TWI636007B - Method for producing carbon composite manganese iron iron phosphate particle powder, carbon composite manganese iron iron particle particle powder, and nonaqueous electrolyte secondary battery using the same - Google Patents

Method for producing carbon composite manganese iron iron phosphate particle powder, carbon composite manganese iron iron particle particle powder, and nonaqueous electrolyte secondary battery using the same Download PDF

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TWI636007B
TWI636007B TW102131299A TW102131299A TWI636007B TW I636007 B TWI636007 B TW I636007B TW 102131299 A TW102131299 A TW 102131299A TW 102131299 A TW102131299 A TW 102131299A TW I636007 B TWI636007 B TW I636007B
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iron
lithium
carbon composite
particle powder
iron phosphate
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TW201414668A (en
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三島祐司
西尾尊久
磨
貞村英昭
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戶田工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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

Abstract

本發明提供一種碳複合化磷酸錳鐵鋰粒子粉末之製造方法、粒子粉末、以及使用其之二次電池，上述碳複合化磷酸錳鐵鋰粒子粉末之製造方法係橄欖石型構造之碳複合化磷酸錳鐵鋰(Mn：Fe=0.98：0.02~0.50：0.50莫耳比)粒子粉末之製造方法，其係由下述步驟所成：獲得含有藉由水熱處理所生成之橄欖石型構造之磷酸錳鐵鋰、鋰化合物及/或磷化合物與有機物之水系懸浮液或含水物之第一步驟、使第一步驟中所得之水系懸浮液或含水物乾燥而獲得燒成用前驅物混合粉末之第二步驟、燒成第二步驟中所得之燒成用前驅物混合粉末之第三步驟。藉由該製造方法，可提供低成本、可容易製造、填充性優異之橄欖石型構造之碳複合化磷酸錳鐵鋰正極活性物質。 The present invention provides a method for producing a carbon composite manganese iron iron phosphate particle powder, a particle powder, and a secondary battery using the same, wherein the method for producing the carbon composite manganese iron iron phosphate particle powder is an olivine structure carbon composite A method for producing a lithium manganese iron phosphate (Mn:Fe=0.98:0.02~0.50:0.50 molar ratio) particle powder by the following steps: obtaining a phosphoric acid containing an olivine-type structure formed by hydrothermal treatment a first step of dissolving an aqueous suspension or a hydrate of the lithium iron oxide, the lithium compound and/or the phosphorus compound and the organic compound, and drying the aqueous suspension or the aqueous product obtained in the first step to obtain a mixed powder of the precursor for firing In the second step, the third step of firing the precursor powder for firing in the second step is performed. According to this production method, it is possible to provide a carbon composite manganese iron iron oxide positive electrode active material having an olivine structure which is low in cost and can be easily produced and has excellent filling properties.

Description

碳複合化磷酸錳鐵鋰粒子粉末之製造方法、碳複合化磷酸錳鐵鋰粒子粉末及使用該粒子粉末之非水電解質二次電池 Method for producing carbon composite manganese iron iron phosphate particle powder, carbon composite lithium manganese iron phosphate particle powder, and nonaqueous electrolyte secondary battery using the same

本發明提供一種可以低成本且環境負荷少地製造、顯示高輸出且高能量密度之作為二次電池用之正極活性物質的低溫電流負荷特性優異、且高溫之重複特性優異之碳複合化磷酸錳鐵鋰粒子粉末、及使用其之二次電池。 The present invention provides a carbon composite manganese phosphate which is excellent in low-temperature current load characteristics and excellent in high-temperature repeatability, which is a positive electrode active material for a secondary battery which can be produced at a low cost and with a low environmental load and which exhibits high output and high energy density. Iron lithium particle powder, and a secondary battery using the same.

近年來，AV機器或個人電腦等電子機器、電動工具等之動力工具之可攜帶化、無線化已急速進展，因而對於作為該等之驅動用電源之小型、輕量且具有高能量密度之二次電池之要求隨之提高。且，基於對於地球環境之顧慮，已進行油電混合車、電動車之開發及實用化，因而對輸出特性亦優異之二次電池之要求亦變高。在該等狀況下，具有充放電電容大、且安全性高之優點的鋰離子二次電池備受矚目。 In recent years, the portable and wireless power tools such as electronic equipment and electric tools such as AV equipment and personal computers have been rapidly progressing. Therefore, they are small, lightweight, and have high energy density as the driving power source. The requirements for secondary batteries have increased. In addition, based on the concerns about the global environment, the development and practical use of hybrid electric vehicles and electric vehicles have been carried out, and the demand for secondary batteries having excellent output characteristics has also increased. Under these circumstances, a lithium ion secondary battery having a large charge and discharge capacity and high safety has been attracting attention.

最近，作為高能量密度型之鋰離子二次電池 中有用之正極活性物質，除3.5V級橄欖石型構造之LiFePO4以外，4.1V級之相同構造之LiMnPO4亦受到矚目。然而，由於LiMnPO4比LiFePO4之Li之進出更不容易，故要求改善充放電特性與其重複特性。 Recently, as a positive electrode active material useful in a lithium ion secondary battery of a high energy density type, LiMnPO 4 having the same structure of 4.1 V grade has attracted attention in addition to LiFePO 4 of a 3.5 V grade olivine structure. However, since LiMnPO 4 is less likely to enter and exit than Li of LiFePO 4 , it is required to improve the charge and discharge characteristics and its repeating characteristics.

橄欖石型構造之LiMnPO4係由強固之磷酸4面體骨架與於中心具有有助於氧化還原之錳離子之氧8面體及擔負電流的鋰離子所構成。此外，為提高電子傳導性與電極反應，較好在正極活性物質之粒子表面施以碳被覆。藉此發揮作為二次電池之電極的功能，且以Li作為負極進行充放電時，由於以電容與電壓表示之充放電特性存在停滯期(plateau)區域，故可說是依據下式之二相反應。 The olivine-type LiMnPO 4 system is composed of a strong phosphoric acid tetrahedral skeleton and an oxygen octahedron having a manganese ion which contributes to redox at the center and a lithium ion which is subjected to a current. Further, in order to improve the electron conductivity and the electrode reaction, it is preferred to apply a carbon coating to the surface of the particles of the positive electrode active material. In this case, when Li is used as the electrode of the secondary battery, and Li is used as the negative electrode for charging and discharging, since the charge and discharge characteristics indicated by the capacitance and the voltage have a plateau region, it can be said that the second phase is based on the following formula. reaction.

充電LiMnPO4 → MnPO4+Li++e- Charging LiMnPO 4 → MnPO 4 +Li + +e -

放電MnPO4+Li++e- → LiMnPO4 Discharge MnPO 4 +Li + +e - → LiMnPO 4

依據最近之報導，雖藉由與Li之進出有關之性能面之正極活性物質粒子與碳之充分複合化而獲得高電容之LiMnPO4正極，但關於Li脫離之MnPO4之長期安定性有各種說法。因此，認為有必要防止因充電反應之Li脫離時之粒子破裂所致之微細化，且使Li脫離之物質的結晶構造安定化。作為其例，有使Fe對Mn位置之固熔或活性物質之微粒子化之方法(非專利文獻1~7)。 According to a recent report, a high-capacitance LiMnPO 4 positive electrode is obtained by fully combining the positive electrode active material particles with carbon on the performance surface related to the entry and exit of Li, but there are various opinions on the long-term stability of MnPO 4 in which Li is desorbed. . Therefore, it is considered that it is necessary to prevent the finening of the particles due to the detachment of Li by the charging reaction, and to stabilize the crystal structure of the substance from which Li is detached. As an example, there is a method of solid-melting Fe to the Mn position or fine particles of an active material (Non-Patent Documents 1 to 7).

橄欖石型構造之LiMn1-xFexPO4中，愈於粒子表面被覆碳則低電流時之充放電特性愈好。且，有愈是滿 足前述被覆條件且結晶子尺寸未達100nm之微粒子，在高的電流負荷下之充放電特性愈好之傾向。另外，獲得作為電極之高成型體密度時，有必要以彼等適度凝聚之二次粒子且以石墨化率高之如碳之導電性輔助劑形成網絡之方式，控制各集合狀態。然而，與大量碳複合化之正極體積較大，而發生每單位體積可填充之實質鋰離子密度變低之缺點。因此，為確保每單位體積之充放電電容，必須獲得微細且適度被覆碳之LiMn1-xFexPO4，並且透過少量之導電性輔助劑形成具有高密度之凝集體。 In LiMn 1-x Fe x PO 4 having an olivine structure, the charge-discharge characteristics at a low current are better as the surface of the particles is coated with carbon. Further, the finer particles satisfying the above-mentioned coating conditions and having a crystallite size of less than 100 nm tend to have better charge and discharge characteristics under a high current load. Further, when the density of the high molded body as the electrode is obtained, it is necessary to control the respective aggregate states so that the secondary particles are appropriately agglomerated and the network is formed of a conductive auxiliary agent such as carbon having a high graphitization ratio. However, the positive electrode which is combined with a large amount of carbon is bulky, and the disadvantage that the solid lithium ion density per unit volume can be lowered becomes low. Therefore, in order to secure the charge and discharge capacitance per unit volume, it is necessary to obtain LiMn 1-x Fe x PO 4 which is fine and moderately coated with carbon, and to form agglomerates having a high density by a small amount of the conductive auxiliary agent.

用以高電容化之LiMnPO4粒子與碳之複合化方法一般已知為機械性混合LiMnPO4粒子與碳之機械化學法，但會有粒子粉末附著於裝置腔室內或混入雜質之問題，可有效量產之裝置或條件極少。此外，雖已教示LiMn1-xFexPO4因Fe之觸媒效果且因有機物在惰性氣體中之反應，而於該粒子表面析出碳，並改善其電阻，但碳被覆程度相較於LiFePO4較不充分，因而要求該粒子之進一步表面改質(非專利文獻1~7)。 The method for complexing LiMnPO 4 particles and carbon for high capacitance is generally known as a mechanochemical method for mechanically mixing LiMnPO 4 particles with carbon, but there is a problem that particle powder adheres to the device chamber or is mixed with impurities, which is effective. There are very few devices or conditions for mass production. In addition, although it has been taught that LiMn 1-x Fe x PO 4 has a catalytic effect of Fe and reacts with an organic substance in an inert gas to precipitate carbon on the surface of the particle and improve its electric resistance, the degree of carbon coating is compared with that of LiFePO. 4 is less sufficient, and further surface modification of the particles is required (Non-Patent Documents 1 to 7).

LiMn1-xFexPO4之粒子表面改質方法之一，已提案有於表面形成亦使Li與電子移動之由Li及P所成之非晶相、或包含異種元素之由Li與P所成之氧化物。然而，關於工業之方法很難說已有提及。 One of the surface modification methods of LiMn 1-x Fe x PO 4 has been proposed to have an amorphous phase formed by Li and P on the surface of Li and electrons, or Li and P containing heterogeneous elements. The oxides formed. However, the method of industry is hard to say has been mentioned.

過去，為改善LiMn1-xFexPO4粒子之諸特性，而以固相反應法、水熱反應法、溶凝膠法進行各種改良。例如，已知有與高比表面積之碳複合化獲得高電容之技術 (專利文獻1)、添加異種金屬元素，降低電阻之技術(專利文獻2)、添加異種金屬元素與碳被覆而降低電阻之技術(專利文獻3)、水熱法、及以溶凝膠法合成之技術(專利文獻4~6等)。 In the past, in order to improve the properties of LiMn 1-x Fe x PO 4 particles, various improvements have been made by a solid phase reaction method, a hydrothermal reaction method, or a sol gel method. For example, a technique of obtaining a high capacitance by complexing with a carbon having a high specific surface area (Patent Document 1), a technique of adding a dissimilar metal element, reducing resistance (Patent Document 2), adding a dissimilar metal element and carbon coating to reduce electric resistance are known. Technology (Patent Document 3), hydrothermal method, and technique synthesized by a lyotropic method (Patent Documents 4 to 6, etc.).

〔先前技術文獻〕 [Previous Technical Literature] 〔專利文獻〕 [Patent Document]

專利文獻1：特表2011-517053號公報 Patent Document 1: Special Table 2011-517053

專利文獻2：特開2004-063270號公報 Patent Document 2: JP-A-2004-063270

專利文獻3：特表2008-130525號公報 Patent Document 3: Special Table 2008-130525

專利文獻4：特開2010-251302號公報 Patent Document 4: JP-A-2010-251302

專利文獻5：特開2010-267501號公報 Patent Document 5: JP-A-2010-267501

專利文獻6：特開2011-213587號公報 Patent Document 6: JP-A-2011-213587

[非專利文獻] [Non-patent literature]

非專利文獻1：A.K. Padhi等，J. Electrochem. Soc., 1997, Vol. 144, p.A1188-1194。 Non-Patent Document 1: A. K. Padhi et al., J. Electrochem. Soc., 1997, Vol. 144, p. A1188-1194.

非專利文獻2：A. Yamada等，J. Electrochem. Soc., 2001, Vol. 148, p.A960-967。 Non-Patent Document 2: A. Yamada et al., J. Electrochem. Soc., 2001, Vol. 148, p. A960-967.

非專利文獻3：S. -W. Kim等，J. Electrochem. Soc., 2009, Vol. 156, p.A635-638。 Non-Patent Document 3: S.-W. Kim et al., J. Electrochem. Soc., 2009, Vol. 156, p. A635-638.

非專利文獻4：B. Kang等，J. Electrochem. Soc., 2010, Vol. 157, p.A808-811。 Non-Patent Document 4: B. Kang et al., J. Electrochem. Soc., 2010, Vol. 157, p. A808-811.

非專利文獻5：S. -M. -Oh等，Adv. Funct. Mater., 2010, Vol. 20, p.3260-3265。 Non-Patent Document 5: S. -M. -Oh et al., Adv. Funct. Mater., 2010, Vol. 20, p. 3260-3265.

非專利文獻6：S. P. Ong等，Electrochem. Comm., 2010, Vol. 10, p.427-430。 Non-Patent Document 6: S. P. Ong et al., Electrochem. Comm., 2010, Vol. 10, p. 427-430.

非專利文獻7：Y. Mishima等，IOP Conf. Series：Materials Science and Engineering, 2011, Vol. 18, p.122002。 Non-Patent Document 7: Y. Mishima et al., IOP Conf. Series: Materials Science and Engineering, 2011, Vol. 18, p. 122002.

針對作為非水電解質二次電池用之正極活性物質之電阻小、填充性高、充放電重複特性優異之碳複合化LiMn1-xFexPO4(0.02≦x≦0.5)粒子粉末之以低價且對環境負荷少之製造方法，係目前最被要求者，但尚未確定。 The carbon composite LiMn 1-x Fe x PO 4 (0.02≦x≦0.5) particle powder having a small electric resistance, high filling property, and excellent charge and discharge repeatability as a positive electrode active material for a nonaqueous electrolyte secondary battery is low. The manufacturing method with a low price and low environmental load is currently the most requested, but has not yet been determined.

亦即，前述非專利文獻1~7所記載之技術並非為工業上可獲得電阻小、填充性高，充放電重複特性優異之LiMn1-xFexPO4(0.02≦x≦0.5)粒子粉末者。 In other words, the techniques described in the above Non-Patent Documents 1 to 7 are not industrially available LiMn 1-x Fe x PO 4 (0.02 ≦ x ≦ 0.5) particle powder having small electric resistance, high filling property, and excellent charge and discharge repeatability. By.

專利文獻1所記載之技術係提高使用LiMn1-xFexPO4粒子粉末作為正極時之電容的技術，並未觸及對電極之填充性或二次集合狀態之控制。 The technique described in Patent Document 1 is a technique for improving the capacitance when LiMn 1-x Fe x PO 4 particle powder is used as a positive electrode, and does not touch the control of the filling property or the secondary aggregation state of the electrode.

專利文獻2記載之技術並非藉由LiMnPO4粒子粉末與碳之複合化而獲得高電子傳導性之技術，難以說是已獲得高電容之正極活性物質。 The technique described in Patent Document 2 is not a technique for obtaining high electron conductivity by the combination of LiMnPO 4 particle powder and carbon, and it is difficult to say that it is a positive electrode active material which has obtained a high capacitance.

專利文獻3記載之技術係以固相反應法之製 法，由於具有2次熱處理，故難稱為低成本。 The technique described in Patent Document 3 is based on a solid phase reaction method. The method is difficult to call low cost because it has two heat treatments.

專利文獻4記載之水熱法之使用高沸點水溶性有機溶劑、或專利文獻5記載之溶凝膠法之使用乙酸鹽之方法難以稱為低成本。 The method of using a high-boiling water-soluble organic solvent in the hydrothermal method described in Patent Document 4 or the method using the acetate in the lyogel method described in Patent Document 5 is difficult to be called low cost.

此外，專利文獻6記載之Li、Mn、Fe、P之主成分調整法由於係藉乾式進行調整添加劑之混合，故要求以如球磨機之裝置研磨至奈米尺寸之微粉碎與高分散，就量產性之觀點而言，難以說可工業化。 Further, in the principal component adjustment method of Li, Mn, Fe, and P described in Patent Document 6, since the mixing of the additives is performed by the dry type, it is required to grind to a nano-sized fine pulverization and high dispersion by a device such as a ball mill. From the point of view of productivity, it is difficult to say that it can be industrialized.

因此，本發明之技術課題係確立藉由使燒成前之主成分組成比之調整方法最適化，改善了燒成後所得之正極活性物質之結晶性與表面性、電阻小且填充性高之LiMn1-xFexPO4(0.02≦x≦0.5)之環境負荷小之工業上製造方法，以及提供顯示高輸出且高能量密度、低溫之電流負荷特性優異、且高溫下之充放電重複特性優異之碳複合化磷酸錳鐵鋰粒子粉末、及使用其之二次電池之技術。 Therefore, the technical problem of the present invention is to optimize the adjustment method of the main component composition ratio before firing, and to improve the crystallinity and surface properties of the positive electrode active material obtained after firing, and the electrical resistance is small and the filling property is high. LiMn 1-x Fe x PO 4 (0.02 ≦ x ≦ 0.5) of the manufacturing method of a small environmental of the industrial load, and providing a display having high output and high energy density, excellent current low temperature of the load characteristics and the charge-discharge under the high temperature and repetition characteristics An excellent carbon composite lithium manganese iron phosphate particle powder and a secondary battery using the same.

前述技術課題可藉如下之本發明達成。 The above technical problems can be achieved by the present invention as follows.

亦即，本發明係一種碳複合化磷酸錳鐵鋰粒子粉末之製造方法，其係於橄欖石型構造之碳複合化磷酸錳鐵鋰(Mn：Fe=0.98：0.02~0.50：0.50莫耳比)粒子粉末之製造方法中，且由獲得含有以水熱處理所生成之橄欖石型構造之磷酸錳鐵鋰、鋰化合物及/或磷化合物與有機物之水系懸浮液或含水物之第一步驟、使第一步驟中所得 之水系懸浮液或含水物乾燥而獲得燒成用前驅物混合粉末之第二步驟、燒成第二步驟中所得之燒成用前驅物混合粉末之第三步驟所成之碳複合化磷酸錳鐵鋰粒子粉末之製造方法，其特徵係第一步驟中之水系懸浮液或含水物以莫耳比計滿足0.98≦Li/(Mn+Fe)≦1.20、0.98≦P/(Mn+Fe)≦1.20、P≦Li，且鋰化合物及/或磷化合物之60wt%以上為Li1-yH2+yPO4(0≦y≦1)，前述有機物相對於水熱處理後之磷酸錳鐵鋰為1~20wt%(本發明1)。 That is, the present invention is a method for producing a carbon composite manganese iron iron phosphate particle powder, which is based on an olivine-type carbon composite lithium manganese iron phosphate (Mn:Fe=0.98:0.02~0.50:0.50 molar ratio) In the method for producing a particle powder, the first step of obtaining an aqueous suspension or hydrate containing lithium iron manganese phosphate, a lithium compound, and/or a phosphorus compound and an organic substance in an olivine structure formed by hydrothermal treatment is used. The second step of the aqueous suspension or the hydrate obtained in the first step to obtain a mixed powder of the precursor for firing, and the third step of the third step of the mixed precursor powder for firing in the second step A method for producing a composite lithium manganese iron phosphate particle powder, characterized in that the aqueous suspension or hydrate in the first step satisfies 0.98 ≦Li/(Mn+Fe)≦1.20, 0.98≦P/(Mn in terms of molar ratio +Fe)≦1.20, P≦Li, and 60% by weight or more of the lithium compound and/or the phosphorus compound is Li 1-y H 2+y PO 4 (0≦y≦1), and the organic substance is phosphoric acid after hydrothermal treatment The lithium iron manganese is 1 to 20% by weight (Invention 1).

且，本發明為如本發明1之碳複合化磷酸錳鐵鋰粒子粉末之製造方法，其中碳複合化磷酸錳鐵鋰粒子粉末之製造方法的第一步驟中，有機物為水可溶性之有機物(本發明2)。 Further, the present invention provides a method for producing a carbon composite manganese iron iron phosphate particle powder according to the present invention, wherein in the first step of the method for producing a carbon composite manganese iron iron phosphate particle powder, the organic substance is a water-soluble organic substance (this embodiment) Invention 2).

又，本發明為如本發明之1或2之碳複合化磷酸錳鐵鋰粒子粉末之製造方法，其中碳複合化磷酸錳鐵鋰粒子粉末之製造方法的第一步驟中，有機物為屬含羥基(-OH)或羧基(-COOH)之多元醇、糖或有機酸之有機物(本發明3)。 Further, the present invention provides a method for producing a carbon composite manganese iron iron phosphate particle powder according to the first or second aspect of the present invention, wherein in the first step of the method for producing a carbon composite manganese iron iron phosphate particle powder, the organic substance is a hydroxyl group. An organic substance of (-OH) or a carboxyl group (-COOH), a sugar or an organic acid (Invention 3).

且，本發明為如本發明1~3中任一項之碳複合化磷酸錳鐵鋰粒子粉末之製造方法，其中碳複合化磷酸錳鐵鋰粒子粉末之製造方法的第二步驟中之乾燥溫度為40℃~250℃(本發明4)。 Further, the present invention is the method for producing a carbon composite manganese iron iron phosphate particle powder according to any one of the inventions 1 to 3, wherein the drying temperature in the second step of the method for producing the carbon composite manganese iron iron phosphate particle powder It is 40 ° C to 250 ° C (Invention 4).

此外，本發明為一種碳複合化磷酸錳鐵鋰粒子粉末，其係以本發明1~4中任一項之碳複合化磷酸錳鐵鋰粒子粉末之製造方法所得者(本發明5)。 Furthermore, the present invention is a carbon composite manganese iron iron phosphate particle powder obtained by the method for producing a carbon composite manganese iron iron phosphate particle powder according to any one of the inventions 1 to 4 (Invention 5).

又，本發明為一種非水電解質二次電池，其係使用如本發明5之碳複合化磷酸錳鐵鋰粒子粉末而製作者(本發明6)。 Moreover, the present invention is a nonaqueous electrolyte secondary battery produced by using the carbon composite manganese iron iron phosphate particle powder of the present invention 5 (Invention 6).

本發明之碳複合化磷酸錳鐵鋰粒子粉末之製造方法可藉低成本、且對環境負荷小地進行製造，以該方法獲得之粉末為電阻小、填充性高者。且，使用其作為正極活性物質之二次電池針對低溫下之電流負荷特性亦可獲得高電容，且即使在高溫下對於重複充放電亦具充分耐受性。據此，本發明之碳複合化磷酸錳鐵鋰粒子粉末適合作為非水電解質二次電池用之正極活性物質。 The method for producing the carbon composite manganese iron iron phosphate particle powder of the present invention can be produced at a low cost and with a small environmental load, and the powder obtained by the method has a small electric resistance and a high filling property. Further, a secondary battery using the same as a positive electrode active material can also obtain a high capacitance against a current load characteristic at a low temperature, and is sufficiently resistant to repeated charge and discharge even at a high temperature. According to this, the carbon composite manganese iron iron phosphate particle powder of the present invention is suitable as a positive electrode active material for a nonaqueous electrolyte secondary battery.

圖1係實施例1所得之碳複合化磷酸錳鐵鋰粒子粉末之掃描型電子顯微鏡的高倍二次電子影像。 Fig. 1 is a high-order secondary electron image of a scanning electron microscope of the carbon composite manganese iron iron phosphate particle powder obtained in Example 1.

圖2係實施例1所得之碳複合化磷酸錳鐵鋰粒子粉末之掃描型電子顯微鏡之低倍二次電子影像。 2 is a low-power secondary electron image of a scanning electron microscope of the carbon composite manganese iron iron phosphate particle powder obtained in Example 1. FIG.

圖3係使實施例1所得之碳複合化磷酸錳鐵鋰粒子粉末予以正極化，使用硬幣電池在25℃與0℃評估之放電電容之電流負荷關係。 Fig. 3 is a graph showing the current load relationship of the discharge capacitors evaluated by the coin battery at 25 ° C and 0 ° C by positive electrode formation of the carbon composite manganese iron iron phosphate particle powder obtained in Example 1.

圖4係使實施例1所得之碳複合化磷酸錳鐵鋰粒子粉末予以正極化，使用硬幣電池在0℃評估之放電曲線之電 流負荷關係。 4 is a graph showing that the carbon composite manganese iron iron phosphate particle powder obtained in Example 1 was anodized, and the discharge curve was evaluated at 0 ° C using a coin battery. Flow load relationship.

圖5係使實施例1所得之碳複合化磷酸錳鐵鋰粒子粉末予以正極化，使用硬幣電池評價在60℃、2.0~4.5V間之循環特性時之充放電曲線(n=1、2、12、...、10×i，i=1~6)與各循環之放電電容。 Fig. 5 shows that the carbon composite manganese iron iron phosphate particle powder obtained in Example 1 was positively ionized, and the charge and discharge curves (n = 1, 2) when the cycle characteristics between 60 ° C and 2.0 to 4.5 V were evaluated using a coin battery. 12, ..., 10 × i, i = 1 ~ 6) and the discharge capacitance of each cycle.

圖6係使實施例1所得之碳複合化磷酸錳鐵鋰粒子粉末予以正極化，使用硬幣電池評價在60℃、2.0~4.3V間之循環特性時之充放電曲線(n=1、2、12、...、10×i，i=1~6)與各循環之放電電容。 6 is a graph showing that the carbon composite manganese iron iron phosphate particle powder obtained in Example 1 was anodized, and the charge and discharge curves (n=1, 2) when the cycle characteristics between 60 ° C and 2.0 to 4.3 V were evaluated using a coin battery. 12, ..., 10 × i, i = 1 ~ 6) and the discharge capacitance of each cycle.

若更詳細說明本發明之構成則如下。 The structure of the present invention will be described in more detail as follows.

首先，針對本發明之碳複合化磷酸錳鐵鋰粒子粉末之製造方法加以描述。 First, a method for producing the carbon composite manganese iron iron phosphate particle powder of the present invention will be described.

本發明之碳複合化磷酸錳鐵鋰粒子粉末之製造方法係以經水熱處理獲得之磷酸錳鐵鋰為原料予以製作。 The method for producing the carbon composite manganese iron iron phosphate particle powder of the present invention is produced by using lithium manganese iron phosphate obtained by hydrothermal treatment as a raw material.

所謂水熱處理係混合原料化合物之水溶液，在高溫高壓下合成化合物之方法。本發明中對於藉由水熱處理獲得磷酸錳鐵鋰之方法並不侷限，但為了以高的生成率獲得微細之磷酸錳鐵鋰，較好使用以下方法。 The hydrothermal treatment is a method in which an aqueous solution of a raw material compound is mixed and a compound is synthesized under high temperature and high pressure. In the present invention, the method for obtaining lithium iron manganese phosphate by hydrothermal treatment is not limited, but in order to obtain fine lithium iron iron phosphate at a high production rate, the following method is preferably used.

以水熱處理所得之產物較好為結晶子尺寸為200nm以下之微細Li1-αMn1-xFexP1-βO4-δ(0.02≦x≦0.5，0≦α,β≦0.2)。此處，α、β及γ為結晶學上之參數，α與 β不得超過0.2。此外，δ係為了滿足電中性條件而附加之參數。 The product obtained by hydrothermal treatment is preferably fine Li 1-α Mn 1-x Fe x P 1-β O 4-δ (0.02≦x≦0.5, 0≦α, β≦0.2) having a crystallite size of 200 nm or less. . Here, α, β and γ are crystallographic parameters, and α and β must not exceed 0.2. In addition, the δ system is a parameter added to satisfy the electrical neutral condition.

本發明之碳複合化磷酸錳鐵鋰之原料中，作為Li源有LiOH．H2O、Li2CO3，作為Mn原料有MnSO4．H2O、MnCO3，作為Fe原料有FeSO4．nH2O、FeCO3，作為P原料有H3PO4、(NH4)H2PO4、(NH4)2HPO4、(NH4)3PO4等。且，作為使主原料複合化之原料有Li3PO4、M3(PO4)2．nH2O、(NH4)MPO4．nH2O(以上，M=Mn、Fe)等。 In the raw material of the carbon composite manganese iron iron phosphate of the present invention, LiOH is used as the Li source. H 2 O, Li 2 CO 3 , as Mn raw material, MnSO 4 . H 2 O, MnCO 3 , FeSO 4 as Fe raw material. nH 2 O, FeCO 3 , and P raw materials include H 3 PO 4 , (NH 4 )H 2 PO 4 , (NH 4 ) 2 HPO 4 , (NH 4 ) 3 PO 4 , and the like. Further, as a raw material for compositing the main raw material, Li 3 PO 4 and M 3 (PO 4 ) 2 are used . nH 2 O, (NH 4 ) MPO 4 . nH 2 O (above, M = Mn, Fe) and the like.

水熱處理中，為了在生成多數磷酸錳鐵鋰之結晶核之條件下快速進行原料之混合或溶解．析出，較好使原料微粒子化。使漿液中之原料粒子之微粒子化時，可使用ZrO2球之介質施以粉碎或以高濃度進行原料混合。粉碎中使用之裝置列舉為球磨機、介質攪拌型研磨機等，又，作為高濃度原料混合裝置，列舉為輥或捏合機等。 In hydrothermal treatment, in order to rapidly mix or dissolve the raw materials under the conditions of generating a majority of the crystal nucleus of lithium manganese iron phosphate. Precipitation preferably makes the raw material fine particles. When the fine particles of the raw material particles in the slurry are used, the medium of the ZrO 2 sphere can be used for pulverization or the raw material can be mixed at a high concentration. The apparatus used for the pulverization is exemplified by a ball mill, a medium agitation type grinding machine, and the like, and a high-concentration material mixing device is exemplified by a roll or a kneader.

另外，亦可使用抗壞血酸或檸檬酸等有機酸，或葡萄糖等還原糖作為水熱處理時之Fe之抗氧化劑。其量相對於(Mn+Fe)較好為1~20mol%，而有提高水熱處理後之Li1-αMn1-xFexP1-βO4-δ(0.02≦x≦0.5，0≦α,β≦0.2)之反應率，且使該產物之一次粒徑微細化之傾向。 Further, an organic acid such as ascorbic acid or citric acid or a reducing sugar such as glucose may be used as an antioxidant of Fe in hydrothermal treatment. The amount thereof is preferably from 1 to 20 mol% relative to (Mn + Fe), and Li 1-α Mn 1-x Fe x P 1-β O 4-δ (0.02 ≦ x ≦ 0.5, 0) after hydrothermal treatment is increased. The reaction rate of ≦α, β≦0.2) and the tendency to make the primary particle diameter of the product fine.

另一方面，作為水熱處理時之鹼源可使用LiOH、NH3、NaOH、Na2CO3、NH3、尿素、乙醇胺等。為提高水熱處理後之磷酸錳鐵鋰之反應率時，pH需為 5.5~12.5。 On the other hand, as the alkali source in the hydrothermal treatment, LiOH, NH 3 , NaOH, Na 2 CO 3 , NH 3 , urea, ethanolamine or the like can be used. In order to increase the reaction rate of lithium manganese iron phosphate after hydrothermal treatment, the pH needs to be 5.5 to 12.5.

水熱處理愈需要溫度及時間時，有磷酸錳鐵鋰之反應率與粒徑愈增大之傾向，但以在90~300℃反應2~3小時較佳。 When the temperature and time of the hydrothermal treatment are required, the reaction rate and the particle size of lithium manganese iron phosphate tend to increase, but it is preferable to react at 90 to 300 ° C for 2 to 3 hours.

以本方法獲得之水熱處理後之產物以X射線繞射測定時觀察到75%以上之橄欖石型構造的結晶相。以本方法獲得之水熱處理後之產物為幾乎不含異相之磷酸錳鐵鋰。 The product of the hydrothermal treatment obtained by the present method was observed to have a crystalline phase of more than 75% of the olivine-type structure when measured by X-ray diffraction. The hydrothermally treated product obtained by this method is lithium manganese iron phosphate which contains almost no heterogeneous phase.

以本方法獲得之水熱處理後之磷酸錳鐵鋰之反應率超過80wt%。水熱處理後之磷酸錳鐵鋰之反應率係使所得粒子粉末在惰性氣體氛圍中、700℃熱處理2小時後，自該熱處理前後之重量減少量比例算出。例如，產生3wt%之重量減少時，反應率為100-3=97wt%。以本方法獲得之水熱處理後之產物幾乎為單相，故其重量減少認為是因水或二氧化碳等造成。 The reaction rate of the lithium manganese iron phosphate after the hydrothermal treatment obtained by the method exceeds 80% by weight. The reaction rate of the lithium iron phosphate after the hydrothermal treatment was calculated by subjecting the obtained particle powder to heat treatment at 700 ° C for 2 hours in an inert gas atmosphere, and then calculating the ratio of the weight loss before and after the heat treatment. For example, when a weight loss of 3 wt% is produced, the reaction rate is 100-3 = 97 wt%. The product obtained by the hydrothermal treatment obtained by the present method is almost single phase, so that the weight reduction is considered to be caused by water or carbon dioxide.

水熱處理後，視情況亦可進行產物之過濾洗淨或傾析洗淨以去除雜質之硫酸離子或銨離子與調整Li、Mn、Fe、P組成比。至於裝置有加壓過濾器、過濾濃縮機(filter thickener)等。 After the hydrothermal treatment, depending on the case, the product may be subjected to filtration washing or decantation washing to remove the sulfate ion or ammonium ion of the impurity and adjust the composition ratio of Li, Mn, Fe, and P. As for the device, there are a pressure filter, a filter thickener, and the like.

本發明中，將獲得含有以水熱處理生成之橄欖石型構造之磷酸錳鐵鋰與鋰化合物及/或磷化合物、與有機物之水系懸浮液或含水物設為第一步驟。至於獲得含有以水熱處理生成之磷酸錳鐵鋰與鋰化合物及/或磷化合物、與有機物之水系懸浮液或含水物之方法，有於以水熱 處理獲得之磷酸錳鐵鋰之水系漿液中添加鋰化合物及/或磷化合物與有機物之方法；或將鋰化合物及/或磷化合物與有機物添加混合於以水熱處理獲得之磷酸錳鐵鋰之水系漿液經脫水而成之濾餅中，作成含水物之方法；將鋰化合物及/或磷化合物與有機物及水添加混合於使以水熱處理獲得之磷酸錳鐵鋰之水系漿液予以乾燥、微粉碎而成之粉末中，作成含水物之方法等。 In the present invention, the first step is to obtain a lithium manganese iron phosphate and a lithium compound and/or a phosphorus compound containing an olivine structure formed by hydrothermal treatment, and an aqueous suspension or hydrate of an organic substance. A method for obtaining a water-based suspension or a hydrate containing lithium manganese iron phosphate and a lithium compound and/or a phosphorus compound formed by hydrothermal treatment, and an organic substance a method of adding a lithium compound and/or a phosphorus compound and an organic substance to an aqueous slurry of the obtained lithium iron manganese phosphate; or adding a lithium compound and/or a phosphorus compound and an organic substance to the aqueous slurry of lithium manganese iron phosphate obtained by hydrothermal treatment a method for preparing a hydrate by a dehydrated filter cake; mixing a lithium compound and/or a phosphorus compound with an organic substance and water, and drying and finely pulverizing the aqueous slurry of lithium manganese iron phosphate obtained by hydrothermal treatment In the powder, a method of preparing a hydrate or the like.

藉水熱處理生成之磷酸錳鐵鋰為結晶中具有較多缺陷者。因此，為了形成缺陷少之期望磷酸錳鐵鋰固熔體，必須調整燒結前之主成分組成比。亦即，必須藉由添加鋰化合物及/或磷化合物而調整為相對於以水熱處理獲得之磷酸錳鐵鋰，主成分組成比以mol比計成為0.98≦Li/(Mn+Fe)≦1.15，0.98≦P/(Mn+Fe)≦1.15，P≦Li。在特定之組成比以外時，會過度生成雜質相，成為使電池特性惡化之主因。亦即，Li/(Mn+Fe)過小時α-Fe、(Mn+Fe)2P、(Mn+Fe)3P、(Mn+Fe)2P2O7等過量生成，大為過量時會殘留過量Li2CO3。且，P/(Mn+Fe)過小時會生成過量之α-Fe、(Mn+Fe)2O3等，過大時會過量生成Li3PO4、Li4P2O7等。 Lithium iron manganese phosphate produced by heat treatment of water is a defect in crystals. Therefore, in order to form a desired lithium manganese iron phosphate solid solution having a small defect, it is necessary to adjust the main component composition ratio before sintering. That is, it is necessary to adjust to a lithium iron phosphate obtained by hydrothermal treatment by adding a lithium compound and/or a phosphorus compound, and the main component composition ratio is 0.98 ≦Li/(Mn+Fe)≦1.15 in terms of a molar ratio. 0.98 ≦P / (Mn + Fe) ≦ 1.15, P ≦ Li. When the specific composition ratio is out of the range, the impurity phase is excessively generated, which is a main cause of deterioration of battery characteristics. That is, when Li/(Mn+Fe) is too small, α-Fe, (Mn+Fe) 2 P, (Mn+Fe) 3 P, (Mn+Fe) 2 P 2 O 7 and the like are excessively formed, and when it is excessively large, Excess Li 2 CO 3 will remain. Further, when P/(Mn+Fe) is too small, an excessive amount of α-Fe, (Mn+Fe) 2 O 3 or the like is formed, and when it is too large, Li 3 PO 4 , Li 4 P 2 O 7 or the like is excessively formed.

本發明之主成分組成比調整所用之鋰化合物可使用LiOH、Li2CO3等。 As the lithium compound used for the adjustment of the main component composition ratio of the present invention, LiOH, Li 2 CO 3 or the like can be used.

本發明中主成分組成比調整所用之磷化合物可使用H3PO4、(NH4)H2PO4、(NH4)2HPO4、(NH4)3PO4等。 In the present invention, H 3 PO 4 , (NH 4 )H 2 PO 4 , (NH 4 ) 2 HPO 4 , (NH 4 ) 3 PO 4 or the like can be used as the phosphorus compound used for the adjustment of the main component composition ratio.

又，主成分組成比調整所用之含鋰及磷之化合物可使用LiH2PO4、Li3PO4、LiPO3等。 Further, LiH 2 PO 4 , Li 3 PO 4 , LiPO 3 or the like can be used as the compound containing lithium and phosphorus used for the adjustment of the main component composition ratio.

而且，本發明中主成分組成比調整中亦可併用鋰化合物、磷化合物、含鋰及磷之化合物。 Further, in the adjustment of the main component composition ratio in the present invention, a lithium compound, a phosphorus compound, a compound containing lithium and phosphorus may be used in combination.

本發明中用以調整組成比而添加之鋰化合物及/或磷化合物之60wt%以上為Li1-yH2+yPO4(0≦y≦1)。藉由較多地使用Li1-yH2+yPO4作為主成分組成比調整用之鋰化合物及/或磷化合物，大體上減低了燒結後獲得之碳複合化磷酸錳鐵鋰之各元素固有之位置的晶格子缺陷，提高了結晶性，而可獲得高性能之正極活性物質。較好對於添加之鋰化合物及/或磷化合物，Li1-yH2+yPO4使用75wt%以上。為調整組成比而添加之Li1-yH2+yPO4，較好使用60wt%以上，更好75wt%以上之LiH2PO4。LiH2PO4之使用量未達60wt%時，主成分組成比之調整無法以各個粒子等級成為均一，會過量生成粗大之Li3PO4或Li4P2O4，而成為電池特性惡化之要因。 60% by weight or more of the lithium compound and/or the phosphorus compound added to adjust the composition ratio in the present invention is Li 1-y H 2+y PO 4 (0≦y≦1). By using Li 1-y H 2+y PO 4 as a main component composition ratio lithium compound and/or a phosphorus compound, the elements of the carbon composite manganese iron iron obtained after sintering are substantially reduced. A crystal lattice defect at an intrinsic position improves crystallinity, and a high-performance positive electrode active material can be obtained. It is preferred to use 75 wt% or more of Li 1-y H 2+y PO 4 for the added lithium compound and/or phosphorus compound. In order to adjust the composition ratio of Li 1-y H 2+y PO 4 , it is preferred to use 60% by weight or more, more preferably 75% by weight or more of LiH 2 PO 4 . When the amount of LiH 2 PO 4 used is less than 60% by weight, the adjustment of the main component composition ratio cannot be uniform for each particle level, and coarse Li 3 PO 4 or Li 4 P 2 O 4 is excessively formed, which deteriorates battery characteristics. The cause.

且，Li3PO4由於容易形成50nm以下之水不溶性微粒子，且可與燒結前之磷酸錳鐵鋰容易地均勻混合，故可較好地使用。 Further, since Li 3 PO 4 is easily formed into water-insoluble fine particles of 50 nm or less and can be easily and uniformly mixed with lithium manganese iron phosphate before sintering, it can be preferably used.

本發明中，第一步驟所得之水系懸浮液或含水物中，相對於以水熱處理獲得之磷酸錳鐵鋰必須含1~20wt%之有機物。有機物之量較好為5~15wt%。有機物之添加量太少時，燒結後之殘留碳量減少，藉燒結使磷酸錳鐵鋰與碳之複合化變不充分。另外，有機物之添加量過 多時促進了雜質相之α-Fe、(Mn+Fe)2P、(Mn+Fe)3P之生成，成為電池特性惡化之要因。所添加之有機物可使用水可溶性或水分散性之有機物，尤其是使用水可溶性有機物時，由於均一改善了磷酸錳鐵鋰粒子表面故較佳。亦可使用水可溶性有機物與水分散性之有機物兩者。 In the present invention, the aqueous suspension or the aqueous product obtained in the first step must contain 1 to 20% by weight of the organic matter relative to the lithium manganese iron phosphate obtained by hydrothermal treatment. The amount of the organic substance is preferably from 5 to 15% by weight. When the amount of the organic substance added is too small, the amount of residual carbon after sintering is reduced, and the composite of lithium manganese iron phosphate and carbon is insufficient by sintering. Further, when the amount of the organic substance added is too large, the formation of α-Fe, (Mn+Fe) 2 P, and (Mn+Fe) 3 P in the impurity phase is promoted, which is a factor for deterioration of battery characteristics. The organic substance to be added may be a water-soluble or water-dispersible organic substance, and particularly when a water-soluble organic substance is used, it is preferable since the surface of the lithium iron phosphate particles is uniformly improved. Both water-soluble organic matter and water-dispersible organic matter can also be used.

水可溶性有機物宜為屬於含羥基(-OH)、或羧基(-COOH)之多元醇、糖或有機酸之水可溶性有機物，具體而言有聚乙烯醇(PVA)、蔗糖、檸檬酸、乙二醇等。 The water-soluble organic matter is preferably a water-soluble organic substance belonging to a polyol, a sugar or an organic acid containing a hydroxyl group (-OH) or a carboxyl group (-COOH), specifically polyvinyl alcohol (PVA), sucrose, citric acid, and ethylene. Alcohol, etc.

另外，作為水分散性之有機物，有施以親水化處理之合成纖維或碳黑，例如，對於聚乙烯粒子、乙炔黑(電氣化學工業(股)製)或科琴黑(Lion(股)製)，有必要以具有親水基與疏水基之PVA、或非離子性界面活性劑(例如，聚氧伸乙基醚)、或LiOH等鹼性溶液進行表面改質。 Further, as the water-dispersible organic substance, there are synthetic fibers or carbon black which are subjected to hydrophilization treatment, for example, polyethylene particles, acetylene black (manufactured by Electric Chemical Industry Co., Ltd.) or Ketchen Black (Lion) It is necessary to carry out surface modification by an alkaline solution such as PVA having a hydrophilic group and a hydrophobic group, or a nonionic surfactant (for example, polyoxyethyl ether) or LiOH.

本發明中，在水存在下混合由水熱處理生成之橄欖石型構造之磷酸錳鐵鋰與用以調整主成分組成之鋰化合物及/或磷化合物與有機物而呈均勻混合。藉此，改善磷酸錳鐵鋰之粒子表面，而為可以對環境負荷小之工業上製造方法獲得具備高的電池特性之橄欖石型構造之磷酸錳鐵鋰粒子粉末者。 In the present invention, lithium iron manganese phosphate having an olivine structure formed by hydrothermal treatment and a lithium compound and/or a phosphorus compound and an organic compound for adjusting a main component are uniformly mixed in the presence of water. In this way, the surface of the particles of lithium iron phosphate is improved, and the lithium iron phosphate particle powder having an olivine structure having high battery characteristics can be obtained by an industrial production method having a small environmental load.

尤其，本發明之第一步驟中，用於調整主成分組成比之鋰化合物及/或磷化合物為Li1-yH2+yPO4(0≦y≦1)，且使用水可溶性有機物作為添加之有機物 時，由於在第二步驟中經乾燥獲得燒結用前驅物混合粉末時藉加熱之脫水而引起磷酸酯反應與聚合反應，故認為Li-P非晶質相與燒結獲得之碳一起改善了磷酸錳鐵鋰粒子表面。 In particular, in the first step of the present invention, the lithium compound and/or the phosphorus compound for adjusting the composition ratio of the principal components is Li 1-y H 2+y PO 4 (0≦y≦1), and water-soluble organic matter is used as When the organic substance is added, since the phosphate reaction and the polymerization reaction are caused by dehydration by heating when the mixed precursor powder for sintering is obtained by drying in the second step, it is considered that the Li-P amorphous phase is improved together with the carbon obtained by sintering. The surface of the lithium iron phosphate particles.

本發明之第二步驟中，使第一步驟中獲得之磷酸錳鐵鋰之水系懸浮液或含水物乾燥，獲得燒結用前驅物混合粉末。乾燥溫度較好為40~250℃。水系懸浮液或含水物之乾燥方法列舉為以分散機等混合水系漿液，且以通常之乾燥機乾燥之方法；或以噴霧乾燥機或漿液乾燥機進行乾燥之方法；以滾筒或捏合機混練將水添加於水系濾餅或乾燥粉末中之含水物，且以通常之乾燥機進行乾燥之方法等。本發明中，主成分組成比調整用所用之Li1-yH2+yPO4為酸性，故宜短時間內進行乾燥(例如，針對500g之漿液為1小時以內)，以致不會對水熱處理後之磷酸錳鐵鋰粒子造成損傷。 In the second step of the present invention, the aqueous suspension or hydrate of the lithium manganese iron phosphate obtained in the first step is dried to obtain a precursor powder for sintering. The drying temperature is preferably from 40 to 250 °C. The method for drying the aqueous suspension or the hydrate is exemplified by mixing the aqueous slurry with a dispersing machine or the like, and drying it in a usual dryer; or drying by a spray dryer or a slurry dryer; mixing by a drum or a kneader A method in which water is added to a water-based filter cake or a hydrated material in a dry powder, and dried in a usual dryer. In the present invention, Li 1-y H 2+y PO 4 used for the adjustment of the main component composition ratio is acidic, so it is preferred to carry out drying in a short time (for example, within 1 hour for 500 g of the slurry) so that water is not The manganese iron iron phosphate particles after the heat treatment cause damage.

本發明之碳複合化磷酸錳鐵鋰粒子粉末之凝集粒徑，在燒結前後之凝集粒徑幾乎沒有變化。因此，在第一步驟至第二步驟之間，或第三步驟後必須調整凝集粒徑。凝集粒徑之調整可藉由各步驟中之混合．乾燥方法或分級．粉碎予以控制。至於粉碎裝置有高速衝擊式粉碎機、瑪瑙研缽等。 The aggregated particle diameter of the carbon composite manganese iron iron phosphate particle powder of the present invention hardly changes in the aggregated particle diameter before and after the sintering. Therefore, the agglomerated particle size must be adjusted between the first step to the second step or after the third step. The adjustment of the agglomerated particle size can be achieved by mixing in each step. Drying method or classification. Crush is controlled. As for the pulverizing device, there are a high-speed impact pulverizer, an agate mortar, and the like.

本發明之第三步驟中，係在氧濃度0.1%以下之惰性氣體或還原性氣體氛圍下，於溫度250~850℃下燒成第二步驟中獲得之燒結用前驅物混合粉末。進行燒結之 裝置有氣體流通式箱型馬弗爐、氣體流通式旋轉爐、流動熱處理爐等。作為惰性氣體係使用N2、Ar、H2O、CO2或其混合氣體。作為還原性氣體係使用H2或CO、或該等氣體與前述惰性氣體之混合氣體。 In the third step of the present invention, the mixed precursor powder for sintering obtained in the second step is fired at a temperature of 250 to 850 ° C in an inert gas or a reducing gas atmosphere having an oxygen concentration of 0.1% or less. The apparatus for sintering includes a gas flow type box muffle furnace, a gas flow type rotary furnace, a flow heat treatment furnace, and the like. As the inert gas system, N 2 , Ar, H 2 O, CO 2 or a mixed gas thereof is used. As the reducing gas system, H 2 or CO or a mixed gas of the gases and the inert gas described above is used.

Fe原料中所含之微量Fe3+由於可藉由有機物、或還原性氣體而轉化成Fe2+，生成磷酸錳鐵鋰，故有必要在氧濃度0.1%以下之氛圍中進行燒結用前驅物混合粉末之燒結。為使未反應物之反應完全，且自添加有機物形成電子傳導性高之石墨相，較好在400~800℃進行數小時之熱處理。 Since a trace amount of Fe 3+ contained in the Fe raw material can be converted into Fe 2+ by an organic substance or a reducing gas to form lithium manganese iron phosphate, it is necessary to carry out a sintering precursor in an atmosphere having an oxygen concentration of 0.1% or less. Sintering of mixed powders. In order to complete the reaction of the unreacted material and form a graphite phase having high electron conductivity from the addition of the organic substance, it is preferred to carry out heat treatment at 400 to 800 ° C for several hours.

接著，針對本發明之碳複合化磷酸錳鐵鋰粒子粉末加以描述。 Next, the carbon composite manganese iron iron phosphate particle powder of the present invention will be described.

本發明之碳複合化磷酸錳鐵鋰粒子粉末之鋰與磷之含量相對於過渡金屬以莫耳比計，各為0.98~1.15，且鋰之含量為磷以上。鋰與磷之含量在該範圍之外時，磷酸錳鐵鋰含較多之異相，故無法獲得高的電池特性。較好鋰與磷之含量相對於過渡金屬以莫耳比計各為1.01至1.10，且鋰之含量為磷以上。 The content of lithium and phosphorus in the carbon composite manganese iron iron phosphate particle powder of the present invention is 0.98 to 1.15 in terms of a molar ratio with respect to the transition metal, and the lithium content is phosphorus or more. When the content of lithium and phosphorus is out of this range, lithium iron manganese phosphate contains a large amount of out-of-phase, so that high battery characteristics cannot be obtained. Preferably, the content of lithium and phosphorus is 1.01 to 1.10 in terms of molar ratio with respect to the transition metal, and the content of lithium is phosphorus or more.

本發明之碳複合化磷酸錳鐵鋰粒子粉末之單位晶胞體積由於比由下述式1所示之Vegard定律推測之橄欖石型構造的LiMn1-xFexPO4之單位晶胞體積VUC(Å3)小，故認為結晶內幾乎沒有晶格缺陷。 The unit cell volume of the carbon composite manganese iron iron phosphate particle powder of the present invention is a unit cell volume V of LiMn 1-x Fe x PO 4 which is estimated by the olivine type structure estimated by Vegard's law shown by the following formula 1. UC (Å 3 ) is small, so it is considered that there are almost no lattice defects in the crystal.

VUC(Å3)=11.4×(1-x)+291.21...(1) V UC (Å 3 )=11.4×(1-x)+291.21...(1)

據此，本發明之碳複合化磷酸錳鐵鋰粒子粉末之單位 晶胞體積對於式(1)之單位晶胞體積VUC之比例較好為99.950%以下。 Accordingly, the ratio of the unit cell volume of the carbon composite manganese iron iron phosphate particle powder of the present invention to the unit cell volume V UC of the formula (1) is preferably 99.950% or less.

本發明之碳複合化磷酸錳鐵鋰粒子粉末之BET比表面積較好為6~70m2/g。BET比表面積值未達6m2/g時，會有磷酸錳鐵鋰粒子為大粒子之情況，結晶中之Li離子之移動緩慢，因此難以取出電流。超過70m2/g時，由於正極之填充密度降低或與電解液之反應性增加故不佳。更好為8~28m2/g，又更好為9~20m2/g。 The carbon composite manganese iron iron phosphate particle powder of the present invention preferably has a BET specific surface area of 6 to 70 m 2 /g. When the BET specific surface area value is less than 6 m 2 /g, the lithium manganese iron phosphate particles are large particles, and the movement of Li ions in the crystal is slow, so that it is difficult to take out the current. When it exceeds 70 m 2 /g, it is not preferable because the packing density of the positive electrode is lowered or the reactivity with the electrolytic solution is increased. More preferably 8 ~ 28m 2 / g, and more preferably 9 ~ 20m 2 / g.

本發明之碳複合化磷酸錳鐵鋰粒子粉末之殘留碳量較好為0.7~8.0wt%。碳含有率未達0.7wt%時，所得粉體之電阻變高，而使二次電池之充放電特性惡化。且超過8.0wt%時，正極填充密度降低，且二次電池之每體積之能量密度變小。更好為1.0~4.0wt%。 The residual carbon content of the carbon composite manganese iron iron phosphate particle powder of the present invention is preferably from 0.7 to 8.0% by weight. When the carbon content is less than 0.7% by weight, the electric resistance of the obtained powder becomes high, and the charge and discharge characteristics of the secondary battery are deteriorated. When the amount exceeds 8.0% by weight, the positive electrode packing density is lowered, and the energy density per volume of the secondary battery becomes small. More preferably 1.0 to 4.0 wt%.

本發明之碳複合化磷酸錳鐵鋰粒子粉末藉由使雜質硫量為0.08wt%以下，而獲得非水電解質二次電池之良好保存特性。前述殘留量超過0.08wt%時，會形成硫酸鋰等雜質，在充放電中該等雜質引起分解反應，使高溫循環特性時之電阻上升激烈。更好為0.05wt%以下。 The carbon composite manganese iron iron phosphate particle powder of the present invention obtains good storage characteristics of the nonaqueous electrolyte secondary battery by setting the impurity sulfur amount to 0.08 wt% or less. When the residual amount exceeds 0.08 wt%, impurities such as lithium sulfate are formed, and during the charge and discharge, the impurities cause a decomposition reaction, and the resistance at high temperature cycle characteristics is highly increased. More preferably, it is 0.05% by weight or less.

本發明之碳複合化磷酸錳鐵鋰粒子粉末，除橄欖石構造以外，亦可檢測出5.0wt%以下之Li3PO4之結晶相。Li3PO4本身由於無助於積極之充放電故較好為5.0wt%以下，但另一方面檢測出Li3PO4時，也會有放電電容變高之情況，更好為0.1~3.0wt%。基於電流負荷特性或高溫循環特性之結果，雜質結晶相之M2P2O7(M=Mn、 Fe)或Fe2P之金屬相期望儘可能沒有。 In the carbon composite lithium manganese iron phosphate particle powder of the present invention, in addition to the olivine structure, a crystal phase of Li 3 PO 4 of 5.0 wt% or less can be detected. Li 3 PO 4 itself is preferably 5.0 wt% or less because it does not contribute to positive charge and discharge. On the other hand, when Li 3 PO 4 is detected, the discharge capacity may become high, preferably 0.1 to 3.0. Wt%. As a result of the current load characteristics or the high temperature cycle characteristics, the metal phase of the impurity crystal phase of M 2 P 2 O 7 (M = Mn, Fe) or Fe 2 P is desirably not present as much as possible.

本發明之碳複合化磷酸錳鐵鋰粒子粉末之結晶子尺寸較好為25~300nm。以本發明之製造方法量產滿足其他粉體特性並且結晶子尺寸未達25nm之粉末極為困難，且超過300nm之結晶子尺寸時，使Li於粒子內移動需要時間，結果，使二次電池之電流負荷特性惡化。更好為30~200nm，又更好為40~150nm。 The carbon composite manganese manganese iron lithium particle powder of the present invention preferably has a crystallite size of 25 to 300 nm. It is extremely difficult to mass-produce a powder satisfying other powder characteristics and having a crystallite size of less than 25 nm by the production method of the present invention, and when it exceeds the crystallite size of 300 nm, it takes time for Li to move inside the particle, and as a result, the secondary battery is made. The current load characteristics deteriorate. More preferably 30 to 200 nm, and even more preferably 40 to 150 nm.

本發明之碳複合化磷酸錳鐵鋰粒子粉末之凝集粒徑較好為0.3~30μm。凝集粒徑未達0.3μm時，正極填充密度降低或與電解液之反應性增加故不佳。另一方面，凝集粒徑超過30μm時，更接近電極膜厚，會發生對於電極之膜厚方向僅裝載二、三個粒子之情況，極難以薄片化。更好為0.5~25μm，又更好為1.0~20μm。 The agglomerated particle diameter of the carbon composite manganese iron iron phosphate particle powder of the present invention is preferably from 0.3 to 30 μm. When the aggregated particle diameter is less than 0.3 μm, the positive electrode packing density is lowered or the reactivity with the electrolytic solution is increased, which is not preferable. On the other hand, when the aggregated particle diameter exceeds 30 μm, the thickness of the electrode film is closer to the thickness of the electrode, and only two or three particles are loaded in the film thickness direction of the electrode, and it is extremely difficult to form a sheet. More preferably, it is 0.5 to 25 μm, and more preferably 1.0 to 20 μm.

本發明之碳複合化磷酸錳鐵鋰粒子粉末之壓縮成型體密度較好為1.8g/cc以上。若接近真密度則越接近填充性越良好，相對於作為二次電池之正極活性物質良好使用之層狀化合物LiCoO2之真密度為5.1g/cc，磷酸錳鐵鋰之真密度低如3.5g/cc。因此，較佳之壓縮成型體密度為超過真密度之50%之2.0g/cc以上。另一方面，以本發明之製造方法量產滿足其他粉體特性同時壓縮成型體密度超過2.8g/cc之粉末極為困難。本發明之碳複合化磷酸錳鐵鋰粒子粉末之殘留碳量少，且一次粒子彼此適度凝集，故認為壓縮成型體密度高。 The density of the compression molded body of the carbon composite manganese iron iron phosphate particle powder of the present invention is preferably 1.8 g/cc or more. When the density is close to the true density, the closer the filling property is, the better the true density of the layered compound LiCoO 2 which is used as a positive electrode active material for a secondary battery is 5.1 g/cc, and the true density of lithium manganese iron phosphate is as low as 3.5 g. /cc. Therefore, the density of the compression molded body is preferably 2.0 g/cc or more which is more than 50% of the true density. On the other hand, it is extremely difficult to mass-produce a powder satisfying other powder characteristics while compressing a molded body density exceeding 2.8 g/cc by the production method of the present invention. In the carbon composite manganese iron iron phosphate particle powder of the present invention, the amount of residual carbon is small, and the primary particles are appropriately aggregated, so that the density of the compression molded body is considered to be high.

本發明之碳複合化磷酸錳鐵鋰粒子粉末之壓 縮成型體之電阻率較好為1.0×103Ω．cm以下。若電阻率低，則可減低製作正極薄片時之導電材之添加量，可獲得密度高之正極薄片。 The compression molded body of the carbon composite manganese iron iron phosphate particle powder of the present invention preferably has a resistivity of 1.0×10 3 Ω. Below cm. When the specific resistance is low, the amount of the conductive material added when the positive electrode sheet is formed can be reduced, and a positive electrode sheet having a high density can be obtained.

接著，針對使用本發明之碳複合化磷酸錳鐵鋰作為正極活性物質之非水電解質二次電池加以描述。 Next, a nonaqueous electrolyte secondary battery using the carbon composite manganese iron iron phosphate of the present invention as a positive electrode active material will be described.

使用本發明之正極活性物質製造正極薄片時，係根據常用方法，添加混合導電劑與黏著劑。作為導電劑較好為碳黑、石墨等，至於黏著劑較好為聚四氟乙烯、聚偏氟化乙烯等。使用例如N-甲基吡咯烷酮作為溶劑，將含有篩分出75μm以下之該正極活性物質與該添加物之漿液混練至成為蜂蜜狀。以溝槽為25~500μm之刮板將所得漿液塗佈於集電體上。該塗佈速度約為60cm/sec，至於集電體，通常使用約20μm之Al箔。為去除溶劑與黏著劑軟化，故在80~180℃進行乾燥。以使該薄片承受1~3t/cm2的壓力之方式進行軋光輥處理。前述薄片化之步驟中，由於在室溫下亦會發生Fe2+氧化成Fe3+之反應，故宜儘可能在非氧化性氛圍中進行。 When the positive electrode sheet is produced by using the positive electrode active material of the present invention, a conductive agent and an adhesive are added in accordance with a usual method. The conductive agent is preferably carbon black, graphite or the like, and the adhesive is preferably polytetrafluoroethylene or polyvinylidene fluoride. For example, N-methylpyrrolidone is used as a solvent, and the positive electrode active material having a sieved content of 75 μm or less is kneaded with a slurry of the additive to have a honey form. The resulting slurry was applied to a current collector with a squeegee having a groove of 25 to 500 μm. The coating speed is about 60 cm/sec, and as for the current collector, an Al foil of about 20 μm is usually used. In order to remove the solvent and the adhesive softening, it is dried at 80 to 180 °C. The calender roll treatment was carried out so that the sheet was subjected to a pressure of 1 to 3 t/cm 2 . In the step of flaking, since the reaction of Fe 2+ to Fe 3+ occurs at room temperature, it is preferably carried out in a non-oxidizing atmosphere as much as possible.

本發明之正極薄片，由於該正極或性物質之壓縮成型體密度高如1.8g/cc以上，且該正極活性物質之壓縮成型體之電阻率低如0.1~104Ω．cm，故可減低薄片製作時之碳添加量，且，由於該正極活性物質之BET比表面積低如6~70m2/g，故可減低黏著劑添加量，結果獲得密度高之正極薄片。 In the positive electrode sheet of the present invention, the density of the compression molded body of the positive electrode or the substance is as high as 1.8 g/cc or more, and the resistivity of the compression molded body of the positive electrode active material is as low as 0.1 to 10 4 Ω. Since the amount of carbon added during the production of the sheet is reduced, and the BET specific surface area of the positive electrode active material is as low as 6 to 70 m 2 /g, the amount of the binder can be reduced, and as a result, a positive electrode sheet having a high density can be obtained.

作為負極活性物質可使用鋰金屬、鋰/鋁合 金、鋰/錫合金、石墨等，與正極同樣地利用刮板法或金屬壓延製作負極薄片。 As the negative electrode active material, lithium metal, lithium/aluminum can be used. In the same manner as the positive electrode, gold, lithium/tin alloy, graphite, or the like is used to produce a negative electrode sheet by a doctor blade method or metal rolling.

且，電解液之溶劑除了碳酸伸乙酯與碳酸二乙酯之組合以外，亦可使用含有碳酸伸丙酯、碳酸二甲酯等碳酸酯類、或二甲氧基乙烷等醚類之至少1種之有機溶劑。 Further, in addition to the combination of ethyl carbonate and diethyl carbonate, the solvent of the electrolytic solution may be at least a carbonate such as propyl carbonate or dimethyl carbonate or an ether such as dimethoxyethane. 1 kind of organic solvent.

再者，作為電解質，除六氟磷酸鋰以外，亦可將過氯酸鋰、四氟化硼酸鋰等鋰鹽之至少1種溶解於上述溶劑中而使用。 Further, as the electrolyte, at least one of lithium salts such as lithium perchlorate or lithium tetrafluoroborate may be dissolved in the above solvent in addition to lithium hexafluorophosphate.

使用本發明之正極薄片製造之二次電池之特性為在25℃之0.1C下之放電電容為150mAh/g以上，於室溫之1C下之放電電容為140mAh/g以上，於室溫之5C下之放電電容為120mAh/g以上。此處，所謂0.1C係於20小時內LiMn1-xFexPO4(0.02≦x≦0.5)之理論電容170mAh/g之流過電流固定之電流值，1C為在1小時內理論電容170mAh/g之流過電流固定之電流值，且，5C為在1/5小時內理論電容170mAh/g之流過電流固定之電流值。C之係數愈高，意指愈高的電流負荷特性。 The secondary battery manufactured using the positive electrode sheet of the present invention has a discharge capacity of 150 mAh/g or more at 0.1 C at 25 ° C, a discharge capacity of 140 mAh/g or more at room temperature of 1 C, and 5 C at room temperature. The discharge capacitance is 120 mAh/g or more. Here, the 0.1C is a current value of 170mAh/g of the theoretical capacitance of LiMn 1-x Fe x PO 4 (0.02≦x≦0.5) within 20 hours, and 1C is the theoretical capacitance of 170mAh in 1 hour. /g flows through the current value of the fixed current, and 5C is the current value of the current flowing through the current of the theoretical capacitance of 170 mAh/g in 1/5 hours. The higher the coefficient of C, the higher the current load characteristics.

且，使用本發明之正極薄片所製造之二次電池，如圖3~6所示，顯示關於低溫下之電流負荷特性、高溫下之循環特性均優異之特性。 Further, as shown in FIGS. 3 to 6, the secondary battery produced by using the positive electrode sheet of the present invention exhibits characteristics excellent in current load characteristics at low temperatures and cycle characteristics at high temperatures.

〈作用〉 <effect>

本發明之碳複合化磷酸錳鐵鋰粒子粉末藉由水熱處理 與熱處理製造，可以低成本、環境負荷小地製造。依據本發明之製造方法，由於所得碳複合化磷酸錳鐵鋰粒子粉末之結晶性與粒子表面及凝集粒徑受到控制，故本發明人推定為於使用作為二次電池之正極活性物質時，關於室溫、及低溫下之電流負荷特性均可獲得高電容，且能在高溫下重複地進行充分的充放電。 The carbon composite manganese iron iron phosphate particle powder of the invention is hydrothermally treated by water It is manufactured by heat treatment and can be manufactured at low cost and with low environmental load. According to the production method of the present invention, since the crystallinity of the obtained carbon composite manganese iron iron phosphate particle powder and the particle surface and the aggregated particle diameter are controlled, the inventors presume that when a positive electrode active material as a secondary battery is used, High current capacity can be obtained at room temperature and current load characteristics at low temperatures, and sufficient charge and discharge can be repeatedly performed at high temperatures.

實施例 Example

本發明之代表實施形態如下。 Representative embodiments of the present invention are as follows.

鋰、及含磷主原料的Li、P濃度係使用pH計與鹽酸或NaOH試藥，藉中和滴定而測定。鐵原料之Fe濃度係藉由滴定(JIS K5109)，錳原料之Mn濃度亦藉由滴定(分析化學便覽日本分析化學會編)定量化。以該等分析結果為依據，決定反應濃度與饋入原料之比。添加劑之重量比係以饋入量計算。 The Li and P concentrations of lithium and the phosphorus-containing main raw material were measured by a pH meter and hydrochloric acid or NaOH, and were measured by neutralization titration. The Fe concentration of the iron raw material is titrated (JIS K5109), and the Mn concentration of the manganese raw material is also quantified by titration (analytical chemistry, edited by the Analytical Chemistry Society of Japan). Based on the results of these analyses, the ratio of the reaction concentration to the feedstock is determined. The weight ratio of the additive is calculated based on the amount of feed.

水熱處理之反應率之評價係使用氛圍管狀爐(HS10S-2050TF，Heat System(股)製)以熱分析進行。在惰性氣體氛圍中，使藉由水熱處理獲得之磷酸錳鐵鋰之乾燥粉末在700℃熱處理2小時，由熱處理前後之重量減少量之比例算出。 The evaluation of the reaction rate of the hydrothermal treatment was carried out by thermal analysis using an atmosphere tubular furnace (HS10S-2050TF, manufactured by Heat System Co., Ltd.). The dry powder of lithium manganese iron phosphate obtained by hydrothermal treatment was heat-treated at 700 ° C for 2 hours in an inert gas atmosphere, and was calculated from the ratio of the weight reduction amount before and after the heat treatment.

各步驟之磷酸錳鐵鋰之結晶相評價係使用X射線繞射裝置SmartLab[Rigaku(股)製]，在Cu-Kα、45kV、200mA之條件下測定，且使用Rietveld法。X射線繞射圖型係以使最高波峰強度之計數數成為 8000~15000之方式，以0.02°之步進，以計數時間3.0秒於2θ為15~90°之範圍內進行測定。使用NIST(National Institute of Standards and Technology，國際標準及技術協會)之SRM674b作為外部標準試料，於Rietveld解析程式係使用RIETAN2000。此時，假定為結晶子並無異向擴展，且使用TCH擬Voigt函數(Pseudo-Voigt function)作為分佈函數(Profile function)，對其函數之非對稱化係使用Finger等之手法，以使信賴度因子S值不高於2.0之方式進行解析。對於電極活性物質之晶格常數(單位晶胞體積)與結晶子尺寸之評價係使用相同方法。 The crystal phase evaluation of lithium manganese iron phosphate in each step was carried out under the conditions of Cu-Kα, 45 kV, and 200 mA using an X-ray diffraction apparatus SmartLab [manufactured by Rigaku Co., Ltd.), and the Rietveld method was used. The X-ray diffraction pattern is such that the count of the highest peak intensity becomes The method of 8000~15000 is carried out in the range of 0.02°, and the measurement time is 3.0 seconds in the range of 15 to 90°. SRM674b from NIST (National Institute of Standards and Technology) was used as an external standard sample, and RIETAN2000 was used in the Rietveld analysis program. At this time, it is assumed that the crystallizer does not spread in the opposite direction, and the TCH pseudo Voigt function (Pseudo-Voigt function) is used as the profile function, and the asymmetry of the function is performed using Finger et al. The degree factor S value is not higher than 2.0 for analysis. The same method was used for the evaluation of the lattice constant (unit cell volume) of the electrode active material and the crystallite size.

〈參考文獻〉 <references>

F. Izumi and T. Ikeda, Mater. Sci. Forum, 2000, Vol, 321-324, p.198.各步驟之磷酸錳鐵鋰之Li、Mn、Fe、P主元素係使用發光電漿分析裝置ICAP-6500[Thermo Fisher Scientific公司製]，藉由ICP測定進行測定。試料溶解係使用高壓釜，在200℃之酸溶液中溶解。 F. Izumi and T. Ikeda, Mater. Sci. Forum, 2000, Vol, 321-324, p.198. Li, Mn, Fe, P main elements of lithium manganese iron phosphate in each step use luminescent plasma analysis device ICAP-6500 [manufactured by Thermo Fisher Scientific Co., Ltd.] was measured by ICP measurement. The sample was dissolved in an autoclave and dissolved in an acid solution at 200 °C.

以下，進行由本發明所得之碳複合化磷酸錳鐵鋰粒子粉末之粉體評價。 Hereinafter, the powder evaluation of the carbon composite manganese iron iron phosphate particle powder obtained by the present invention was carried out.

BET比表面積係使試料在氮氣下，於120℃乾燥脫氣45分鐘後，使用MONOSORB[YUASA-Ionics(股)製]。 The BET specific surface area was such that the sample was dried and degassed at 120 ° C for 45 minutes under nitrogen, and then MONOSORB [manufactured by YUASA-Ionics Co., Ltd.] was used.

殘留碳與殘留硫量係使用EMIA-820[HORIBA製作所(股)製]，在燃燒爐內於氧氣流中燃燒，並定量 化。 The amount of residual carbon and residual sulfur is EMIA-820 [manufactured by HORIBA Manufacture Co., Ltd.], burned in a gas stream in a combustion furnace, and quantified. Chemical.

凝集粒徑係使用濕式法之雷射繞射．散射型粒度分佈計之MicroTrack[日機裝(股)製]，以中值徑D50定量化。 The agglomerated particle size is a laser diffraction using a wet method. The MicroTrack [Nikkiso Co., Ltd.] of the scattering type particle size distribution meter was quantified by the median diameter D 50 .

壓縮成型體密度係以13mm 之治具以1.5t/cm2進行壓粉，由重量與體積算出。且，同時藉由2端子法測定壓縮成型體之電阻率。 Compressed molded body density is 13mm The jig was pressed at 1.5 t/cm 2 and was calculated from the weight and volume. Further, the resistivity of the compression molded body was measured by a two-terminal method.

對本發明所得之碳複合化磷酸錳鐵鋰之形狀觀察係使用日立製之S-4300型掃描型電子顯微鏡(SEM)。 The shape of the carbon composite manganese iron iron phosphate obtained by the present invention was observed using a S-4300 scanning electron microscope (SEM) manufactured by Hitachi.

使用碳複合化磷酸錳鐵鋰粒子粉末，以CR2032型硬幣電池評價二次電池特性。 The secondary battery characteristics were evaluated using a carbon composite manganese iron iron phosphate particle powder using a CR2032 type coin battery.

所用之導電輔助劑之碳為乙炔黑。所用之黏著劑係聚合度63萬之聚偏氟化乙烯(KUREHA(股)製之KF聚合物)，並溶解於N-甲基吡咯烷酮(關東化學(股)製)中。至於電極組成比A，以重量比計，係以成為電極活性物質：乙炔黑：PVDF=88：4：8之方式，調整正極材漿液，以250μm間隙之刮板塗佈於Al集電體上，在120℃於空氣中乾燥10分鐘，將乾燥之薄片以3t/cm2進行加壓，製作30~40μm左右膜厚之正極薄片。且，作為電極組成比B，以重量比計係以成為電極活性物質：乙炔黑：PVDF=86：7：7之方式調整正極材漿液，且進行相同處理。 The carbon of the conductive auxiliary used is acetylene black. The adhesive used was a polyvinylidene fluoride (KFEHA KFE polymer) having a polymerization degree of 630,000, and was dissolved in N-methylpyrrolidone (manufactured by Kanto Chemical Co., Ltd.). As for the electrode composition ratio A, in terms of a weight ratio, the positive electrode material slurry was adjusted in such a manner as to become an electrode active material: acetylene black: PVDF = 88:4:8, and a 250 μm gap scraper was applied to the Al current collector. The film was dried in air at 120 ° C for 10 minutes, and the dried sheet was pressed at 3 t / cm 2 to prepare a positive electrode sheet having a film thickness of about 30 to 40 μm. Further, as the electrode composition ratio B, the positive electrode material slurry was adjusted so as to be an electrode active material: acetylene black: PVDF = 86:7:7 by weight ratio, and the same treatment was carried out.

使用沖壓成2cm2之正極薄片、沖壓成 17mm 之厚度0.15mm Li負極、19mm 之隔離片(Celgard #2400)、溶解1mol/l之LiPF6之EC與DMC(碳酸伸乙酯：碳酸二甲酯=3：7體積比)混合之電解液(KISHIDA化學製)，製作CR2032型硬幣電池(寶泉(股)製造)。 Using a positive electrode sheet punched into 2 cm 2 and punched into 17 mm Thickness 0.15mm Li negative, 19mm A separator (Celgard #2400), an electrolyte in which 1 mol/l of LiPF 6 is dissolved, and an electrolyte (made by Kishida Chemical Co., Ltd.) in which DMC (ethyl carbonate: dimethyl carbonate = 3:7 by volume) is mixed to prepare a CR2032 type. Coin battery (made by Baoquan (stock)).

以使用電極組成比A之正極薄片之硬幣電池於25℃以0.1C、1C、5C之定電流評價放電電容。 The discharge capacity was evaluated at a constant current of 0.1 C, 1 C, and 5 C at 25 ° C using a coin battery using a positive electrode sheet having an electrode composition ratio A.

以使用電極組成比B之正極薄片之硬幣電池，評價於0℃、25℃之電流負荷特性。充電時之電流值係使用0.1C之定電流值，且以相當於0.1~5C之定電流值進行放電。 The current load characteristics at 0 ° C and 25 ° C were evaluated using a coin battery using a positive electrode sheet having an electrode composition ratio B. The current value during charging is a constant current value of 0.1 C, and is discharged at a constant current value equivalent to 0.1 to 5 C.

另外，以使用電極組成比B的正極薄片之硬幣電池，評價於60℃之充放電曲線．放電電容。以相當於0.2C之定電流值進行充電，且測定以相當於0.2C之定電流值進行第1、2、12、...、10×i+2(i=1~6)次之放電，以相當於1C之定電流值進行其他放電時之各循環之放電電容。以充電與放電時之電壓範圍下限為2.0V、上限為4.5V及下限為2.0V、上限為4.3V進行。 In addition, a coin battery using a positive electrode sheet having an electrode composition ratio B was evaluated at a charge and discharge curve of 60 ° C. Discharge capacitor. Charging with a constant current value equivalent to 0.2 C, and measuring the discharge of the first, second, second, ..., 10 × i + 2 (i = 1 to 6) times with a constant current value equivalent to 0.2 C The discharge capacitance of each cycle at the time of other discharge is performed at a constant current value equivalent to 1C. The lower limit of the voltage range during charging and discharging is 2.0 V, the upper limit is 4.5 V, the lower limit is 2.0 V, and the upper limit is 4.3 V.

[實施例1] [Example 1]

過渡金屬之物質收支於各步驟中設為100%時，以可為約88g(約0.56mol)之LiMn0.8Fe0.2PO4之方式計量原料。以使過渡金屬成為5.6mol/L之方式，混合MnSO4、FeSO4、H3PO4、NH4OH及純水，在室溫下藉中和反應獲 得NH4MnPO4與NH4FePO4。過濾沉澱物，以純水洗淨後，添加LiOH．H2O、H3PO4及抗壞血酸之溶液，以使莫耳比成為Li：Mn：Fe：P=1.05：0.8：0.2：1.05之方式調整原料饋入比，獲得水系漿液。漿液中之主結晶相為NH4MnPO4。以球磨機混合該漿液，且粉碎凝集粒子而調整粒度。 When the material content of the transition metal is 100% in each step, the raw material is metered in such a manner that it can be about 88 g (about 0.56 mol) of LiMn 0.8 Fe 0.2 PO 4 . MnSO 4 , FeSO 4 , H 3 PO 4 , NH 4 OH and pure water were mixed in such a manner that the transition metal became 5.6 mol/L, and NH 4 MnPO 4 and NH 4 FePO 4 were obtained by neutralization reaction at room temperature. The precipitate was filtered, washed with pure water, and then added with LiOH. A solution of H 2 O, H 3 PO 4 and ascorbic acid was adjusted so that the molar ratio became Li:Mn:Fe:P=1.05:0.8:0.2:1.05, and an aqueous slurry was obtained. The main crystalline phase in the slurry is NH 4 MnPO 4 . The slurry was mixed in a ball mill, and the aggregated particles were pulverized to adjust the particle size.

於180℃對該漿液進行水熱處理3小時，以純水使用吸濾器(Nutsche)洗淨所得磷酸錳鐵鋰，獲得濾餅。於評價用中，取一部份在105℃乾燥隔夜。評價用之乾燥粉末由XRD繞射圖型之Rietveld解析，為含Li1-αMn0.8Fe0.2P1-βO4-δ(0≦α,β≦0.2)與3.4wt%之雜質相Li3PO4者。其組成比以ICP測定為Li：Mn：Fe：P=1.00：0.8：0.2：0.98，藉熱分析可確認5.0wt%重量減少，故該反應率為95.0wt%。 The slurry was hydrothermally treated at 180 ° C for 3 hours, and the obtained lithium manganese iron phosphate was washed with pure water using a suction filter (Nutsche) to obtain a cake. For evaluation, a portion was dried overnight at 105 °C. The dry powder for evaluation was analyzed by Rietveld of the XRD diffraction pattern and was an impurity phase containing Li 1-α Mn 0.8 Fe 0.2 P 1-β O 4-δ (0≦α, β≦0.2) and 3.4% by weight. 3 PO 4 persons. The composition ratio was determined by ICP to be Li:Mn:Fe:P=1.00:0.8:0.2:0.98, and it was confirmed by thermal analysis that the weight loss was 5.0 wt%, so the reaction rate was 95.0% by weight.

使所得濾餅進行解膠，製作漿液後，由反應率與主成分組成比之結果，以成為表1所記載之主成分組成比之方式，添加鋰化合物及/或磷化合物與有機物並混合。藉由ICP測定而確定主成分組成比。此處表1所記載之有機物之重量%之添加量係對於使水熱處理後所得之磷酸錳鐵鋰之濾餅乾燥時所得之固體成分之量的值(第一步驟)。 The obtained cake was subjected to degumming, and after the slurry was prepared, the lithium compound and/or the phosphorus compound and the organic substance were added and mixed so as to have a composition ratio of the main component as shown in Table 1 as a result of the ratio of the reaction ratio to the main component. The principal component composition ratio was determined by ICP measurement. The amount of the weight % of the organic matter described in Table 1 is the value of the amount of the solid component obtained when the filter cake of the lithium iron manganese phosphate obtained after the hydrothermal treatment is dried (first step).

調整主成分組成比後，在大氣中於105℃乾燥。以咖啡磨豆機粉碎乾燥物，以75μm進行篩分，獲得凝集粒徑經控制之前驅物混合粉末(第二步驟)。 After adjusting the main component composition ratio, it was dried at 105 ° C in the atmosphere. The dried product was pulverized by a coffee grinder and sieved at 75 μm to obtain a mixture of powders before the control of the agglomerated particle size (second step).

將所得燒結用前驅物混合粉末放入氧化鋁製坩堝中，在700℃、氮氣氛圍下施以熱處理5小時。將升溫速度設為200℃/hr，N2氣體流量設為1L/min。隨後，以瑪瑙研缽粉碎，以使成為45μm以下之方式進行篩分(第三步驟)。 The obtained precursor powder for sintering was placed in a crucible made of alumina, and heat-treated at 700 ° C for 5 hours in a nitrogen atmosphere. The temperature increase rate was set to 200 ° C / hr, and the N 2 gas flow rate was set to 1 L / min. Subsequently, it was pulverized in an agate mortar to be sieved so as to be 45 μm or less (third step).

所得粉末係微細且為碳複合化磷酸錳鐵鋰粒子粉末。又，ICP測定之結果，與第一步驟中調整之Li、Mn、Fe、P之組成比並無不同。圖1與2中顯示所得之碳複合化磷酸錳鐵鋰粒子粉末之高倍與低倍之SEMM照片(二次電子影像)。可知所得粉末係由100nm以下之一次粒子與凝集一次粒子而成之十數μm之凝集粒子構成。 The obtained powder was fine and was a carbon composite manganese iron iron phosphate particle powder. Further, as a result of the ICP measurement, there was no difference in composition ratios of Li, Mn, Fe, and P adjusted in the first step. The high- and low-magnification SEMM photographs (secondary electron image) of the obtained carbon-composite lithium manganese iron phosphate particle powder are shown in FIGS. 1 and 2. The obtained powder was composed of primary particles of 100 nm or less and aggregated particles of ten μm obtained by aggregating primary particles.

所得粉末之粉體特性示於表2。以電極組成比A予以正極化，以硬幣電池評價之電池特性示於表3，且以電極組成比B之電池特性示於圖3至6。如表3及圖3至6所示，於25℃之電池特性以外，於0℃之電流負荷特性及60℃下之循環特性亦獲得良好之結果。 The powder properties of the obtained powder are shown in Table 2. The electrode composition ratio was positively measured by the electrode composition ratio A, the battery characteristics evaluated by the coin cell are shown in Table 3, and the battery characteristics of the electrode composition ratio B are shown in Figs. 3 to 6. As shown in Table 3 and Figures 3 to 6, in addition to the battery characteristics at 25 ° C, the current load characteristics at 0 ° C and the cycle characteristics at 60 ° C also obtained good results.

以下之實施例及比較例之實驗條件列於表1，粉體特性列於表2，電池特性列於表3。 The experimental conditions of the following examples and comparative examples are shown in Table 1, the powder characteristics are shown in Table 2, and the battery characteristics are shown in Table 3.

[實施例2、3] [Examples 2, 3]

對於以與實施例1相同規格獲得之水熱處理、水洗後之含磷酸錳鐵鋰粒子之濾餅，其隨後之步驟中，除改變表1所記載之鋰化合物及/或磷化合物與碳源以外，餘與實施例1同樣，進行乾燥、粉碎．分級、燒結、及粉碎．分 級，獲得磷酸錳鐵鋰粒子粉末。表2、3中顯示評價結果。 The hydrous heat-treated and water-washed lithium iron phosphate-containing lithium phosphate particle cake obtained in the same manner as in Example 1 was subjected to the subsequent steps except that the lithium compound and/or the phosphorus compound and the carbon source described in Table 1 were changed. The same as in Example 1, drying and pulverizing. Grading, sintering, and crushing. Minute In the grade, a lithium iron manganese phosphate particle powder is obtained. The evaluation results are shown in Tables 2 and 3.

[實施例4] [Example 4]

使以與實施例1相同規格之水熱處理、水洗後之含磷酸錳鐵鋰粒子之濾餅乾燥後，使用表1所記載之鋰化合物及/或磷化合物與碳源，對於乾燥物添加7.5wt%之水，以咖啡磨豆機進行混合。其以後之處理係以實施例1所記載之方法進行，獲得磷酸錳鐵鋰粒子粉末。表2、3中顯示評價結果。 After drying the filter cake containing the lithium iron phosphate particles after hydrothermal treatment and washing with the same specifications as in Example 1, the lithium compound and/or the phosphorus compound and the carbon source described in Table 1 were used, and 7.5 wt was added to the dried product. % water, mixed with a coffee grinder. The subsequent treatment was carried out in the same manner as described in Example 1, to obtain lithium manganese iron phosphate particles. The evaluation results are shown in Tables 2 and 3.

[實施例5、6] [Examples 5 and 6]

相對於實施例1所記載之原料饋入比，除變更為Mn：Fe=85：15以外，餘進行與實施例1同樣之水熱反應用前驅物處理、水熱處理及水洗，獲得濾餅。評價用時，係將水洗後之樣品抽取一部份在105℃乾燥隔夜者以XRD繞射圖型之Rietveld解析，判知為含Li1-αMn0.85Fe0.15P1-βO4-δ(0≦α,β≦0.2)與4.3wt%之雜質相Li3PO4者。其組成比以ICP測定為Li：Mn：Fe：P=0.98：0.85：0.15：0.96，由於以熱分析可確認5.4wt%重量減少，故該反應率為94.6wt%。 The raw material feed ratio described in Example 1 was changed to Mn:Fe=85:15, and the precursor treatment for hydrothermal reaction, hydrothermal treatment, and water washing in the same manner as in Example 1 was carried out to obtain a cake. For the evaluation, a part of the sample after washing was taken out and dried at 105 ° C overnight. The Rietveld analysis of the XRD diffraction pattern was carried out, and it was found to contain Li 1-α Mn 0.85 Fe 0.15 P 1-β O 4-δ. (0 ≦ α, β ≦ 0.2) and 4.3 wt% of the impurity phase Li 3 PO 4 . The composition ratio was determined by ICP as Li:Mn:Fe:P=0.98:0.85:0.15:0.96, and the reaction rate was 94.6 wt% because it was confirmed by thermal analysis that the weight loss was 5.4 wt%.

對於使所得濾餅解膠之含磷酸錳鐵鋰粒子之漿液，除改變表1所記載之鋰化合物及/或磷化合物與碳源以外，餘與實施例1同樣，進行乾燥、粉碎．分級、燒 結、及粉碎．分級，獲得磷酸錳鐵鋰粒子粉末。表2、3中顯示評價結果。 The slurry containing the lithium manganese iron phosphate particles obtained by dissolving the obtained filter cake was dried and pulverized in the same manner as in Example 1 except that the lithium compound and/or the phosphorus compound and the carbon source described in Table 1 were changed. Grading, burning Knot, and crush. By classification, a lithium iron manganese phosphate particle powder was obtained. The evaluation results are shown in Tables 2 and 3.

[比較例1] [Comparative Example 1]

除了對於實施例1所記載之原料饋入比變更為Mn：Fe=100：0以外，餘進行與實施例1同樣之水熱反應用前驅物處理、水熱處理及水洗，獲得濾餅。評價用時，係將水洗後之樣品抽取一部份在105℃乾燥隔夜者以XRD繞射圖型之Rietveld解析，判知為含3.0wt%之雜質相Li3PO4與Li1-αMnP1-βO4-δ(0≦α,β≦0.2)。其組成比以ICP測定為Li：Mn：Fe：P=0.98：1.00：0.0：0.96，由於以熱分析可確認4.8wt%重量減少，故該反應率為95.2wt%。 The pretreatment of hydrothermal reaction, hydrothermal treatment, and water washing were carried out in the same manner as in Example 1 except that the raw material feed ratio described in Example 1 was changed to Mn:Fe=100:0, and a cake was obtained. For the evaluation, a portion of the sample after washing was taken out and dried at 105 ° C overnight. The Rietveld analysis of the XRD diffraction pattern was judged to be 3.0 wt% of the impurity phase Li 3 PO 4 and Li 1-α MnP. 1-β O 4-δ (0≦α, β≦0.2). The composition ratio was determined by ICP as Li:Mn:Fe:P=0.98:1.00:0.0:0.96, and the reaction rate was 95.2% by weight because it was confirmed by thermal analysis that the weight loss was 4.8 wt%.

對於使所得濾餅解膠之含磷酸錳鐵鋰粒子之漿液，除改變表1所記載之鋰化合物及/或磷化合物與碳源以外，餘與實施例1同樣，進行乾燥、粉碎．分級、燒結、及粉碎．分級，獲得磷酸錳鐵鋰粒子粉末。表2、3中顯示評價結果。使用電極組成比B之硬幣電池，獲得在0℃下128mAh/g(1C)之放電電容，且於60℃之62次循環後之電容維持率為98%。 The slurry containing the lithium manganese iron phosphate particles obtained by dissolving the obtained filter cake was dried and pulverized in the same manner as in Example 1 except that the lithium compound and/or the phosphorus compound and the carbon source described in Table 1 were changed. Grading, sintering, and crushing. By classification, a lithium iron manganese phosphate particle powder was obtained. The evaluation results are shown in Tables 2 and 3. Using a coin battery having an electrode composition ratio of B, a discharge capacitance of 128 mAh/g (1 C) at 0 ° C was obtained, and the capacitance retention rate after 62 cycles of 60 ° C was 98%.

所得粉末係微細，但也許因為LiMnPO4本身難以作成缺陷構造，故獲得接近式(1)之單位晶胞體積。另一方面，電池特性非常差，認為是碳被覆不充分。同時，碳量較多，凝集粒徑較小，故壓縮成型體密度降低。 The obtained powder is fine, but it may be difficult to form a defect structure by LiMnPO 4 itself, so that a unit cell volume close to the formula (1) is obtained. On the other hand, the battery characteristics are very poor, and it is considered that the carbon coating is insufficient. At the same time, the amount of carbon is large, and the aggregated particle size is small, so the density of the compression molded body is lowered.

[比較例2] [Comparative Example 2]

對於以與實施例1相同規格獲得之水熱處理、水洗後之含磷酸錳鐵鋰粒子之濾餅，除改變表1所記載之鋰化合物及/或磷化合物與碳源以外，餘與實施例4同樣，使該濾餅乾燥後，混合鋰化合物及/或磷化合物與碳源及水，再進行乾燥、粉碎．分級、燒結、及粉碎．分級，獲得磷酸錳鐵鋰粒子粉末。表2、3中顯示評價結果。 The hydrous heat-treated and water-washed lithium iron phosphate-containing lithium phosphate particle cake obtained in the same manner as in Example 1 was changed to Example 4 except that the lithium compound and/or the phosphorus compound and the carbon source described in Table 1 were changed. Similarly, after drying the filter cake, the lithium compound and / or phosphorus compound and carbon source and water are mixed, and then dried and pulverized. Grading, sintering, and crushing. By classification, a lithium iron manganese phosphate particle powder was obtained. The evaluation results are shown in Tables 2 and 3.

比較例2中所添加之碳源量不足，表2中之殘留碳量亦不足，電阻變高。因此，電池特性亦不良。 The amount of carbon source added in Comparative Example 2 was insufficient, and the amount of residual carbon in Table 2 was also insufficient, and the electric resistance was high. Therefore, the battery characteristics are also poor.

[比較例3與4] [Comparative Examples 3 and 4]

對於以與實施例1相同規格獲得之水熱處理、水洗後之含磷酸錳鐵鋰粒子之濾餅，除改變表1所記載之鋰化合物及/或磷化合物與碳源以外，餘與實施例1同樣，使濾餅解膠後，進行混合、乾燥、粉碎．分級、燒結、及粉碎．分級，獲得磷酸錳鐵鋰粒子粉末。表2、3中顯示評價結果。 The water-heat-treated and water-washed lithium manganese iron phosphate-containing filter cake obtained in the same manner as in Example 1 was changed to Example 1 except that the lithium compound and/or the phosphorus compound and the carbon source described in Table 1 were changed. Similarly, after the filter cake is degummed, it is mixed, dried and pulverized. Grading, sintering, and crushing. By classification, a lithium iron manganese phosphate particle powder was obtained. The evaluation results are shown in Tables 2 and 3.

比較例3與4由於組成比調整中未使用Li1-yH2+yPO4，故生成較不佳之雜質結晶相。結果，該粒子之表面改質變不充分，推測無法獲得充分之電池特性。 In Comparative Examples 3 and 4, Li 1-y H 2+y PO 4 was not used in the composition ratio adjustment, so that a poor impurity crystal phase was formed. As a result, the surface modification of the particles was insufficient, and it was presumed that sufficient battery characteristics could not be obtained.

[比較例5] [Comparative Example 5]

對於與實施例1同樣之於第二步驟所得之燒結用前驅 物混合粉末，在比其他例高100℃之800℃下進行燒結，且進行粉碎．分級，獲得磷酸錳鐵鋰粒子粉末。表2、3中顯示評價結果。 For the sintering precursor obtained in the second step as in the first embodiment The powder was mixed and sintered at 800 ° C higher than other examples, and pulverized. By classification, a lithium iron manganese phosphate particle powder was obtained. The evaluation results are shown in Tables 2 and 3.

自比較例5所得之磷酸錳鐵鋰檢測出雜質相之Fe2P，也許是來自橄欖石構造中之Fe減低，而使單位晶胞體積變大。且，或許是該雜質相抑制了粒子表面之改質，而使表3記載之電池特性難稱為良好者。 The ferromanganese phosphate obtained in Comparative Example 5 detected the Fe 2 P of the impurity phase, perhaps the Fe from the olivine structure was reduced, and the unit cell volume was increased. Further, it is possible that the impurity phase suppresses the modification of the particle surface, and it is difficult to say that the battery characteristics described in Table 3 are good.

使用比較例5所得之磷酸錳鐵鋰以電極組成B測定0℃之電流負荷特性後，遠低於圖3與4所記載之實施例1之特性。且，在2.0~4.5V間進行60℃之充放電循環試驗後，電容在40至50次循環之間急遽下降，在60次循環後幾乎為0。此認為係雜質相之Fe2P分解，而在負極側析出，產生內部短路或Li負極表面污染。 Using the ferromanganese phosphate obtained in Comparative Example 5, the current load characteristics at 0 ° C were measured in the electrode composition B, which was much lower than the characteristics of Example 1 shown in Figs. Moreover, after a 60 ° C charge and discharge cycle test between 2.0 and 4.5 V, the capacitance dropped sharply between 40 and 50 cycles, and was almost zero after 60 cycles. This is considered to be decomposition of Fe 2 P in the impurity phase, and precipitation on the negative electrode side, resulting in internal short circuit or contamination of the surface of the Li negative electrode.

由以上之結果可知，本發明之碳複合化磷酸錳鐵鋰粒子粉末之製造方法為低成本、環境負荷少之製法。且，本發明之碳複合化磷酸錳鐵鋰粒子粉末可製作高填充性之正極薄片，確認使用其之二次電池在25℃及0℃之電流負荷特性均獲得高電容。同時在60℃之高溫充放電循環試驗之結果，亦可確認98%以上之電容維持率。 From the above results, it is understood that the method for producing the carbon composite manganese iron iron phosphate particle powder of the present invention is a method of low cost and low environmental load. Further, the carbon composite manganese iron iron phosphate particle powder of the present invention can produce a highly filled positive electrode sheet, and it is confirmed that the secondary battery using the same has a high capacitance at a current load characteristic of 25 ° C and 0 ° C. At the same time, the result of the high temperature charge and discharge cycle test at 60 ° C can also confirm the capacity retention rate of 98% or more.

〔產業上之可利用性〕 [Industrial Applicability]

本發明中，藉由以低成本、環境負荷少之製法製作之橄欖石型構造之碳複合化磷酸錳鐵鋰粒子粉末作為二次電池正極活性物質使用，可獲得每體積之能量密度高、於低溫之高電流負荷特性亦獲得高電容、高溫之循環特性之電容維持率亦高之非水溶劑系二次電池。 In the present invention, the carbon composite lithium manganese iron phosphate particle powder having an olivine structure produced by a low-cost method and a low environmental load is used as a positive electrode active material for a secondary battery, whereby a high energy density per volume can be obtained. A low-temperature high-current load characteristic also obtains a non-aqueous solvent-based secondary battery having a high capacitance and high-temperature cycle characteristics and a high capacitance retention rate.

Claims (5)

一種橄欖石型構造之碳複合化磷酸錳鐵鋰粒子粉末之製造方法，其係於橄欖石型構造之碳複合化磷酸錳鐵鋰(Mn：Fe=0.98：0.02~0.50：0.50莫耳比)粒子粉末之製造方法中，由獲得含有以水熱處理所生成之橄欖石型構造之磷酸錳鐵鋰、鋰化合物及/或磷化合物與有機物之水系懸浮液或含水物之第一步驟、使第一步驟中所得之水系懸浮液或含水物乾燥而獲得燒成用前驅物混合粉末之第二步驟、燒成第二步驟中所得之燒成用前驅物混合粉末之第三步驟所成之碳複合化磷酸錳鐵鋰粒子粉末之製造方法，其特徵係前述第一步驟中之水系懸浮液或含水物以莫耳比計滿足0.98≦Li/(Mn+Fe)≦1.20、0.98≦P/(Mn+Fe)≦1.20、P≦Li，且鋰化合物及/或磷化合物之60wt%以上為LiH2PO4，前述有機物相對於水熱處理後之磷酸錳鐵鋰為1~20wt%，前述碳複合化磷酸錳鐵鋰粒子粉末之鋰與磷之含量相對於過渡金屬以莫耳比計，各為0.98~1.15，且鋰之含量為磷以上。 A method for producing a carbon composite manganese iron iron phosphate particle powder of an olivine structure, which is a carbon composite manganese iron iron phosphate (Mn:Fe=0.98:0.02~0.50:0.50 molar ratio) in an olivine structure. In the method for producing a particle powder, the first step of obtaining an aqueous suspension or hydrate containing lithium iron manganese phosphate, a lithium compound, and/or a phosphorus compound and an organic substance in an olivine structure formed by hydrothermal treatment is used. The second step of the aqueous suspension or the hydrate obtained in the step is dried to obtain a mixed powder of the precursor for firing, and the third step of the third step of firing the precursor powder for firing obtained in the second step is carbon compounding. A method for producing a lithium iron phosphate particle powder, characterized in that the aqueous suspension or hydrate in the first step satisfies 0.98 ≦Li/(Mn+Fe)≦1.20, 0.98≦P/(Mn+) in terms of molar ratio. Fe) ≦1.20, P≦Li, and 60% by weight or more of the lithium compound and/or the phosphorus compound is LiH 2 PO 4 , and the organic substance is 1 to 20% by weight based on the lithium manganese iron phosphate after the hydrothermal treatment, and the carbon composite phosphoric acid Lithium iron oxide particle powder has a relative content of lithium and phosphorus Transition metal molar ratio, each of 0.98 to 1.15, and the content of lithium of more phosphorus. 如請求項1之製造方法，其中碳複合化磷酸錳鐵鋰粒子粉末之製造方法的第一步驟中，有機物為水可溶性之有機物。 The manufacturing method of claim 1, wherein in the first step of the method for producing a carbon composite manganese iron iron phosphate particle powder, the organic substance is a water-soluble organic substance. 如請求項1或2之製造方法，其中碳複合化磷酸錳鐵鋰粒子粉末之製造方法的第一步驟中，有機物為屬含 羥基(-OH)或羧基(-COOH)之多元醇類、糖或有機酸之有機物。 The manufacturing method of claim 1 or 2, wherein in the first step of the method for producing a carbon composite manganese iron iron phosphate particle powder, the organic substance is a genus An organic substance of a hydroxyl group (-OH) or a carboxyl group (-COOH), a sugar or an organic acid. 如請求項1之製造方法，其中碳複合化磷酸錳鐵鋰粒子粉末之製造方法的第二步驟中之乾燥溫度為40℃~250℃。 The production method of claim 1, wherein the drying temperature in the second step of the method for producing the carbon composite manganese iron iron phosphate particle powder is from 40 ° C to 250 ° C. 一種非水電解質二次電池，其係使用以如請求項1~4中任一項之製造方法所得之碳複合化磷酸錳鐵鋰粒子粉末而製作者。 A non-aqueous electrolyte secondary battery produced by using the carbon composite manganese iron iron phosphate particle powder obtained by the production method according to any one of claims 1 to 4.
TW102131299A 2012-08-31 2013-08-30 Method for producing carbon composite manganese iron iron phosphate particle powder, carbon composite manganese iron iron particle particle powder, and nonaqueous electrolyte secondary battery using the same TWI636007B (en)

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