JP6333192B2 - Thermoelectric material manufacturing method - Google Patents
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- 239000000463 material Substances 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000007791 liquid phase Substances 0.000 claims description 24
- 229910052714 tellurium Inorganic materials 0.000 claims description 13
- 229910052797 bismuth Inorganic materials 0.000 claims description 10
- 238000010335 hydrothermal treatment Methods 0.000 claims description 10
- 229910052711 selenium Inorganic materials 0.000 claims description 10
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- 239000011246 composite particle Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000012298 atmosphere Substances 0.000 description 14
- 239000011669 selenium Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- VIEXQFHKRAHTQS-UHFFFAOYSA-N chloroselanyl selenohypochlorite Chemical compound Cl[Se][Se]Cl VIEXQFHKRAHTQS-UHFFFAOYSA-N 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- SPRIOUNJHPCKPV-UHFFFAOYSA-N hydridoaluminium Chemical compound [AlH] SPRIOUNJHPCKPV-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Description
本発明は、液相中で熱電材料、特にｎ型熱電材料を製造する方法に関する。 The present invention relates to a method for producing a thermoelectric material, particularly an n-type thermoelectric material, in a liquid phase.
熱電材料は、熱エネルギーと電気エネルギーとを相互に変換することのできる材料である。様々な熱電材料及びその製造方法が報告されている（例えば、特許文献１〜４）。 Thermoelectric materials are materials that can convert thermal energy and electrical energy to each other. Various thermoelectric materials and production methods thereof have been reported (for example, Patent Documents 1 to 4).
特許文献１は、Ｂｉ２−ｘＳｂｘＴｅ３−ｙＳｅｙ（０≦ｘ≦２，０≦ｙ≦３）によって表される合金を粉砕し、酸化雰囲気下に暴露し、次に還元雰囲気下又は不活性雰囲気下で焼成することを含む、熱電材料の製造方法を開示している。 Patent Document 1 discloses that an alloy represented by Bi 2-x Sb x Te 3-y Se y (0 ≦ x ≦ 2, 0 ≦ y ≦ 3) is pulverized, exposed to an oxidizing atmosphere, and then reduced. Disclosed is a method for producing a thermoelectric material, comprising firing under or under an inert atmosphere.
特許文献２は、酸素親和性元素（アルカリ金属又はアルカリ土類金属）と熱電材料構成元素を、メカニカルアロイング法を用いて微粒子状態で混合することを含む、熱電材料の製造方法を開示している。 Patent Document 2 discloses a method for producing a thermoelectric material, which includes mixing an oxygen affinity element (alkali metal or alkaline earth metal) and a thermoelectric material constituent element in a fine particle state using a mechanical alloying method. Yes.
特許文献３は、Ｂｉ及びＴｅ並びに過剰量のＳｂ（脱酸剤）の単体元素粉末を真空又は不活性雰囲気下で混合し、大気雰囲気下でプレスによる予備成形体の形成及びその加圧焼結を行うことを含む、熱電材料の製造方法を開示している。
In
特許文献４は、Ｂｉ及びＴｅ並びに過剰量のＳｂを溶解し、還元し、水熱処理することを含む、熱電材料の製造方法を開示している。
特許文献１の方法では、合金の粉砕時における表面酸化が問題となる。そのため、その後に還元雰囲気下で熱処理することが知られている。しかし、表面酸化を防止するために雰囲気を厳密に管理したり、還元雰囲気下での熱処理工程を追加すると、コストが増加してしまう。 In the method of Patent Document 1, surface oxidation during pulverization of the alloy becomes a problem. For this reason, it is known that heat treatment is subsequently performed in a reducing atmosphere. However, if the atmosphere is strictly controlled to prevent surface oxidation or a heat treatment step in a reducing atmosphere is added, the cost increases.
特許文献２では、アルカリ金属又はアルカリ土類金属を酸素親和性元素として使用しているが、これらの元素は水やアルコール等の溶媒と容易に反応し、酸化してしまう。そのため、特許文献２の方法を液相中で実施することはできない。 In Patent Document 2, alkali metal or alkaline earth metal is used as an oxygen affinity element, but these elements easily react with a solvent such as water or alcohol and are oxidized. Therefore, the method of Patent Document 2 cannot be performed in the liquid phase.
特許文献３では、脱酸剤としてのＳｂを粗大な粒子として使用している。ここで、特許文献３の方法を液相法に適用しても、十分な耐酸化性能を得ることはできない。実際、液相中に粗大なＳｂ粒子を添加しても、予備成形体の形成及びその加圧焼結を大気雰囲気下で行うと熱電材料が酸化することが確認されている。この理由としては、液相法の場合、得られる熱電材料の粒径が非常に小さく、酸化されうる表面の割合が多いことが推測される（特許文献３の方法による粒径は約１００μｍであり、液相法による粒径は約１０ｎｍである）。
In
特許文献３及び４では、過剰量のＳｂを使用している。しかし、ｎ型熱電材料に多量のＳｂを含有させるとｐ型熱電材料となる虞がある。
In
本発明が対象とするｎ型熱電材料（Ｂｉ２（Ｔｅ，Ｓｅ）３系材料）は、酸化の影響を受けやすく、各製造工程を不活性雰囲気下で実施しても酸化してしまう（以下の比較例１を参照）。この原因は、各製造工程間（例えば輸送）における瞬間的な大気暴露にあると推測される。それ故、ｎ型熱電材料の製造においては、不活性雰囲気を極めて高度に制御することが要求されており、このままでは実用化に耐えることはできなかった。 The n-type thermoelectric material (Bi 2 (Te, Se) 3 -based material) targeted by the present invention is susceptible to oxidation, and oxidizes even if each manufacturing process is carried out in an inert atmosphere (hereinafter referred to as “inductive atmosphere”). See Comparative Example 1). This is presumed to be due to instantaneous atmospheric exposure between manufacturing processes (for example, transportation). Therefore, in manufacturing the n-type thermoelectric material, it is required to control the inert atmosphere to a very high degree, and it has not been possible to withstand practical use as it is.
本発明は、耐酸化性能を有する熱電材料、特にｎ型熱電材料を液相中で製造する方法を提供することを課題とする。 An object of the present invention is to provide a method for producing a thermoelectric material having oxidation resistance, particularly an n-type thermoelectric material, in a liquid phase.
本発明者等は、鋭意検討した結果、Ｂｉ、Ｔｅ及びＳｅ並びに所定の量のＳｂを液相中で還元し、水熱処理することにより、耐酸化性能を有するｎ型熱電材料が得られることを見出した。 As a result of intensive studies, the present inventors have found that an n-type thermoelectric material having oxidation resistance can be obtained by reducing Bi, Te, and Se and a predetermined amount of Sb in a liquid phase and hydrothermally treating them. I found it.
本発明によれば、耐酸化性能を有するｎ型熱電材料を提供することができる。 According to the present invention, an n-type thermoelectric material having oxidation resistance can be provided.
本発明は、液相還元工程及び水熱処理工程を含む熱電材料、特にｎ型熱電材料の製造方法に関する。ｎ型熱電材料は、例えばＢｉ２（Ｔｅ,Ｓｅ）３±ｘ（ｘ＝０〜１）で表すことができる。 The present invention relates to a thermoelectric material including a liquid phase reduction step and a hydrothermal treatment step, particularly to a method for producing an n-type thermoelectric material. The n-type thermoelectric material can be represented by, for example, Bi 2 (Te, Se) 3 ± x (x = 0 to 1).
＜液相還元工程＞
液相還元工程は、Ｂｉ（ビスマス）、Ｔｅ（テルル）、Ｓｅ（セレン）及びＳｂ（アンチモン）を液相中で還元して、複合粒子を形成する工程である。
<Liquid phase reduction process>
The liquid phase reduction step is a step of forming composite particles by reducing Bi (bismuth), Te (tellurium), Se (selenium) and Sb (antimony) in the liquid phase.
Ｓｂの量は、Ｂｉ、Ｔｅ、Ｓｅ及びＳｂの合計量に対して、３．３ｍｏｌ％以下である。この量のＳｂを使用することにより、ｎ型熱電材料の性能を維持し、当該熱電材料の酸化を抑制し、且つ当該熱電材料のキャリア濃度を低く維持することができる。 The amount of Sb is 3.3 mol% or less with respect to the total amount of Bi, Te, Se and Sb. By using this amount of Sb, the performance of the n-type thermoelectric material can be maintained, oxidation of the thermoelectric material can be suppressed, and the carrier concentration of the thermoelectric material can be kept low.
Ｓｂの量の下限は、０ｍｏｌ％でなければ特に限定されないが、例えば、０．０１ｍｏｌ％、０．１ｍｏｌ％、０．５ｍｏｌ％、１．０ｍｏｌ％、１．５ｍｏｌ％、２．０ｍｏｌ％等を例示することができる。 The lower limit of the amount of Sb is not particularly limited unless it is 0 mol%. For example, 0.01 mol%, 0.1 mol%, 0.5 mol%, 1.0 mol%, 1.5 mol%, 2.0 mol%, etc. It can be illustrated.
Ｂｉ、Ｔｅ、Ｓｅ及びＳｂの原料は、液相に溶解するものであればよい。例えば、Ｂｉ、Ｔｅ、Ｓｅ及びＳｂの塩化物、水酸化物、硫酸塩、硝酸塩、酢酸塩等を例示することができる。 The raw materials for Bi, Te, Se, and Sb may be any materials that can be dissolved in the liquid phase. For example, Bi, Te, Se and Sb chlorides, hydroxides, sulfates, nitrates, acetates and the like can be exemplified.
液相を構成する溶媒は、特に限定されないが、水及び有機溶媒等を例示することができる。有機溶媒としては、アルコール、アミド、ケトン等を例示することができる。アルコールとしては、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール等を例示することができる。アミドとしては、アセトアミド、Ｎ−メチル−２−ピロリドン等を例示することができる。ケトンとしては、アセトン、メチルエチルケトン等を例示することができる。 Although the solvent which comprises a liquid phase is not specifically limited, Water, an organic solvent, etc. can be illustrated. Examples of the organic solvent include alcohol, amide, ketone and the like. Examples of the alcohol include methanol, ethanol, propanol, isopropanol, butanol and the like. Examples of amides include acetamido and N-methyl-2-pyrrolidone. Examples of ketones include acetone and methyl ethyl ketone.
液相中の還元のために使用される還元剤は、特に限定されないが、水素化ホウ素ナトリウム（ＮａＢＨ４）、水素化ホウ素リチウム（ＬｉＢＨ４）、水素化ホウ素カリウム（ＫＢＨ４）、水素化アルミニウムリチウム（ＬｉＡｌＨ４）、水素化ジイソブチルアルミニウム（[（ＣＨ３）２ＣＨＣＨ２]２ＡｌＨ）、ヒドラジン（Ｎ２Ｈ４）、フェニルヒドラジン（ＰｈＨＮＮＨ２）等を例示することができる。 The reducing agent used for the reduction in the liquid phase is not particularly limited, hydrogen sodium borohydride (NaBH 4), lithium borohydride (LiBH 4), potassium borohydride (KBH 4), aluminum hydride Examples include lithium (LiAlH 4 ), diisobutylaluminum hydride ([(CH 3 ) 2 CHCH 2 ] 2 AlH), hydrazine (N 2 H 4 ), and phenylhydrazine (PhHNNH 2 ).
液相還元工程は不活性雰囲気下（窒素雰囲気下、アルゴン雰囲気下等）で実施することが好ましい。 The liquid phase reduction step is preferably performed under an inert atmosphere (such as a nitrogen atmosphere or an argon atmosphere).
＜水熱処理工程＞
水熱処理工程は、液相還元工程で得られた複合粒子を水熱処理して、熱電材料を形成する工程である。
<Hydrothermal treatment process>
The hydrothermal treatment step is a step of forming a thermoelectric material by hydrothermally treating the composite particles obtained in the liquid phase reduction step.
水熱処理の温度は、特に限定されないが、１００〜４００℃、１５０〜３５０℃、２００〜３００℃等を例示することができる。 Although the temperature of hydrothermal treatment is not specifically limited, 100-400 degreeC, 150-350 degreeC, 200-300 degreeC etc. can be illustrated.
水熱処理の時間は、特に限定されないが、４〜１６時間、６〜１４時間、８〜１２時間等を例示することができる。 The time for the hydrothermal treatment is not particularly limited, and examples thereof include 4 to 16 hours, 6 to 14 hours, and 8 to 12 hours.
＜乾燥工程＞
本発明の製造方法は、更に乾燥工程を含んでいてもよい。乾燥工程は、水熱処理工程で製造された熱電材料の粉末を乾燥する工程である。乾燥工程は不活性雰囲気下（窒素雰囲気下、アルゴン雰囲気下等）で実施することが好ましい。
<Drying process>
The production method of the present invention may further include a drying step. The drying step is a step of drying the thermoelectric material powder produced in the hydrothermal treatment step. The drying step is preferably performed under an inert atmosphere (such as a nitrogen atmosphere or an argon atmosphere).
＜バルク化処理工程＞
本発明の製造方法は、更にバルク化処理工程を含んでいてもよい。バルク化処理工程は、水熱処理工程で製造された熱電材料の粉末、又は乾燥工程で乾燥された熱電材料の粉末をバルク化する工程である。バルク化処理の方法は、特に限定されないが、熱電材料の粉末を圧粉形成し、放電プラズマ焼結する方法を例示することができる。
<Bulkization process>
The production method of the present invention may further include a bulking treatment step. The bulking process is a process of bulking the thermoelectric material powder produced in the hydrothermal treatment process or the thermoelectric material powder dried in the drying process. The method of bulking treatment is not particularly limited, and examples thereof include a method of compacting a thermoelectric material powder and performing discharge plasma sintering.
放電プラズマ焼結の温度は、特に限定されないが、３００〜５００℃、３５０〜４５０℃等を例示することができる。 Although the temperature of discharge plasma sintering is not specifically limited, 300-500 degreeC, 350-450 degreeC etc. can be illustrated.
放電プラズマ焼結の時間は、特に限定されないが、５〜６０分、５〜４０分、５〜２０分等を例示することができる。 Although the time of discharge plasma sintering is not specifically limited, 5-60 minutes, 5-40 minutes, 5-20 minutes etc. can be illustrated.
放電プラズマ焼結の圧力は、特に限定されないが、２０〜８０ＭＰａ、３０〜７０ＭＰａ、４０〜６０ＭＰａ等を例示することができる。 Although the pressure of discharge plasma sintering is not specifically limited, 20-80 MPa, 30-70 MPa, 40-60 MPa etc. can be illustrated.
以下、実施例、参考例及び比較例を用いて本発明をより詳細に説明するが、本発明の技術的範囲はこれに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, a reference example, and a comparative example, the technical scope of this invention is not limited to this.
＜熱電材料の製造及びその特性測定＞
［実施例１］
（１）原料溶液の調製
塩化ビスマス（１４．２７ｇ）、塩化テルル（１７．９９ｇ）、塩化セレン（０．２５ｇ）、及び塩化アンチモン（Ｂｉ、Ｔｅ、Ｓｅ及びＳｂの合計量に対してＳｂの量が２．０ｍｏｌ％となる量）をエタノール（１７００ｍｌ）に溶解させて、原料溶液を調製した。
<Manufacture of thermoelectric materials and measurement of their characteristics>
[Example 1]
(1) Preparation of raw material solution Sb with respect to the total amount of bismuth chloride (14.27 g), tellurium chloride (17.99 g), selenium chloride (0.25 g), and antimony chloride (Bi, Te, Se, and Sb) An amount of 2.0 mol%) was dissolved in ethanol (1700 ml) to prepare a raw material solution.
（２）還元剤溶液の調製
水素化ホウ素ナトリウム（１９．５８ｇ）をエタノール（１７００ｍｌ）に溶解させて、還元剤溶液を調製した。
(2) Preparation of reducing agent solution Sodium borohydride (19.58 g) was dissolved in ethanol (1700 ml) to prepare a reducing agent solution.
（３）液相還元
窒素雰囲気下で還元剤溶液を原料溶液に滴下して、複合粒子を形成した。複合粒子は水及びエタノールで洗浄した。ここで、ナノ粒子を導入することで分散相が形成され、材料の性能が向上する。
(3) Liquid phase reduction The reducing agent solution was dropped into the raw material solution in a nitrogen atmosphere to form composite particles. The composite particles were washed with water and ethanol. Here, by introducing nanoparticles, a dispersed phase is formed, and the performance of the material is improved.
（４）水熱処理
複合粒子をエタノール（２００ｍｌ）と混合し、水熱処理（１０時間、２４０℃）して、熱電材料の粉末を得た。熱電材料の粉末はエタノールで洗浄した。
(4) Hydrothermal treatment The composite particles were mixed with ethanol (200 ml) and hydrothermally treated (10 hours, 240 ° C) to obtain a thermoelectric material powder. The thermoelectric material powder was washed with ethanol.
（５）乾燥
熱電材料の粉末を不活性雰囲気下で乾燥した。
(5) Drying The powder of the thermoelectric material was dried under an inert atmosphere.
（６）バルク化処理
乾燥させた熱電材料の粉末を圧粉成形し、放電プラズマ焼結（１０分間、４００℃、５０ＭＰａ）によりバルク化した。
(6) Bulking treatment The dried thermoelectric material powder was compacted and bulked by discharge plasma sintering (10 minutes, 400 ° C., 50 MPa).
（７）特性測定
Ｘ線回折装置（株式会社リガク製、水平型Ｘ線回折装置ＳｍａｒｔＬａｂ）を用いて、酸化物の有無を測定した。
(7) Characteristic measurement The presence or absence of an oxide was measured using an X-ray diffractometer (manufactured by Rigaku Corporation, horizontal X-ray diffractometer SmartLab).
Ｒｅｓｉ−ｔｅｓｔ９３４０ＤＣ（株式会社東陽テクニカ製）を用いて、キャリア濃度を測定した。 The carrier concentration was measured using Resi-test 9340DC (manufactured by Toyo Corporation).
［参考例１］
実施例１の「（１）原料溶液の調製」におけるＳｂの量を３．９ｍｏｌ％に変更したこと以外は、実施例１と同様の操作を行った。
[Reference Example 1]
The same operation as in Example 1 was performed except that the amount of Sb in “(1) Preparation of raw material solution” in Example 1 was changed to 3.9 mol%.
［参考例２］
実施例１の「（１）原料溶液の調製」におけるＳｂの量を５．７ｍｏｌ％に変更したこと以外は、実施例１と同様の操作を行った。
[Reference Example 2]
The same operation as in Example 1 was performed except that the amount of Sb in “(1) Preparation of raw material solution” in Example 1 was changed to 5.7 mol%.
［比較例１］
実施例１の「（１）原料溶液の調製」において塩化アンチモンを使用しなかったこと以外は、実施例１と同様の操作を行った。
[Comparative Example 1]
The same operation as in Example 1 was performed except that antimony chloride was not used in “(1) Preparation of raw material solution” in Example 1.
＜結果＞
Ｓｂの量が増加するにつれて、熱電材料の代わりに酸化されたＳｂの酸化物相が確認された。
<Result>
As the amount of Sb increased, an oxidized Sb oxide phase was observed instead of a thermoelectric material.
Ｓｂの量が増加するにつれて、キャリア濃度が低下したが、一定の量を超えると、逆にキャリア濃度が上昇した（図１）。キャリア濃度の上昇は、Ｓｂが酸化されずに熱電材料内に合金化されることが原因であると推測される。 As the amount of Sb increased, the carrier concentration decreased. However, when the amount exceeded a certain amount, the carrier concentration increased conversely (FIG. 1). The increase in carrier concentration is presumed to be caused by the fact that Sb is not oxidized but alloyed in the thermoelectric material.
上述の通り、液相法を利用する本発明によって得られる熱電材料の表面積は大きく、酸化の影響を受けやすいため、酸化を抑制するためにＳｂを多量に使用することが予測される。しかし、キャリア濃度の観点から、Ｓｂの量は３．３ｍｏｌ％以下であることが好ましい。 As described above, since the surface area of the thermoelectric material obtained by the present invention using the liquid phase method is large and easily affected by oxidation, it is predicted that a large amount of Sb is used to suppress oxidation. However, from the viewpoint of carrier concentration, the amount of Sb is preferably 3.3 mol% or less.
キャリア濃度を増加させることなく、少量のＳｂで効果的に酸化を抑制できる理由は、Ｓｂが他の元素よりも還元されにくく、液相における熱電材料粒子の合成時にＳｂがｉｎ−ｓｉｔｕで合成されるため、熱電材料粒子の表面にＳｂが薄い保護膜のように形成されることによると推測される。 The reason why oxidation can be effectively suppressed with a small amount of Sb without increasing the carrier concentration is that Sb is less likely to be reduced than other elements, and Sb is synthesized in-situ during the synthesis of thermoelectric material particles in the liquid phase. Therefore, it is estimated that Sb is formed on the surface of the thermoelectric material particle like a thin protective film.
なお、キャリア濃度を測定する際に、電子及び正孔の数を測定した結果、実施例、参考例及び比較例で製造された熱電材料はいずれもｎ型熱電材料であった。 When the carrier concentration was measured, the number of electrons and holes was measured. As a result, the thermoelectric materials produced in the examples, reference examples, and comparative examples were all n-type thermoelectric materials.
Claims (2)
液相還元工程で得られた複合粒子を水熱処理して、熱電材料を形成する水熱処理工程；を含み、
液相還元工程におけるＳｂの量が、Ｂｉ、Ｔｅ、Ｓｅ及びＳｂの合計量に対して、３．３ｍｏｌ％以下である、ｎ型熱電材料の製造方法。 A liquid phase reduction step in which Bi, Te, Se and Sb are reduced in the liquid phase to form composite particles; and a hydrothermal treatment in which the composite particles obtained in the liquid phase reduction step are hydrothermally treated to form a thermoelectric material. Comprising the steps of:
The method for producing an n-type thermoelectric material, wherein the amount of Sb in the liquid phase reduction step is 3.3 mol% or less with respect to the total amount of Bi, Te, Se, and Sb.
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