ましいことが明らかとなった。 The preferred value of the oxygen partial pressure at 700 ° C. as calculated from the formula (1) is in the range of from 10 -17.1 atm 10 -11.8 atm. As described above, it is preferable to use a gas that satisfies the range of the general formula (1) as the low oxygen partial pressure gas atmosphere, and the low oxygen partial pressure gas atmosphere includes a gas capable of releasing oxygen such as CO 2 ; it was revealed that more desirable to be adjusted from a mixture of gases which react with oxygen as H 2.
水蒸気添加量を３０体積％に固定し、基板にそれぞれＡｌ、Ｔｉ、Ｎｉを用いたこと以外は実施例１と同様にして薄膜極板を作製した。ただし、Ａｌ基板を用いた場合のみ、熱処理温度を６００℃とした。これを実施例７とする。 A thin-film electrode plate was produced in the same manner as in Example 1 except that the amount of water vapor was fixed at 30% by volume and Al, Ti, and Ni were used for the substrate, respectively. However, the heat treatment temperature was set to 600 ° C. only when an Al substrate was used. This is Example 7.
水蒸気添加量を３０体積％に固定し、基板にそれぞれＣｕを用いたこと以外は実施例１と同様にして薄膜極板を作製した。これを実施例８とする。 A thin film electrode plate was prepared in the same manner as in Example 1 except that the amount of water vapor was fixed at 30% by volume and Cu was used for each substrate. This is Example 8.
水蒸気添加量を３０体積％に固定し、基板にそれぞれＡｇを用いたこと以外は実施例１と同様にして薄膜極板を作製した。これを実施例９とする。 A thin-film electrode plate was produced in the same manner as in Example 1 except that the amount of water vapor was fixed at 30% by volume and Ag was used for each substrate. This is Example 9.
実施例５及び比較例４、５についても先述の方法で電池を構成し、評価を行った。結果を表３に示す。 Regarding Example 5 and Comparative Examples 4 and 5, batteries were constructed by the above-described method and evaluated. The results are shown in Table 3.
Ａｌ基板を用いた場合、実施例１のＳＵＳ基板を用いた場合に比べて利用率低下が見られた。これは熱処理温度が低かったこと、及び熱力学的には本熱処理雰囲気においてＡｌが不安定な領域であるため、Ａｌ表面の酸化被膜とＬｉＦｅＰＯ4とが副反応を起こした可能性が考えられるが詳細は不明である。一方、ＴｉやＮｉを基板に用いた場合、良好な初期利用率及びサイクル寿命特性が得られた。 When the Al substrate was used, the utilization rate was reduced as compared with the case where the SUS substrate of Example 1 was used. This is because the heat treatment temperature was low, and thermodynamically, Al is an unstable region in this heat treatment atmosphere, so there is a possibility that a side reaction occurred between the oxide film on the Al surface and LiFePO 4. Details are unknown. On the other hand, when Ti or Ni was used for the substrate, good initial utilization and cycle life characteristics were obtained.
一方、Ｃｕ、Ａｇを基板として用いた実施例８及び実施例９においては、最初の充電において４．０Ｖまで電圧が上昇せず、電池が内部短絡を起こしていることが分かった。これはＣｕ、Ａｇが初充電時に溶解し、負極へと析出してセパレータを貫通したものと考えられる。 On the other hand, in Example 8 and Example 9 which used Cu and Ag as a board | substrate, it turned out that a voltage does not rise to 4.0V in the first charge, but has caused the internal short circuit. This is presumably because Cu and Ag were dissolved during the initial charge, deposited on the negative electrode, and penetrated the separator.
以上のように、本発明によればＳＵＳの他、Ａｌ、Ｔｉ及びＮｉを基板として用いることが可能であることが明らかとなった。 As described above, according to the present invention, it has become clear that Al, Ti and Ni can be used as a substrate in addition to SUS.
次に、種々の前駆体溶液を作製し、検討を行った。 Next, various precursor solutions were prepared and examined.
ＬｉＯｉ−Ｐｒ２２０ｍｇ、フェロセン６２０ｍｇ、ＰＯ（ＯＥｔ）3６０７ｍｇをそれぞれ秤量し、エルレンマイヤーフラスコに投入した後、ＴＨＦ１０ｍＬへと溶解させて前駆体溶液を調整した。本前駆体溶液を直径１５ｍｍ、厚さ１ｍｍのＮｉ基板上に３０００ｒｐｍにてスピンコートし、真空中１００℃で乾燥させた。この後、実施例７と同様に、水蒸気添加量を３０体積％として最高温度７００℃で熱処理を行い薄膜極板を作製した。これを実施例１０とする。 LiOi-Pr 220 mg, ferrocene 620 mg, and PO (OEt) 3 607 mg were weighed and put into an Erlenmeyer flask, and then dissolved in 10 mL of THF to prepare a precursor solution. This precursor solution was spin-coated at 3000 rpm on a Ni substrate having a diameter of 15 mm and a thickness of 1 mm, and dried at 100 ° C. in a vacuum. Thereafter, in the same manner as in Example 7, a heat treatment was performed at a maximum temperature of 700 ° C. with a water vapor addition amount of 30% by volume to produce a thin film electrode plate. This is Example 10.
ＬｉＯｉ−Ｐｒ２２０ｍｇ、Ｆｅ（ＩＩ）（ＳＯ4）2・７Ｈ2Ｏ１２５１ｍｇ、Ｈ3ＰＯ4３２７ｍｇをそれぞれ秤量し、Ａｒ置換したＳｃｈｌｅｎｋチューブへ投入し、脱酸素した酢酸１０ｍＬを加えて溶解させて前駆体溶液を調整した。本前駆体溶液を直径１５ｍｍ、厚さ１ｍｍのＮｉ基板上に３０００ｒｐｍにてスピンコートし、真空中１００℃で乾燥させた。なお、本系においてはスピンコートをＡｒグローブボックス中で行い、前駆体溶液塗布後のＮｉ基板を出来るだけ空気に触れさせないように操作した。この後、実施例７と同様に、水蒸気添加量を３０体積％として最高温度７００℃で熱処理を行い薄膜極板を作製した。これを実施例１１とする。 LiOi-Pr 220 mg, Fe (II) (SO 4 ) 2 · 7H 2 O 1251 mg, H 3 PO 4 327 mg were weighed, put into an Ar-substituted Schlenk tube, dissolved in 10 mL of deoxygenated acetic acid, and precursor. The solution was adjusted. This precursor solution was spin-coated at 3000 rpm on a Ni substrate having a diameter of 15 mm and a thickness of 1 mm, and dried at 100 ° C. in a vacuum. In this system, spin coating was performed in an Ar glove box, and the Ni substrate after applying the precursor solution was operated so as not to be exposed to air as much as possible. Thereafter, in the same manner as in Example 7, a heat treatment was performed at a maximum temperature of 700 ° C. with a water vapor addition amount of 30% by volume to produce a thin film electrode plate. This is Example 11.
Ｆｅ（ＯＣＯＣＨ3）2 ８７０ｍｇ、ＬｉＯＣＯＣＨ3・２Ｈ2Ｏ ５１０ｍｇ、Ｈ3ＰＯ4 ４９０ ｍｇをそれぞれ秤量し、エルレンマイヤーフラスコへ投入し、エチレングリコール１５ｍＬへ溶解させて前駆体溶液を調整した。本前駆体溶液を直径１５ｍｍ、厚さ１ｍｍのＮｉ基板上に３０００ｒｐｍにてスピンコートし、真空中１００℃で乾燥させた。この後、実施例７と同様に、水蒸気添加量を３０体積％として最高温度７００℃で熱処理を行い薄膜極板を作製した。これを実施例１２とする。 Fe (OCOCH 3 ) 2 870 mg, LiOCOCH 3 .2H 2 O 510 mg, and H 3 PO 4 490 mg were weighed, put into an Erlenmeyer flask, and dissolved in 15 mL of ethylene glycol to prepare a precursor solution. This precursor solution was spin-coated at 3000 rpm on a Ni substrate having a diameter of 15 mm and a thickness of 1 mm, and dried at 100 ° C. in a vacuum. Thereafter, in the same manner as in Example 7, a heat treatment was performed at a maximum temperature of 700 ° C. with a water vapor addition amount of 30% by volume to produce a thin film electrode plate. This is Example 12.
実施例１０から１２についても先述の方法で電池を構成し、評価を行った。結果を表４に示す。 Regarding Examples 10 to 12, batteries were constructed by the above-described method and evaluated. The results are shown in Table 4.
実施例１０〜１２についても実施例１と同様に、比較的良好な１サイクル目利用率及び良好な充放電サイクル寿命特性が得られた。以上のように、本発明によれば、種々のＬｉ、Ｆｅ、Ｐ源の化合物を用いることが可能であり、種々の溶媒が適用可能であることが明らかとなった。中でも、Ｌｉ源としては酢酸リチウム二水和物、リチウムアルコキシドの使用が好ましく、Ｆｅ源としては酢酸塩、硫酸塩７水和物、フェロセン及びその誘導体の使用が好ましく、Ｐ源としてはリン酸、リン酸エステル（アルコキシドの炭素数は１〜６）の使用が好ましい。 In Examples 10 to 12, as in Example 1, comparatively good first cycle utilization and good charge / discharge cycle life characteristics were obtained. As described above, according to the present invention, it has become clear that various Li, Fe, and P source compounds can be used, and various solvents can be applied. Among them, the lithium source is preferably lithium acetate dihydrate and lithium alkoxide, the Fe source is preferably acetate, sulfate heptahydrate, ferrocene and derivatives thereof, and the P source is phosphoric acid, Use of phosphoric acid esters (alkoxides having 1 to 6 carbon atoms) is preferred.
また、前駆体溶液の溶媒としてはＴＨＦ、酢酸、エチレングリコール、Ｎ−メチルピロリドンが適用可能であり、他にもエタノール、イソプロパノール、アセトン、水などが適用可能である。
次に、前駆体溶液の粘度を上昇させて薄膜極板の活物質層厚みを厚くする検討を行った。
Moreover, THF, acetic acid, ethylene glycol, and N-methylpyrrolidone are applicable as the solvent for the precursor solution, and ethanol, isopropanol, acetone, water, and the like are also applicable.
Next, studies were made to increase the thickness of the active material layer of the thin film electrode plate by increasing the viscosity of the precursor solution.
実施例１０で調整した前駆体溶液にポリビニルピロリドン１００ｍｇを添加したほかは実施例１０と同様に薄膜極板を作製した。これを実施例１３とする。 A thin film electrode plate was prepared in the same manner as in Example 10 except that 100 mg of polyvinylpyrrolidone was added to the precursor solution prepared in Example 10. This is Example 13.
実施例１０で調整した前駆体溶液にポリビニルブチラール１００ｍｇを添加したほかは実施例１０と同様に薄膜極板を作製した。これを実施例１４とする。 A thin-film electrode plate was prepared in the same manner as in Example 10 except that 100 mg of polyvinyl butyral was added to the precursor solution prepared in Example 10. This is Example 14.
実施例１０で調整した前駆体溶液にポリエチレンオキシド１００ｍｇを添加したほかは
実施例１０と同様に薄膜極板を作製した。これを実施例１５とする。
A thin film electrode plate was prepared in the same manner as in Example 10 except that 100 mg of polyethylene oxide was added to the precursor solution prepared in Example 10. This is Example 15.
実施例１３から１５についても先述の方法で電池を構成し、評価を行った。ただし、本系では活物質利用率ではなく、極板容量を評価した。結果を実施例１０と合わせて表５に示す。 For Examples 13 to 15, batteries were constructed by the above-described method and evaluated. However, in this system, not the active material utilization rate but the electrode plate capacity was evaluated. The results are shown in Table 5 together with Example 10.
実施例１３〜１５は実施例１０と比べて電極容量が約１．５倍程度であり、１０サイクル目容量もほぼ同程度であり、充放電サイクル寿命特性にも優れていることが分かった。容量が増加した要因は、前駆体溶液に種々の添加剤を加えることで溶液の粘度が増加し、スピンコート時の前駆体塗膜の厚みが増し、活物質層が厚くなったためと考えられる。 In Examples 13 to 15, the electrode capacity was about 1.5 times that in Example 10, the capacity at the 10th cycle was almost the same, and it was found that the charge / discharge cycle life characteristics were also excellent. The reason for the increased capacity is thought to be that the viscosity of the solution increased by adding various additives to the precursor solution, the thickness of the precursor coating film during spin coating increased, and the active material layer became thicker.
このように、本発明によれば、前駆体溶液中にポリビニルピロリドン、ポリビニルブチラール、ポリエチレンオキシドを添加して粘度を上昇させることで、極板厚みが制御できることが明らかとなった。 Thus, according to the present invention, it has been clarified that the electrode plate thickness can be controlled by increasing the viscosity by adding polyvinyl pyrrolidone, polyvinyl butyral, or polyethylene oxide to the precursor solution.
本発明によれば、安価にリン酸鉄リチウムの薄膜電極を提供することが可能となる。 According to the present invention, a lithium iron phosphate thin film electrode can be provided at low cost.
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