WO2016135783A1 - 電極活物質、二次電池用電極及び二次電池 - Google Patents

電極活物質、二次電池用電極及び二次電池 Download PDF

Info

Publication number
WO2016135783A1
WO2016135783A1 PCT/JP2015/003107 JP2015003107W WO2016135783A1 WO 2016135783 A1 WO2016135783 A1 WO 2016135783A1 JP 2015003107 W JP2015003107 W JP 2015003107W WO 2016135783 A1 WO2016135783 A1 WO 2016135783A1
Authority
WO
WIPO (PCT)
Prior art keywords
active material
electrode active
carbon black
electrode
secondary battery
Prior art date
Application number
PCT/JP2015/003107
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
峰夫 佐藤
大 岡田
東吾 山口
望 有満
Original Assignee
旭カーボン株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 旭カーボン株式会社 filed Critical 旭カーボン株式会社
Priority to CN201580076814.6A priority Critical patent/CN107251289B/zh
Publication of WO2016135783A1 publication Critical patent/WO2016135783A1/ja

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

Definitions

  • the present invention relates to an electrode active material, a secondary battery electrode including the same, and a secondary battery.
  • an electrode is produced using a conductive agent in addition to the electrode active material.
  • the conductive agent increases the conductivity of the electrode by forming a conductive path between individual electrode active material particles or covering the surface of the electrode active material to enhance the current collecting effect.
  • Non-patent Document 1 Non-patent Document 1
  • carbon coating carbon coating
  • hydrocarbons have been studied as carbonaceous materials for carbon coats, but other preferred carbonaceous materials (such as carbon black) have not yet been examined, and the structure of carbon black that is optimal for carbon coats is also not available. It remains unexamined.
  • an electrode active material (LFP (LiFePO 4 )) that is superior in discharge capacity, cost, safety, etc., but is inferior in conductivity to LCO (LiCoO 2 ), LNO (LiNiO 4 ), and the like conventionally used.
  • LVP Li 3 V 2 (PO 4 ) 3 ], etc.
  • An electrode active material coated with a carbonaceous material wherein the carbonaceous material is carbon black and hydrocarbon, and the carbon black is the number of primary particles PPA (pieces) forming the aggregate. And an electrode active material having a ratio “PPA / d” of 8 or more to the primary particle diameter d (nm).
  • a secondary battery in which at least one of the positive electrode and the negative electrode is the secondary battery electrode according to [4].
  • the present invention it is possible to provide an electrode active material whose surface is efficiently coated with a suitable carbonaceous material and which has an improved current collecting effect. Moreover, according to this invention, the secondary battery electrode containing this electrode active material and the secondary battery with improved battery characteristics can be provided.
  • the physical properties of carbon black for electrode use have been specified by specific surface area, DBP absorption amount, and the like. Therefore, as in the present invention, the shape of the carbon black aggregate is measured from the viewpoint of the development degree of the aggregate evaluated by the particle size of the primary particles constituting the aggregate and the number of primary particles, and the secondary battery.
  • the carbon black used in the present invention is a carbon black that defines the optimum conditions for the shape of the aggregate, and cannot be achieved by using a conventional carbonaceous material alone or a carbon coat that uses a carbon black that is not specified in this application. There is an effect.
  • FIG. 1 shows a schematic diagram of the shape of carbon black used in the present invention.
  • the carbon black aggregate 2 is obtained by aggregating many primary particles 1 as shown in the figure.
  • the primary particle diameter d refers to the diameter (nm) of the primary particles 1 constituting the carbon black aggregate 2, and is defined by ASTM D3849-13, and is the average particle diameter derived by CB morphological analysis using an electron microscope (during specification) M).
  • PPA Particle number Per Aggregate
  • PPA particle number Per Aggregate
  • the primary particle diameter d is preferably 15 nm or less. If the primary particle diameter d is 15 nm or less, the contact area between the electrode active material and the hydrocarbon used in combination increases, and the surface conductive effect is improved. As for the lower limit of the primary particle diameter d, it is very difficult to produce carbon black of less than 8 nm with the current production technology, and 8 nm is the lower limit in production, but 8 nm is the lower limit as a characteristic of carbon black. Do not mean.
  • the ratio “PPA / d” between the number PPA (number) of primary particles and the primary particle diameter d (nm) is 8 or more, preferably 8-12. If it is this range, it will become a shape suitable for the carbon black aggregate to coat
  • “PPA / d” is less than 8, that is, when the primary particle diameter d is larger than the size of the carbon black aggregate, or when the number of primary particles is small and the length of the carbon black aggregate is short. In the carbon coating process, it is difficult to apply a shearing stress, and it becomes difficult to disperse the carbon black.
  • the carbon black can be manufactured using a general carbon black manufacturing furnace.
  • the carbon black is a carbon black production furnace in which a fuel introduction part, a raw material introduction part, a narrow cylindrical part, and a reaction continuation / cooling chamber provided with a quench water pressure spraying device for reaction stop are connected from the upstream part.
  • Production conditions include the amount of air, the air preheating temperature, the amount of fuel, the amount of raw material introduced, the amount of water for stopping the reaction, etc., and these may be appropriately controlled.
  • the carbon black having the specific shape is excellent in covering properties and is suitable as a carbonaceous material for covering an electrode active material.
  • a hydrocarbon as a carbonaceous material, it is possible to obtain an electrode active material with improved conductivity and surface current collection effect, in which the entire surface is more strongly carbon-coated.
  • the ratio (mass ratio) of carbon black and hydrocarbon is not particularly limited as long as carbon coating can be appropriately performed, but is, for example, 4:96 to 80:20, and preferably 10:90 to 60:40.
  • the hydrocarbon include polystyrene, polyethylene glycol, ascorbic acid, glucose, pitch, acetylene, methane and the like.
  • the electrode for secondary batteries produced using this electrode active material for a positive electrode and / or a negative electrode the electrode stability of a secondary battery improves and the current collection effect of a secondary battery increases. Therefore, by using this electrode active material, a secondary battery having excellent battery characteristics such as discharge capacity and rate characteristics can be produced.
  • the electrode active material LFP LiFePO 4
  • Electrode active materials such as LVP (Li 3 V 2 (PO 4 ) 3 ), LTO (lithium titanate), LiMnPO 4 and the like are also subjected to temporary firing, pulverization mixing, and main firing in the same manner as described above. Can be carbon coated.
  • Table 1 shows the production conditions (operation conditions) of carbon black used in the examples and comparative examples.
  • CB1 to CB6 are the production conditions of the carbon black for the examples
  • CB11 to CB12 are the production conditions of the carbon black for the comparative example.
  • the DBP absorption amount, nitrogen adsorption specific surface area (N 2 SA), PPA, and primary particle diameter d of carbon black obtained under the production conditions shown in Table 1 were measured. The results are shown in Table 2. For comparison, Table 2 also shows the characteristics of acetylene black (AB: Denka Black, Denki Kagaku Kogyo Co., Ltd.), which is a carbon black conventionally used for conductive materials.
  • N 2 SA nitrogen adsorption specific surface area
  • PPA primary particle diameter d of carbon black obtained under the production conditions shown in Table 1 were measured. The results are shown in Table 2. For comparison, Table 2 also shows the characteristics of acetylene black (AB: Denka Black, Denki Kagaku Kogyo Co., Ltd.), which is a carbon black conventionally used for conductive materials.
  • the DBP absorption amount is the amount of dibutyl phthalate absorbed per 100 g of carbon black (mL / 100 g carbon black), and was measured by the method described in JIS K6217-4: 2008. DBP absorption is a general index for evaluating the structural characteristics of carbon black aggregates.
  • the N 2 SA is a specific surface area per unit weight (m 2 / g), and was measured by the method described in JIS K6217-2: 2001.
  • the PPA (the number of primary particles constituting the carbon black aggregate) and the primary particle diameter d were subjected to CB morphological analysis with a field emission scanning microscope (JSM-6700F, JEOL Ltd.) in accordance with ASTM D3849-13.
  • the average particle size (m in the specification) and the total number of particles (nt in the specification) were derived.
  • the derived average particle size (m in the specification) is defined as the primary particle size d, and the value obtained by dividing the derived total particle number (nt in the specification) by the number of observed carbon black aggregates is expressed as PPA. did.
  • the carbon black produced under the conditions of CB1 to CB6 satisfied the regulations in the present invention. That is, “PPA / d” of these carbon blacks was 8 or more, and the primary particle diameter d of these carbon blacks was 15 nm or less.
  • carbon black and acetylene black (AB) produced under the conditions of CB11 to CB12 did not satisfy the provisions of the present invention. That is, the “PPA / d” of these carbon blacks was less than 8, and the primary particle diameter d of these carbon blacks was larger than 15 nm.
  • LFP (electrode active material)
  • LFP LiFePO 4
  • carbon black was dry mixed by a ball mill.
  • polystyrene and organic solvent xylene were further added and wet-mixed with a ball mill, and then xylene was evaporated.
  • a conductive material, a binder (polyvinylidene fluoride) and a solvent (N-methylpyrrolidone) were mixed with the carbon-coated LFP at a predetermined ratio to prepare an electrode slurry.
  • the slurry was applied to an aluminum foil, dried, and then pressed to prepare a secondary battery electrode.
  • charge / discharge characteristics were evaluated. The results are shown in Table 4.
  • the charge / discharge characteristics were measured using a charge / discharge battery test system (PFX2011, Kikusui Electronics Co., Ltd.). The measurement conditions are a temperature of 25 ° C., a cut-off voltage of 2.0 to 4.0 V, and the C rate is increased stepwise to 0.5, 1, 2, 5, 10, 20, 30, 40, 50, 60. It was.
  • the initial capacity is a measured value at 0.5C.
  • the rate characteristic is a relative value of each rate when 0.5C is set to 100.
  • Reference Examples 1 and 2 are examples in which only polystyrene is used as a carbonaceous material for carbon coating.
  • a carbon-coated LFP was prepared in the same manner as in the example except that the carbon black dry mixing step was omitted, and then a secondary battery electrode and a secondary battery were manufactured.
  • Reference examples 3 to 4 are examples in which only CB1 or AB is used as the carbonaceous material for carbon coating. Except that the wet mixing step of polystyrene was omitted, a carbon-coated LFP was produced in the same manner as in the example, and then a secondary battery electrode and a secondary battery were produced.
  • the secondary batteries of the examples maintain higher rate characteristics than the secondary batteries of the comparative examples, and exhibit high charge / discharge capacities. That is, it can be seen that the secondary battery having excellent battery characteristics can be obtained by the electrode active material according to the present invention, which is provided with a carbon coat using a specific shape of carbon black and hydrocarbon (polystyrene).
  • the electrode active material and the secondary battery electrode according to the present invention can be used for secondary batteries used in various applications.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
PCT/JP2015/003107 2015-02-27 2015-06-22 電極活物質、二次電池用電極及び二次電池 WO2016135783A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201580076814.6A CN107251289B (zh) 2015-02-27 2015-06-22 被碳质材料覆盖的电极活性物质、二次电池用电极及二次电池

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-038732 2015-02-27
JP2015038732A JP6437348B2 (ja) 2015-02-27 2015-02-27 電極活物質、二次電池用電極、二次電池

Publications (1)

Publication Number Publication Date
WO2016135783A1 true WO2016135783A1 (ja) 2016-09-01

Family

ID=56789404

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/003107 WO2016135783A1 (ja) 2015-02-27 2015-06-22 電極活物質、二次電池用電極及び二次電池

Country Status (3)

Country Link
JP (1) JP6437348B2 (zh)
CN (1) CN107251289B (zh)
WO (1) WO2016135783A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020524192A (ja) * 2017-06-15 2020-08-13 キャボット コーポレイションＣａｂｏｔ Ｃｏｒｐｏｒａｔｉｏｎ カーボンブラック粒子を含む電極および関連する方法
CN114284465A (zh) * 2021-12-22 2022-04-05 蜂巢能源科技股份有限公司 正极浆料的制备方法、正极极片及锂离子电池

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111211296B (zh) * 2018-11-22 2022-03-18 杭州长凯能源科技有限公司 含微纳导电网络结构的电池活性材料
CN111211297B (zh) * 2018-11-22 2022-03-18 杭州长凯能源科技有限公司 含微纳导电网络结构的电池活性材料的制备

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001092151A1 (fr) * 2000-05-31 2001-12-06 Showa Denko K.K. Composite a base de carbone electriquement conducteur a fines particules, catalyseur pour pile a combustible a polymere solide et batterie de piles
JP2002042786A (ja) * 2000-07-25 2002-02-08 Sharp Corp 非水電解質二次電池
JP2003308845A (ja) * 2002-04-17 2003-10-31 Mikuni Color Ltd リチウム二次電池用電極及びこれを用いたリチウム二次電池
JP2003346804A (ja) * 2002-05-28 2003-12-05 Sony Corp 負極材料、非水電解質電池及び負極材料の製造方法
JP2005307070A (ja) * 2004-04-23 2005-11-04 Denki Kagaku Kogyo Kk カーボンブラック、その製造方法、及びそれを含有した組成物
JP2006210007A (ja) * 2005-01-25 2006-08-10 Mitsubishi Chemicals Corp 電気化学素子用電極およびそれを用いたリチウム二次電池
JP2007165079A (ja) * 2005-12-13 2007-06-28 Matsushita Electric Ind Co Ltd 非水電解質二次電池用負極とそれを用いた非水電解質二次電池
JP2010086955A (ja) * 2008-09-04 2010-04-15 Toyo Ink Mfg Co Ltd 電池電極用複合材料
JP2011070908A (ja) * 2009-09-25 2011-04-07 Mikuni Color Ltd 導電材分散液、電極ペーストおよび導電材被覆活物質
WO2013073562A1 (ja) * 2011-11-15 2013-05-23 電気化学工業株式会社 複合粒子、その製造方法、二次電池用電極材料及び二次電池

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102544586B (zh) * 2010-12-10 2016-04-27 深圳市比克电池有限公司 锂离子电池制备方法及锂离子电池
JP6088418B2 (ja) * 2013-12-24 2017-03-01 旭カーボン株式会社 カーボンブラックおよびこのカーボンブラックを導電剤として用いた二次電池
JP2016046130A (ja) * 2014-08-25 2016-04-04 旭カーボン株式会社 二次電池用電極、二次電池

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001092151A1 (fr) * 2000-05-31 2001-12-06 Showa Denko K.K. Composite a base de carbone electriquement conducteur a fines particules, catalyseur pour pile a combustible a polymere solide et batterie de piles
JP2002042786A (ja) * 2000-07-25 2002-02-08 Sharp Corp 非水電解質二次電池
JP2003308845A (ja) * 2002-04-17 2003-10-31 Mikuni Color Ltd リチウム二次電池用電極及びこれを用いたリチウム二次電池
JP2003346804A (ja) * 2002-05-28 2003-12-05 Sony Corp 負極材料、非水電解質電池及び負極材料の製造方法
JP2005307070A (ja) * 2004-04-23 2005-11-04 Denki Kagaku Kogyo Kk カーボンブラック、その製造方法、及びそれを含有した組成物
JP2006210007A (ja) * 2005-01-25 2006-08-10 Mitsubishi Chemicals Corp 電気化学素子用電極およびそれを用いたリチウム二次電池
JP2007165079A (ja) * 2005-12-13 2007-06-28 Matsushita Electric Ind Co Ltd 非水電解質二次電池用負極とそれを用いた非水電解質二次電池
JP2010086955A (ja) * 2008-09-04 2010-04-15 Toyo Ink Mfg Co Ltd 電池電極用複合材料
JP2011070908A (ja) * 2009-09-25 2011-04-07 Mikuni Color Ltd 導電材分散液、電極ペーストおよび導電材被覆活物質
WO2013073562A1 (ja) * 2011-11-15 2013-05-23 電気化学工業株式会社 複合粒子、その製造方法、二次電池用電極材料及び二次電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020524192A (ja) * 2017-06-15 2020-08-13 キャボット コーポレイションＣａｂｏｔ Ｃｏｒｐｏｒａｔｉｏｎ カーボンブラック粒子を含む電極および関連する方法
CN114284465A (zh) * 2021-12-22 2022-04-05 蜂巢能源科技股份有限公司 正极浆料的制备方法、正极极片及锂离子电池

Also Published As

Publication number Publication date
JP6437348B2 (ja) 2018-12-12
JP2016162548A (ja) 2016-09-05
CN107251289A (zh) 2017-10-13
CN107251289B (zh) 2020-07-28

Similar Documents

Publication Publication Date Title
US10193148B2 (en) Carbon-silicon composite and manufacturing method thereof
KR101637068B1 (ko) 음극 활물질용 복합체 및 이의 제조방법
JP7209089B2 (ja) リチウム二次電池用負極活物質、その製造方法、およびこれを含むリチウム二次電池
CN113690406B (zh) 负极和用于制备负极的方法
JP2017204374A (ja) 酸化珪素系粉末負極材
CN108807933B (zh) 一种正极材料及其制备方法
JP7128290B2 (ja) リチウム二次電池用の負極活物質及びこれを含むリチウム二次電池
KR102373313B1 (ko) 무기 전해액을 포함하는 리튬 이차전지
US20160006019A1 (en) Carbon-silicon composite and manufacturing mehtod of the same
KR101882975B1 (ko) 리튬 일차전지의 양극 제조방법
WO2016135783A1 (ja) 電極活物質、二次電池用電極及び二次電池
KR102271632B1 (ko) 탄소-실리콘 복합체 분말의 제조 방법, 이에 의하여 제조된 탄소-실리콘 복합체 분말 및 이를 포함하는 리튬 이차전지
KR20190095835A (ko) 양극 및 상기 양극을 포함하는 이차 전지
KR102485284B1 (ko) 음극 및 상기 음극을 포함하는 이차 전지
EP4287305A1 (en) Negative electrode material for lithium-ion secondary battery, evaluation method therefor, manufacturing method therefor, negative electrode for lithium-ion secondary battery, and lithium-ion secondary battery
KR101795778B1 (ko) 탄소 복합 실리콘 음극 활물질의 제조 방법, 이에 의하여 제조된 탄소 복합 실리콘 음극 활물질 및 이를 포함하는 리튬 이차전지
Qiu et al. Development of a γ-polyglutamic acid binder for cathodes with high mass fraction of sulfur
WO2015098286A1 (ja) カーボンブラック
CN114424364A (zh) 负极活性材料、其制备方法、以及包含该负极活性材料的负极和二次电池
KR20210135552A (ko) 전고체 전지의 제조 방법
JP2015120822A5 (zh)
EP2763215B1 (en) Composite for anode active material and method for manufacturing same
KR20200085587A (ko) 음극 및 이를 포함하는 이차전지
Cech et al. Synthesis of LiFePO4/C composite cathode for lithium-ion batteries
KR20220107977A (ko) 고출력 특성을 가지는 불화탄소 복합소재 및 이를 포함하는 리튬일차전지 양극

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15883083

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15883083

Country of ref document: EP

Kind code of ref document: A1