WO2022230993A1 - 非水電解質二次電池用の負極活物質、それを用いた非水電解質二次電池、および非水電解質二次電池用の負極活物質の製造方法 - Google Patents

非水電解質二次電池用の負極活物質、それを用いた非水電解質二次電池、および非水電解質二次電池用の負極活物質の製造方法 Download PDF

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WO2022230993A1
WO2022230993A1 PCT/JP2022/019359 JP2022019359W WO2022230993A1 WO 2022230993 A1 WO2022230993 A1 WO 2022230993A1 JP 2022019359 W JP2022019359 W JP 2022019359W WO 2022230993 A1 WO2022230993 A1 WO 2022230993A1
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active material
negative electrode
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compound
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French (fr)
Japanese (ja)
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翔 柴田
拡哲 鈴木
基浩 坂田
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to US18/557,308 priority Critical patent/US20240222606A1/en
Priority to CN202280031443.XA priority patent/CN117223125A/zh
Priority to JP2023517629A priority patent/JPWO2022230993A1/ja
Priority to EP22795906.1A priority patent/EP4332062A4/en
Publication of WO2022230993A1 publication Critical patent/WO2022230993A1/ja
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    • 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
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    • 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
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 disclosure relates to a negative electrode active material for non-aqueous electrolyte secondary batteries, a non-aqueous electrolyte secondary battery using the same, and a method for manufacturing the negative electrode active material for non-aqueous electrolyte secondary batteries.
  • Silicon materials such as silicon (Si) and silicon oxide represented by SiOx are known to be able to absorb more lithium ions per unit volume than carbon materials such as graphite, and are used as negative electrodes of lithium ion batteries and the like. is being considered for application to A non-aqueous electrolyte secondary battery using a silicon material as a negative electrode active material has a problem of lower charge/discharge efficiency than a case where graphite is used as a negative electrode active material. Therefore, it has been proposed to use lithium silicate as a negative electrode active material in order to improve charge/discharge efficiency.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2003-160328 describes "a lithium-containing silicon oxide powder represented by the general formula SiLi x O y , wherein the range of x and y is 0 ⁇ x ⁇ 1.0,0 ⁇ A lithium-containing silicon oxide powder characterized in that y ⁇ 1.5, and in which lithium is coalesced and partially crystallized.”
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2014-150068 discloses that "a silicon-containing substance having a surface water content per unit specific surface area (200-300°C) of 0.1 to 20 ppm/(m 2 /g) is added to silane.
  • Non-Patent Document 1 reports that adding a vinyl group-containing silane coupling agent to the electrolyte of a monopolar battery using a Si/C composite improves the capacity retention rate in charge-discharge cycles.
  • one of the objects of the present disclosure is to provide a negative electrode active material that can constitute a non-aqueous electrolyte secondary battery having a high capacity retention rate in charge-discharge cycles.
  • the negative electrode active material includes active material particles containing silicon and a surface layer formed on the surface of the active material particles, and the surface layer is a reaction product of a compound reacted to form a siloxane bond.
  • the compound comprises a structure represented by Si—R1—Si, wherein R1 is at least one selected from the group consisting of a sulfur atom, an oxygen atom, and a nitrogen atom and an alkylene group as constituent elements
  • R1 is at least one selected from the group consisting of a sulfur atom, an oxygen atom, and a nitrogen atom and an alkylene group as constituent elements
  • One of the two Si includes an alkoxy group and an oxyalkylene group having a carbon number in the range of 1 to 6, and -O-(C x1 H 2x1+1 O y1 )
  • a chloro group, and a hydroxyl group is bonded
  • the other of the two Si is a group represented by -O-(C x2 H 2x2+1 O y2 )
  • the nonaqueous electrolyte secondary battery includes a positive electrode, a negative electrode, and a nonaqueous electrolyte, and the negative electrode includes the negative electrode active material according to the present disclosure.
  • Another aspect of the present disclosure relates to a method for producing a negative electrode active material for non-aqueous electrolyte secondary batteries.
  • the manufacturing method includes a first step of contacting a compound or a liquid in which the compound is dissolved with silicon-containing active material particles, and the compound or the liquid and the active material particles are in contact.
  • the compound comprises a structure represented by Si-R1-Si, wherein R1 is a sulfur atom, an oxygen atom, and a nitrogen atom and an atomic group having a chain portion containing an alkylene group as constituent elements, and one of the two Si has a carbon number in the range of 1 to 6 A group including an alkoxy group and an oxyalkylene group and represented by -O-(C x1 H 2x1+1 O y1 ) (x1 is an integer of 2 or more and 6 or less and y1 is an integer of 1 or more and 3 or less), a chloro group , and at least one atomic group selected from the group consisting of a hydroxyl group, and the other of the two Si includes an alkoxy group having a carbon number of 1 to 6, an oxyalkylene group, and -O At least selected from the group consisting of a group represented by -(C x2 H 2x2
  • FIG. 1 is a partially cutaway plan view schematically showing the structure of a non-aqueous electrolyte secondary battery according to an embodiment of the present invention
  • FIG. 2 is a cross-sectional view of the non-aqueous secondary battery shown in FIG. 1 taken along the line X-X';
  • FIG. 1 is a partially cutaway plan view schematically showing the structure of a non-aqueous electrolyte secondary battery according to an embodiment of the present invention
  • FIG. 2 is a cross-sectional view of the non-aqueous secondary battery shown in FIG. 1 taken along the line X-X';
  • a negative electrode active material for a non-aqueous electrolyte secondary battery includes silicon-containing active material particles and a surface layer formed on the surfaces of the active material particles.
  • the negative electrode active material and the surface layer are hereinafter sometimes referred to as “negative electrode active material (N)" and “surface layer (L)".
  • the surface layer (L) contains a reaction product of a given compound reacting to form a siloxane bond.
  • the compound may be hereinafter referred to as "compound (1)”.
  • Compound (1) contains a structure represented by Si--R1--Si.
  • R1 is an atomic group having a chain portion containing at least one selected from the group consisting of a sulfur atom, an oxygen atom and a nitrogen atom and an alkylene group as constituents.
  • One of the two Si is a group represented by -O-(C x1 H 2x1+1 O y1 ) containing an alkoxy group or an oxyalkylene group having a carbon number in the range of 1 to 6 (x1 is 2 or more and 6 or less is an integer and y1 is an integer of 1 or more and 3 or less), a chloro group, and a hydroxyl group.
  • the other of the two Si is a group represented by -O-(C x2 H 2x2+1 O y2 ) containing an alkoxy group and an oxyalkylene group having a carbon number in the range of 1 to 6 (x2 is 2 or more and 6 or less is an integer and y2 is an integer of 1 or more and 3 or less), a chloro group, and a hydroxyl group.
  • An oxyalkylene group is a group represented by —O—C x H 2x —.
  • the oxyalkylene group of oxygen atoms are bonded to Si.
  • -O-(C x H 2x+1 O y ) including an oxyalkylene group containing an oxygen atom bonded to Si (where x is an integer of 2 or more and 6 or less, and y is 1 or more and 3 or less is an integer) is sometimes referred to as an "oxyalkyl group”.
  • y eg, y1, y2, y6 described later
  • y may be 1 or 2.
  • Examples of the oxyalkyl group include a group represented by -OC x4 H 2x4 -OC x5 H 2x5+1 (x4 is an integer of 1 or more and 3 or less, and x5 is an integer of 1 or more and 3 or less), Examples include -OCH 2 CH 2 OCH 3 and the like.
  • the compound (1) may be a compound represented by the following formula (1).
  • At least one selected from the group consisting of R2, R3, and R4 each independently includes an alkoxy group having a carbon number of 1 to 6, an oxyalkylene group, and -O-( C x1 H 2x1+1 O y1 ) (x1 is an integer of 2 or more and 6 or less and y1 is an integer of 1 or more and 3 or less), a chloro group, or a hydroxyl group.
  • At least one selected from the group consisting of R5, R6, and R7 each independently includes an alkoxy group and an oxyalkylene group having 1 to 6 carbon atoms, and -O-(C x2 H 2x2+1 O y2 ) (x2 is an integer of 2 or more and 6 or less and y2 is an integer of 1 or more and 3 or less), a chloro group, or a hydroxyl group.
  • R2 to R7 are each independently a hydrocarbon group having a carbon number in the range of 1 to 6, a hydrogen atom, or a group represented by C x3 H 2x3+y3+1 N y3 O z3 S w3 (x3 is 1 or more and 6 or less y3 is an integer of 0 or more and 3 or less, z3 is an integer of 0 or more and 3 or less, w3 is an integer of 0 or more and 3 or less, and 1 ⁇ y3+z3+w3).
  • R2 to R7 may be the same or different.
  • hydrocarbon groups having 1 to 6 carbon atoms include alkyl, alkenyl and alkynyl groups having 1 to 6 carbon atoms.
  • the group represented by C x3 H 2x3+y3+1 N y3 O z3 S w3 is not an alkoxy group having 1 to 6 carbon atoms and is represented by —O—(C x1 H 2x1+1 O y1 ). is not based on y3, Z3, and w3 may each independently be an integer of 0-2 or an integer of 0-1.
  • the sum of y3, z3, and w3 may be in the range of 1-3, or in the range of 1-2.
  • the sum of y3, z3, and w3 may be 1 or 2, and is 1 in one example.
  • Examples of the group represented by C x3 H 2x3+y3+1 N y3 O z3 S w3 include a group represented by C x3 H 2x3+1 O y3 , an alkylamino group having 1 to 6 carbon atoms, and is in the range of 1 to 6, and the like.
  • the group represented by C x3 H 2x3+1 O y3 is bonded to Si via a carbon atom, for example.
  • Examples of groups represented by C x3 H 2x3+1 O y3 include hydroxyalkyl groups.
  • the rest of R2 to R7 may each independently be a hydrocarbon group having a carbon number in the range of 1 to 6, or a hydrogen atom.
  • the alkoxy group having a carbon number in the range of 1 to 6 and the oxyalkylene group described above are collectively referred to as "-O-( C x6 H 2x6 +1 O y6 ) (x6 is an integer of 2 or more and 6 or less, and y6 is an integer of 0 or more and 3 or less)".
  • an alkoxy group having 1 to 6 carbon atoms and the oxyalkylene group described above may be collectively read as "a group containing an alkoxy group and having 1 to 6 carbon atoms".
  • the surface layer formed on the surface of the active material particles contains a reaction product of compound (0) reacting to form a siloxane bond.
  • Compound (0) is a compound containing two silicon atoms bonded with an atomic group capable of forming a siloxane bond by reaction and R1 connecting the two silicon atoms.
  • the number of such atomic groups bonded to one silicon atom is in the range of 1 to 3, preferably 2, more preferably 3.
  • Examples of atomic groups capable of forming siloxane bonds by reaction include alkoxy groups, hydroxyl groups, chloro groups, and the oxyalkyl groups described above.
  • an alkoxy group, a hydroxyl group, a chloro group, and the above-mentioned oxyalkyl group having 1 to 6 carbon atoms may be collectively referred to as "atomic group (G)".
  • a reaction for example, a hydrolysis/condensation reaction in which a compound having an alkoxysilyl group is reacted to form a siloxane bond is widely known.
  • R1 exemplified for compound (1) can be applied to R1 in compound (0).
  • Examples of compound (0) include at least part of examples of compound (1).
  • compound (0) and compound (1) Commercially available compounds may be used as compound (0) and compound (1).
  • a compound whose synthesis method is known may be synthesized by a known synthesis method.
  • the chain of the chain portion of R1 and the chain connecting two silicon atoms is at least one atom selected from the group consisting of a sulfur atom, an oxygen atom, and a nitrogen atom. and the carbon atoms in the alkylene group.
  • the surface of the active material particles is protected by the reaction product of compound (1). At least part of compound (1) forms a siloxane bond with silicon in the active material particles. In compound (1), silyl groups forming siloxane bonds are linked by R1. Therefore, the surface of the active material particles is protected by forming a siloxane bond between the two silyl groups and the silicon of the active material particles. Since the reaction product of compound (1) contains the R1 portion, it flexibly follows the expansion and contraction of the active material particles due to charge and discharge, and the surface is protected even if the active material particles repeatedly expand and contract due to charge and discharge cycles. Layers are hard to break. Therefore, according to the present disclosure, it is possible to suppress side reactions with components in the electrolytic solution on the surfaces of the active material particles. As a result, according to the present disclosure, it is possible to increase the capacity retention rate in charge/discharge cycles.
  • those that are not the atomic group (G) described above may each independently be the groups described above.
  • those that are not the atomic group (G) described above are each independently a hydrocarbon group having a carbon number in the range of 1 to 6, a hydrogen atom, or the above formula C x3 It may be a group represented by H 2x3+y3+1 N y3 O z3 S w3 .
  • Formula (1) preferably satisfies the following conditions (V1) or (V2), and more preferably satisfies the following conditions (V3) or (V4).
  • Formula (1) may satisfy the following condition (V5) or (V6).
  • V1 The number of carbon atoms contained in each of R2 to R7 is 4 or less.
  • V2 at least two selected from the group consisting of R2, R3, and R4 are alkoxy groups having 1 to 4 carbon atoms, and at least two selected from the group consisting of R5, R6, and R7; is an alkoxy group having 1 to 4 carbon atoms.
  • R2 to R7 those that are not alkoxy groups having 1 to 4 carbon atoms are hydrocarbon groups having 1 to 6 carbon atoms (alkyl groups, alkenyl groups, alkynyl groups), or hydrogen atoms is.
  • All of R2 to R7 are alkoxy groups having 1 to 4 carbon atoms (for example, 1 to 3 carbon atoms).
  • All of R2 to R7 are each independently a methoxy group or an ethoxy group.
  • R2-R7 may be methoxy or ethoxy groups.
  • all of R2 to R7 may be methoxy groups, or all of R2 to R7 may be ethoxy groups.
  • a preferred example of formula (1) satisfies any one of the above conditions (V1) to (V6) and the following condition (W1).
  • a preferred example of formula (1) satisfies any one of the above conditions (V1) to (V6) and satisfies the condition (W2) or (W3).
  • equation (1) may additionally satisfy condition (W4) or (W5).
  • (W1) R1 is an atomic group containing a chain portion composed of at least one selected from the group consisting of a sulfur atom, an oxygen atom and a nitrogen atom, and an alkylene group.
  • (W2) R1 is at least one heteroatom selected from the group consisting of a sulfur atom, an oxygen atom, and a nitrogen atom; It includes a chain-like portion composed of an alkylene group.
  • the number of carbon atoms of the two alkylene groups is independently in the range of 2-4.
  • the two alkylene groups may be directly attached to the heteroatom.
  • R1 is —(CH 2 ) p S n (CH 2 ) q — (1 ⁇ n ⁇ 6, 2 ⁇ p ⁇ 4, 2 ⁇ q ⁇ 4), —(CH 2 ) p O(CH 2 ) q -(2 ⁇ p ⁇ 4, 2 ⁇ q ⁇ 4), -(CH 2 ) p O(CH 2 ) r O(CH 2 ) q -(2 ⁇ p ⁇ 4, 2 ⁇ q ⁇ 4, 2 ⁇ r ⁇ 4), and —(CH 2 ) p NH(CH 2 ) q — (2 ⁇ p ⁇ 4, 2 ⁇ q ⁇ 4).
  • n, p, q, and r are natural numbers.
  • the number of atoms constituting the chain portion of the chain portion is 2 or more, 3 or more, 5 or more, or 6 or more, and 20 or less, 15 or less, or 10 or less. is.
  • the number of atoms can range from 3-20, from 3-15, or from 3-10. The lower limits of these ranges may be replaced by 5 or 6.
  • the number of atoms constituting the chain portion of the chain portion is the number of atoms constituting only the chain connecting two silicon atoms. For example, in the case of alkylene groups, only the number of carbon atoms making up the chain is counted.
  • R1 is a straight chain containing no branched chains.
  • R1 contains at least one heteroatom selected from the group consisting of a sulfur atom, an oxygen atom, and a nitrogen atom
  • the ion coordination ability of the heteroatom causes lithium ions to form from the lithium salt in the electrolytic solution.
  • Dissociation as carrier ions is considered to promote lithium ion conduction in the surface layer. As a result, it is thought that it is possible to reduce the inhibition of the transfer of lithium ions between the active material and the electrolyte during charging and discharging by the surface layer.
  • R1 When R1 contains a nitrogen atom, R1 may contain an amide bond.
  • formula (1) When formula (1) satisfies condition (W1), compound (1) represented by formula (1) may be a sulfide, an ether, or an amine.
  • the mass of the reaction product of compound (1) contained in the surface layer may be in the range of 0.001% to 10% (for example, in the range of 0.05% to 1%) of the mass of the active material particles. This percentage may be analyzed, such as by ICP analysis.
  • the reaction product may have a chemical structure in which Si in the Si-R1-Si structure is bonded to Si in the active material particles through siloxane bonds. That is, the surface layer (L) includes a chemical structure (reaction product of compound (1)) in which Si in a plurality of Si-R1-Si structures is bonded to Si in the active material particles through siloxane bonds. It's okay.
  • the reaction product may have a structure in which Si in a plurality of Si--R1--Si structures are bonded to each other and to Si in the active material particles through siloxane bonds.
  • the surface layer (L) has a chemical structure in which Si in a plurality of Si-R1-Si structures are bonded to each other and to Si in the active material particles by siloxane bonds (reaction product of compound (1) ) may be included.
  • compound (1) in which chain portion of R1 contains sulfur in compound (1) (for example, the compound represented by formula (1)), the chain portion of R1 may contain sulfur.
  • compound (1) may be a bis(alkoxysilylalkyl)sulfide.
  • An example of compound (1) in which the chain portion of R1 contains sulfur is described below.
  • R1 is a sulfide group represented by C t1 H 2t1 S z , and t1 and z are each an integer of 1 or more.
  • At least one of R2 to R4 is at least one selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms, the alkyloxy group described above, a hydroxyl group, and a chloro group.
  • At least one of R5 to R7 is at least one selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms, the alkyloxy group described above, a hydroxyl group, and a chloro group.
  • the rest of R2 to R7 may each independently be the groups described above. Specifically, among R2 to R7, those that are not the atomic group (G) described above are each independently a hydrocarbon group having a carbon number in the range of 1 to 6, a hydrogen atom, or the above formula C x3 It may be a group represented by H 2x3+y3+1 N y3 O z3 S w3 .
  • the atomic group (G) contained in R2 to R4 and R5 to R7 is capable of forming an X—O—Si—R bond with the surface of the material containing the silicon element, and the surface of the material containing the silicon element.
  • the surface can be covered with a Si-R1-Si structure with stable siloxane bonds on both ends. That is, the surface of the material containing elemental silicon is covered with a film containing a bissilyl sulfide structure (a film formed of a reaction product of compound (1), and hereinafter sometimes referred to as an “SSS film”). can be broken
  • the sulfide group (R1) represented by C t1 H 2t1 S z may have a structure represented by R11-S z -R12.
  • R11 and R12 are each independently an alkylene group having 1 or more carbon atoms.
  • Such R1 is considered to have excellent flexibility and a large electron shielding property due to the Sz structure, thereby increasing the effect of suppressing side reactions.
  • R11 and R12 preferably have 1 to 6 carbon atoms, more preferably 2 to 4 carbon atoms.
  • the bis(alkoxysilylalkyl)sulfide is desirably bis(alkoxysilylC 1-6 alkyl)sulfide and may be bis(alkoxysilylC 2-4 alkyl)sulfide.
  • the Sz group constituting R1 has a higher flexibility as the number of continuous sulfur atoms increases, thereby facilitating reversible deformation of the SSS coating.
  • the number of sulfur atoms in the Sz group is preferably 1-6, more preferably 2-4. That is, bis(alkoxysilylalkyl)sulfide is desirably bis(alkoxysilylC 1-6 alkyl)S 1-6 sulfide, and bis(alkoxysilylC 2-4 alkyl)S 2-4 sulfide. good too.
  • the number of carbon atoms in the alkoxy group may be in the range of 1 to 3, and the number of carbon atoms in the oxyalkyl group may be in the range of 2 to 3. .
  • R2-R7 may be groups as described above. Specifically, among R2 to R7, those that are not the atomic group (G) described above are each independently a hydrocarbon group having a carbon number in the range of 1 to 6, a hydrogen atom, or the above formula C x3 It may be a group represented by H 2x3+y3+1 N y3 O z3 S w3 . From the viewpoint of reducing steric hindrance during the reaction, it may have 1 to 3 carbon atoms. R2 to R4 are each independent, and all of R2 to R4 may have the same number of carbon atoms, all of R2 to R4 may have different number of carbon atoms, and two of R2 to R4 may have the same number of carbon atoms.
  • R5 to R7 are each independent, all of R5 to R7 may have the same number of carbon atoms, all of R5 to R7 may have different number of carbon atoms, and two of R5 to R7 may have the same number of carbon atoms. .
  • the two alkoxysilyl groups (R2R3R4Si- or R5R6R7Si-) linked to R1 may be the same or different. However, two alkoxysilyl groups linked to R1 may have the same structure in order to increase the symmetry of the structure of the SSS coating and make it a more stable structure.
  • bis(trialkoxysilylC 1-6 alkyl)S 1-6 sulfides easily available ones include bis(triethoxysilylpropyl) sulfide, bis(triethoxysilylpropyl) disulfide, bis(triethoxysilylpropyl ) trisulfide and bis(triethoxysilylpropyl)tetrasulfide.
  • Bis(triethoxysilylpropyl)tetrasulfide (TESPT, also known as bis[3-(triethoxysilyl)propyl]tetrasulfide) is shown below. These may be commercially available products or may be synthesized by known methods.
  • compound (1) in which the chain portion of R1 contains nitrogen in compound (1) (for example, the compound represented by formula (1)), the chain portion of R1 may contain nitrogen.
  • compound (1) may be a bis(alkoxysilylalkyl)amine.
  • Compound (1) in which the chain portion of R1 contains nitrogen refers to the compound (1) in which the chain portion of R1 contains sulfur in the above description of compound (1) in which the S z group is a secondary amino group (—NH—)
  • it may be a compound substituted with a tertiary amino group.
  • examples of side chains attached to the nitrogen atom include alkyl groups and alkoxysilylalkyl groups.
  • An example of a bis(alkoxysilylalkyl)amine is shown below. These may be commercially available products or may be synthesized by known methods.
  • R1 may have a structure represented by R11-N-R12.
  • R11 and R12 are each independently an alkylene group having 1 or more carbon atoms.
  • Such R1 is considered to have excellent flexibility and high electron-shielding properties, thereby further enhancing the effect of suppressing side reactions.
  • the number of carbon atoms in the alkylene group is desirably 1 to 6 carbon atoms, and more desirably 2 to 4 carbon atoms.
  • the bis(alkoxysilylalkyl)amine is desirably a bis(alkoxysilylC 1-6 alkyl)amine and may be a bis(alkoxysilylC 2-4 alkyl)amine.
  • the compound (1) in which the chain portion of R1 contains an amide bond is a compound in which the Sz group in the above description of the compound (1) containing sulfur in the chain portion of R1 is replaced with an amide group. good.
  • compound (1) in which the chain portion of R1 contains an ether bond the chain portion of R1 may contain an ether bond.
  • compound (1) may be a compound obtained by replacing R1 with an ether bond-containing atomic group in the above description of compound (1) in which the chain portion of R1 contains sulfur.
  • R1 of compound (1) contains an ether bond
  • R1 may have a structure represented by R11-(O-R12) n -O-R13.
  • R11, R12 and R13 are each independently an alkylene group having 1 or more carbon atoms, and n is an integer of 0 or more.
  • Such R1 has excellent flexibility, and the oxygen that binds R11 and R12 and the oxygen that binds R12 and R13 are coordinated to the cation, thereby allowing the cation to move in and out of the material containing the silicon element. can promote It is believed that this increases the cation conductivity and further enhances the effect of suppressing a decrease in the capacity retention rate.
  • n is 2 or more
  • the plurality of R12 contained in the (OR12) unit may all be the same alkylene group, or may contain alkylene groups with different carbon numbers.
  • R11 and R13 preferably have 1 to 6 carbon atoms, more preferably 2 to 4 carbon atoms.
  • the bis(alkoxysilylalkyl) ether is desirably a bis(alkoxysilyl C 1-6 alkyl) ether and may be a bis(alkoxysilyl C 2-4 alkyl) ether.
  • the -O- group that constitutes R1 increases the cation conductivity and contributes to the improvement of the capacity retention rate.
  • the number of —O— groups is desirably 1 to 5, more desirably 1 to 3. That is, the number n of (O-R12) units contained in R1 is desirably 0-4, more desirably 0-2.
  • the number of carbon atoms in R12 is preferably 4 or less, more preferably 2 or more and 4 or less, from the viewpoint of promoting the movement of cations between adjacent oxygen atoms.
  • R1 may be -C 3 H 6 -OC 3 H 6 - or -C 2 H 4 -OC 2 H 4 -OC 3 H 6 -.
  • Each of R2 to R7 may be a methoxy group.
  • alkoxysilyl compounds include bis(alkoxysilylalkyl) ethers represented by the following formula.
  • the surface layer (L) of the negative electrode active material (N) may contain conductive carbon.
  • formula (1) preferably satisfies the above condition (V2) or (V5). Since active materials containing silicon have low electrical conductivity, capacity is likely to decrease during charge-discharge cycles. By arranging conductive carbon on the surface of the active material, it is possible to suppress a decrease in capacity during charge-discharge cycles. However, simply arranging the conductive carbon on the surface reduces the adhesion between the active material and the conductive carbon due to the expansion and contraction of the active material during charge/discharge cycles, and the conductivity between them decreases.
  • the surface layer (L) contains the reaction product of compound (1) and conductive carbon
  • the charge/discharge efficiency of the silicon-containing negative electrode active material can be greatly improved. This may be because the network formed by the reaction product of compound (1) maintains the adhesion between the active material and the conductive carbon.
  • Examples of conductive carbon include amorphous carbon, graphite, graphitizable carbon (soft carbon), and non-graphitizable carbon (hard carbon). Among them, amorphous carbon is preferable because it facilitates formation of a thin conductive layer covering the surface of the composite particles. Examples of amorphous carbon include carbon black, burned pitch, coke, and activated carbon.
  • Graphite includes natural graphite, artificial graphite, graphitized mesophase carbon, and the like.
  • the active material particles contain silicon (silicon element).
  • a material containing silicon is sometimes treated as a kind of alloy-based material.
  • the alloy-based material refers to a material containing an element capable of forming an alloy with lithium.
  • Elements capable of forming an alloy with lithium include silicon and tin, and silicon (Si) is particularly promising.
  • the manufacturing method of the active material particles Active material particles may be produced by a known method, or commercially available ones may be used.
  • Materials containing silicon may be silicon alloys, silicon compounds, or composite materials. Among them, a composite material containing a lithium ion conductive phase and silicon particles dispersed in the lithium ion conductive phase is promising.
  • the lithium ion conductive phase for example, a silicon oxide phase, a silicate phase, a carbon phase, or the like can be used.
  • the silicon oxide phase is a material with relatively high irreversible capacity.
  • the silicate phase is preferable because of its low irreversible capacity.
  • a major component (eg, 95-100% by weight) of the silicon oxide phase may be silicon dioxide.
  • the composition of a composite material comprising a silicon oxide phase and silicon particles dispersed therein can collectively be expressed as SiO x .
  • SiOx has a structure in which silicon fine particles are dispersed in amorphous SiO 2 .
  • the content ratio x of oxygen to silicon is, for example, 0.5 ⁇ x ⁇ 2.0, more preferably 0.8 ⁇ x ⁇ 1.5.
  • the silicate phase may contain, for example, at least one selected from the group consisting of Group 1 elements and Group 2 elements of the long period periodic table.
  • Group 1 elements of the long period periodic table and Group 2 elements of the long period periodic table include lithium (Li), potassium (K), sodium (Na), magnesium (Mg), and calcium (Ca). , strontium (Sr), barium (Ba), and the like.
  • Other elements may include aluminum (Al), boron (B), lanthanum (La), phosphorus (P), zirconium (Zr), titanium (Ti), and the like.
  • a silicate phase containing lithium hereinafter also referred to as a lithium silicate phase
  • a silicate phase containing lithium is preferable because of its small irreversible capacity and high initial charge/discharge efficiency.
  • the lithium silicate phase may be an oxide phase containing lithium (Li), silicon (Si), and oxygen (O), and may contain other elements.
  • the atomic ratio of O to Si: O/Si in the lithium silicate phase is greater than 2 and less than 4, for example.
  • O/Si is greater than 2 and less than 3.
  • the atomic ratio of Li to Si in the lithium silicate phase: Li/Si is greater than 0 and less than 4, for example.
  • Elements other than Li, Si and O that can be contained in the lithium silicate phase include, for example, iron (Fe), chromium (Cr), nickel (Ni), manganese (Mn), copper (Cu), molybdenum (Mo), Examples include zinc (Zn) and aluminum (Al).
  • the carbon phase can be composed of, for example, amorphous carbon with low crystallinity (that is, amorphous carbon).
  • Amorphous carbon may be, for example, hard carbon, soft carbon, or otherwise.
  • Each of the active material particles (N) and the negative electrode mixture layer may contain a material that electrochemically absorbs and releases lithium ions, lithium metal, a lithium alloy, etc., in addition to the material containing the silicon element.
  • a carbon material is preferable as the material for electrochemically intercalating and deintercalating lithium ions.
  • Examples of carbon materials include graphite, graphitizable carbon (soft carbon), and non-graphitizable carbon (hard carbon). Among them, graphite is preferable because it has excellent charging/discharging stability and low irreversible capacity.
  • the active material particles are composite particles containing a lithium silicate phase represented by Li x SiO y (0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 4) and a silicon phase dispersed in the lithium silicate phase.
  • x and y are independent of x and y for compound (1).
  • Such composite particles may be produced, for example, by the method described in Examples, or may be produced by a known method.
  • the crystallite size of the silicon phase may be in the range of 1 nm to 1000 nm (eg, in the range of 200 nm to 500 nm).
  • the crystallite size of the silicon phase is calculated by Scherrer's formula from the half width of the diffraction peak attributed to the (111) plane of the silicon phase (simple elemental Si) in the X-ray diffraction pattern.
  • the active material particles may be composite particles containing a carbon phase and a silicon phase dispersed within the carbon phase.
  • the carbon phase can, for example, consist of amorphous carbon (ie, amorphous carbon).
  • Amorphous carbon may be, for example, hard carbon, soft carbon, or others.
  • Amorphous carbon generally refers to a carbon material having an average interplanar spacing d002 of (002) planes exceeding 0.34 nm as measured by an X-ray diffraction method.
  • a production method according to the present disclosure is a method for producing a negative electrode active material (N) for a non-aqueous electrolyte secondary battery according to the present disclosure.
  • the negative electrode active material (N) may be produced by a method other than the method described below. Since the items described with respect to the negative electrode active material (N) can be applied to the following manufacturing method, redundant description may be omitted. Matters described in the manufacturing method below may be applied to the negative electrode active material according to the present disclosure.
  • This manufacturing method includes a first step and a second step. Included in this order.
  • the first and second steps are carried out under conditions in which compound (1) forms a siloxane bond.
  • the first and second steps may be carried out under the same conditions as those for hydrolyzing and condensing a known alkoxysilyl group-containing silane coupling agent to form a siloxane bond.
  • the first step is to bring the compound (1) or a liquid in which the compound (1) is dissolved into contact with active material particles containing silicon.
  • the liquid may be hereinafter referred to as “liquid (S)”.
  • the first step may be a step of dispersing silicon-containing active material particles in compound (1) or liquid (S).
  • the first step may be a step of applying compound (1) or liquid (S) to the surface of the silicon-containing active material particles.
  • the compound (1) is the compound described above and is represented by formula (1).
  • the active material particles are the active material particles described above.
  • Liquid (S) can be prepared by dissolving compound (1) in a solvent. A part of the compound (1) may react to form a siloxane bond before the second step is performed.
  • Solvents may include lower alcohols (eg, ethanol), water, and acids. Examples of acids include hydrochloric acid and the like.
  • the content of the reaction product of compound (1) in the negative electrode active material (N) can be changed by changing the concentration of compound (1) in liquid (S).
  • the concentration of compound (1) in liquid (S) may be in the range of 0.0001 to 10 mol/liter (eg, in the range of 0.001 to 0.1 mol/liter).
  • the mass of the compound (1) per 1 g mass of the active material particles dispersed in the liquid (S) may be in the range of 0.0001 to 1 g (for example, in the range of 0.001 to 0.1 g).
  • the second step is a step of reacting compound (1) to form a siloxane bond while the compound (1) or liquid (S) is in contact with the active material particles.
  • the second step may be performed, for example, by maintaining the temperature of the liquid (S) and the active material particles at a predetermined temperature for a predetermined period of time.
  • the liquid (S) may be stirred in the second step.
  • the predetermined temperature may be in the range of 10-200° C. (eg, in the range of 40-100° C.).
  • the predetermined time may be in the range of 1-120 hours (eg, in the range of 12-72 hours).
  • a negative electrode active material (N) is obtained by the second step.
  • the negative electrode active material (N) obtained in the second step may be washed and/or dried as necessary.
  • the production method according to the present disclosure includes a step of placing conductive carbon on the surface of the active material particles before the first step, between the first step and the second step, or after the second step. (a) may be included. By performing the step (a), the surface layer (L) containing the reaction product of the compound (1) and the conductive carbon can be formed.
  • the step (a) may be performed by heat-treating a mixture of the active material particles and the conductive carbon.
  • raw materials for the conductive carbon for example, coal pitch, coal tar pitch, petroleum pitch, phenol resin, or the like can be used.
  • the heat treatment may be performed, for example, by heating at a temperature of 450-1000° C. for 1-10 hours.
  • the conductive carbon described above can be used as the conductive carbon.
  • step (a) may form the conductive carbon layer by reacting a hydrocarbon gas on the surface of the composite particles by a gas phase method such as a CVD method. Acetylene, methane, etc. may be used as the hydrocarbon gas. According to these methods, a conductive layer that can be infiltrated by the reaction product of compound (1) can be formed.
  • the present disclosure provides a negative electrode for non-aqueous electrolyte secondary batteries.
  • the negative electrode includes the negative electrode active material (N) according to the present disclosure.
  • a nonaqueous electrolyte secondary battery includes a positive electrode, a negative electrode, and a nonaqueous electrolyte.
  • the negative electrode includes a negative electrode active material (N).
  • N negative electrode active material
  • the configuration of the negative electrode is not particularly limited except that it contains the negative electrode active material (N).
  • An example of a negative electrode according to the present disclosure includes a negative electrode current collector and a negative electrode mixture layer disposed on the surface of the negative electrode current collector. Except for using the negative electrode active material (N), the method for manufacturing the non-aqueous electrolyte secondary battery according to the present disclosure is not limited, and it may be manufactured by a known method.
  • the configuration of the non-aqueous electrolyte secondary battery according to the present disclosure will be described below.
  • the configuration of the non-aqueous electrolyte secondary battery is not limited to the following configuration.
  • the negative electrode includes, for example, a negative electrode current collector and a negative electrode mixture layer formed on the surface of the negative electrode current collector.
  • the negative electrode mixture layer contains a negative electrode active material (N) as an essential component, and may contain optional components such as a binder, a conductive material, and a thickener.
  • the negative electrode mixture layer may contain a negative electrode active material other than the negative electrode active material (N) in addition to the negative electrode active material (N).
  • Known materials can be used for optional components such as the binder, the conductive material, and the thickener.
  • the negative electrode mixture layer is formed, for example, by applying a negative electrode slurry in which a negative electrode mixture containing a negative electrode active material (N) and a predetermined optional component is dispersed in a dispersion medium on the surface of the negative electrode current collector and drying the slurry. can be formed. The dried coating film may be rolled if necessary.
  • the negative electrode mixture layer may be formed on one surface of the negative electrode current collector, or may be formed on both surfaces.
  • a metal sheet or metal foil is used for the negative electrode current collector.
  • materials for the negative electrode current collector include stainless steel, nickel, nickel alloys, copper, copper alloys, and the like.
  • the positive electrode includes, for example, a positive electrode current collector and a positive electrode mixture layer formed on the surface of the positive electrode current collector.
  • the positive electrode mixture layer contains a positive electrode active material as an essential component, and may contain optional components such as a binder, a conductive material, and a thickener. Known materials can be used for optional components such as the binder, the conductive material, and the thickener.
  • the positive electrode mixture layer can be formed, for example, by applying a positive electrode slurry in which a positive electrode mixture containing a positive electrode active material and a predetermined optional component is dispersed in a dispersion medium on the surface of the positive electrode current collector and drying the slurry. The dried coating film may be rolled if necessary.
  • the positive electrode material mixture layer may be formed on one surface of the positive electrode current collector, or may be formed on both surfaces.
  • a lithium-containing composite oxide can be used as the positive electrode active material.
  • a lithium-containing composite oxide can be used as the positive electrode active material.
  • Me is Na , Mg, Sc , Y, Mn, Fe, Co, Ni, Cu, Zn, is at least one selected from the group consisting of Al, Cr, Pb, Sb, and B).
  • a 0-1.2
  • b 0-0.9
  • c 2.0-2.3. Note that the value a, which indicates the molar ratio of lithium, increases or decreases due to charging and discharging.
  • a positive electrode active material usually has the form of secondary particles in which primary particles are aggregated.
  • the average particle size of the positive electrode active material may be, for example, 2 ⁇ m or more and 20 ⁇ m or less.
  • the average particle size refers to the median size at which the cumulative volume is 50% in the volume-based particle size distribution.
  • the volume-based particle size distribution can be measured with a laser diffraction particle size distribution analyzer.
  • a metal sheet or metal foil is used for the positive electrode current collector.
  • materials for the positive electrode current collector include stainless steel, aluminum, aluminum alloys, and titanium.
  • Examples of conductive materials used for the positive electrode mixture layer and the negative electrode mixture layer include carbon materials such as carbon black (CB), acetylene black (AB), ketjen black (KB), carbon nanotubes (CNT), and graphite. be These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • carbon black CB
  • AB acetylene black
  • KB ketjen black
  • CNT carbon nanotubes
  • graphite graphite
  • binders used for the positive electrode mixture layer and the negative electrode mixture layer include fluororesins (polytetrafluoroethylene, polyvinylidene fluoride, etc.), polyacrylonitrile (PAN), polyimide resins, acrylic resins, polyolefin resins, and the like. be These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • a non-aqueous electrolyte secondary battery usually includes a separator disposed between a positive electrode and a negative electrode.
  • the separator has high ion permeability and moderate mechanical strength and insulation.
  • a microporous membrane, a woven fabric, a nonwoven fabric, or the like can be used as the separator.
  • separator materials include polyolefins (polypropylene, polyethylene, etc.).
  • a non-aqueous electrolyte (non-aqueous electrolyte from another point of view) includes a non-aqueous solvent and a salt (solute) dissolved in the non-aqueous solvent.
  • a salt (solute) is an electrolyte salt that ionizes in a non-aqueous solvent.
  • the salt contains at least lithium salt.
  • the non-aqueous electrolyte may contain additives other than the non-aqueous solvent and salt.
  • the non-aqueous electrolyte may contain compound (1) and/or a reaction product of compound (1).
  • cyclic carbonate for example, cyclic carbonate, chain carbonate, cyclic carboxylate, chain carboxylate, and the like are used.
  • Cyclic carbonates include propylene carbonate (PC), ethylene carbonate (EC), vinylene carbonate (VC) and the like.
  • Chain carbonates include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC) and the like.
  • cyclic carboxylic acid esters include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL).
  • Chain carboxylic acid esters include methyl acetate, ethyl acetate, propyl acetate, methyl propionate (MP), ethyl propionate (EP) and the like.
  • the non-aqueous solvent may be used singly or in combination of two or more.
  • the non-aqueous electrolytic solution may contain chain carboxylic acid ester in an amount of 1% by mass or more and 90% by mass or less.
  • chain carboxylic acid esters methyl acetate has a particularly low viscosity. Therefore, 90% by mass or more of the chain carboxylic acid ester may be methyl acetate.
  • non-aqueous solvents include cyclic ethers, chain ethers, nitriles such as acetonitrile, and amides such as dimethylformamide.
  • cyclic ethers examples include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, propylene oxide, 1,2-butylene oxide, 1,3-dioxane, 1,4- dioxane, 1,3,5-trioxane, furan, 2-methylfuran, 1,8-cineol, crown ether and the like.
  • linear ethers examples include 1,2-dimethoxyethane, dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methylphenyl ether, ethylphenyl ether, butylphenyl ether.
  • pentylphenyl ether methoxytoluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, o-dimethoxybenzene, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, 1,1-dimethoxymethane, 1,1-diethoxyethane, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and the like.
  • These solvents may be fluorinated solvents in which some of the hydrogen atoms are substituted with fluorine atoms.
  • Fluoroethylene carbonate (FEC) may be used as a fluorinated solvent.
  • lithium salts include lithium salts of chlorine - containing acids (LiClO4, LiAlCl4 , LiB10Cl10 , etc.), lithium salts of fluorine - containing acids ( LiPF6 , LiPF2O2 , LiBF4 , LiSbF6 , LiAsF6 , LiCF 3 SO 3 , LiCF 3 CO 2 , etc.), lithium salts of fluorine-containing acid imides (LiN(FSO 2 ) 2 , LiN(CF 3 SO 2 ) 2 , LiN(CF 3 SO 2 ) (C 4 F 9 SO 2 ), LiN ( C2F5SO2 ) 2 , etc.), lithium halides ( LiCl, LiBr, LiI, etc.) can be used. Lithium salts may be used singly or in combination of two or more.
  • the concentration of the lithium salt in the non-aqueous electrolyte may be 0.5 mol/liter or more and 2 mol/liter or less, or may be 1 mol/liter or more and 1.5 mol/liter or less. By controlling the lithium salt concentration within the above range, it is possible to obtain a non-aqueous electrolytic solution with excellent ion conductivity and low viscosity.
  • Additives include 1,3-propanesultone, methylbenzenesulfonate, cyclohexylbenzene, biphenyl, diphenyl ether, and fluorobenzene.
  • An example of a non-aqueous electrolyte secondary battery includes an exterior body, and an electrode group and a non-aqueous electrolyte housed in the exterior body.
  • the electrode group may be a wound electrode group formed by winding a positive electrode and a negative electrode with a separator interposed therebetween.
  • the wound electrode group instead of the wound electrode group, other forms of electrode group may be applied.
  • the electrode group may be a laminated electrode group formed by laminating a positive electrode and a negative electrode with a separator interposed therebetween.
  • the non-aqueous electrolyte secondary battery may be in any shape, for example, cylindrical, square, coin, button, sheet (laminate).
  • FIG. 1 is a partially cutaway plan view schematically showing an example of the structure of a non-aqueous electrolyte secondary battery.
  • FIG. 2 is a cross-sectional view taken along line XX' of FIG.
  • the non-aqueous electrolyte secondary battery 100 is a sheet-type battery, and includes an electrode plate group 4 and an exterior case 5 that accommodates the electrode plate group 4 .
  • the electrode plate group 4 has a structure in which a positive electrode 10, a separator 30 and a negative electrode 20 are laminated in this order, and the positive electrode 10 and the negative electrode 20 face each other with the separator 30 interposed therebetween. Thus, the electrode plate group 4 is formed. Electrode group 4 is impregnated with a non-aqueous electrolyte (not shown).
  • the positive electrode 10 includes a positive electrode active material layer 1a and a positive electrode current collector 1b.
  • the positive electrode active material layer 1a is formed on the surface of the positive electrode current collector 1b.
  • the negative electrode 20 includes a negative electrode mixture layer 2a and a negative electrode current collector 2b.
  • the negative electrode mixture layer 2a is formed on the surface of the negative electrode current collector 2b.
  • the negative electrode mixture layer 2a contains the negative electrode active material (N) according to the present disclosure.
  • a positive electrode tab lead 1c is connected to the positive electrode current collector 1b, and a negative electrode tab lead 2c is connected to the negative electrode current collector 2b.
  • the positive electrode tab lead 1c and the negative electrode tab lead 2c extend to the outside of the exterior case 5, respectively.
  • the insulating tab film 6 insulates between the positive electrode tab lead 1c and the outer case 5 and between the negative electrode tab lead 2c and the outer case 5, respectively.
  • An example of compound (1) in which the chain portion of R1 contains oxygen may be synthesized by the following method. First, 1.0 g of allyl ether, 40.0 mL of dichloroethane (C 2 H 4 Cl 2 ), 3.7 g of trimethoxysilane (HSi(OMe) 3 ), cyclooctadiene and 0.1 g of iridium chloride dimer ([Ir(COD)Cl] 2 ) was added and stirred to allow the reaction represented by the following formula to proceed. The mixture was heated and stirred from below room temperature to 50° C. until allyl ether as a raw material disappeared.
  • Brown oil K2 was added to the crude product after distillation, and the purification was again carried out by distillation at an oil bath temperature of 190° C. and a degree of vacuum of 0.1-0.01 mmHg to obtain a colorless oil compound K3 containing alkoxysilyl compound A (13.3 g, 38.8 mol, yield 34.6%). Purity was confirmed by 1 H-NMR and gas chromatography (GC).
  • a distillation purification device was attached to the reactor, dichloromethane was removed at a bath temperature of 50°C, and volatile components were removed under reduced pressure of 20 mmHg/70°C.
  • the residue was purified by distillation (degree of vacuum: 0.1-0.3 mmHg, oil bath temperature: 180-195° C., steam temperature: 139-142° C.), and a light brown solution of compound C (10.4 g, 27.0 g) was obtained. 9 mol, yield 59.6%).
  • the melt was passed through a metal roller to form a flake-like solid, and the solid was heat-treated at 750° C. for 5 hours to obtain a lithium silicate composite oxide present as a mixed phase of amorphous and crystalline.
  • the obtained lithium silicate composite oxide was pulverized to an average particle size of 10 ⁇ m.
  • the sintered body was pulverized and passed through a mesh of 40 ⁇ m. Then, the particles passed through the mesh were mixed with coal pitch (manufactured by JFE Chemical Co., Ltd., MCP250) to obtain a mixture. Next, by heat-treating the mixture at 800° C. for 5 hours in an inert gas atmosphere, the particle surfaces were coated with conductive carbon to form a conductive layer. The coating amount of the conductive layer was 5% by mass with respect to the total mass of the Si-containing lithium silicate composite oxide particles and the conductive layer. After that, using a sieve, active material particles having an average particle size of 5 ⁇ m and having a conductive layer were obtained.
  • active material particles (a0) the active material particles and the conductive layer formed on the surface thereof may be collectively referred to as "active material particles (a0)".
  • Bis[3-(triethoxysilyl)propyl]tetrasulfide (commercial product, hereinafter sometimes referred to as “P1”) was added to the above mother liquor so as to give a concentration of 0.5% by mass, and mixed to obtain P1.
  • a solution was prepared.
  • 22 g of the active material particles (a0) were mixed with the P1 solution to form a suspension, which was stirred at 50° C. for 24 hours using a stirrer. This caused P1 to react to form a siloxane bond.
  • the suspension was suction-filtered using a polytetrafluoroethylene (PTFE) membrane filter, and rinsed with 500 mL of ethanol and then with 500 mL of pure water.
  • the collected particles were vacuum-dried at 100° C. for 24 hours to obtain a negative electrode active material (a1-1).
  • a cross section of this negative electrode active material (a1-1) was observed with a TEM-EDX apparatus (JEM-F200, manufactured by JEOL Ltd.). As a result, it was confirmed that a surface layer was formed on the Si-containing lithium silicate composite oxide particles. It was confirmed that the surface layer contained a conductive layer (conductive carbon layer) and a P1-derived substance (including a reaction product of P1) infiltrated into the conductive layer.
  • the collected particles were vacuum-dried at 100° C. for 24 hours to obtain a negative electrode active material (a2-1).
  • a cross section of this negative electrode active material (a2-1) was observed with a TEM-EDX apparatus (JEM-F200, manufactured by JEOL Ltd.). As a result, it was confirmed that a surface layer was formed on the Si-containing lithium silicate composite oxide particles. It was confirmed that the surface layer contained a conductive layer (conductive carbon layer) and a substance derived from compound C (including a reaction product of compound C) infiltrated into the conductive layer.
  • a paste was obtained by mixing 31 g of the active material particles (a0) with an aqueous compound C solution. Next, the paste was vacuum-dried at 100° C. for 24 hours to obtain a powdery negative electrode active material (a2-2).
  • a cross section of this negative electrode active material (a2-2) was observed with a TEM-EDX apparatus (JEM-F200, manufactured by JEOL Ltd.). As a result, it was confirmed that a surface layer was formed on the Si-containing lithium silicate composite oxide particles. It was confirmed that the surface layer contained a conductive layer (conductive carbon layer) and a substance derived from compound C (including a reaction product of compound C) infiltrated into the conductive layer.
  • a negative electrode slurry was prepared by stirring the mixture using a mixer (TK Hibismix, manufactured by Primix).
  • the negative electrode slurry is applied to both sides of the copper foil (negative electrode current collector), the coating film is dried, and then rolled to form negative electrode mixture layers having a density of 1.6 g/cm 3 on both sides of the copper foil. A formed negative electrode was obtained.
  • NMP N-methyl-2-pyrrolidone
  • the mixture was stirred using a mixer (TK Hibismix manufactured by Primix) to prepare a positive electrode slurry.
  • the positive electrode slurry is applied to both sides of an aluminum foil (positive electrode current collector), the coating film is dried, and then rolled with rolling rollers to obtain a density of 3.6 g/cm 3 on both sides of the positive electrode current collector.
  • a positive electrode on which a positive electrode mixture layer of was formed was produced.
  • EC ethylene carbonate
  • EMC ethylmethyl carbonate
  • DMC dimethyl carbonate
  • a tab was attached to each of the electrodes.
  • the positive electrode, the negative electrode, and the separator were spirally wound so that the separator was arranged between the positive electrode and the negative electrode, thereby producing a wound electrode group.
  • the electrode plate was wound so that the tab was positioned at the outermost periphery.
  • the obtained electrode plate assembly was inserted into an outer package composed of an aluminum laminate sheet having a height of 62 mm and a width of 35 mm, and vacuum-dried at 105° C. for 2 hours.
  • the non-aqueous electrolytic solution was injected into the outer package, and the opening of the outer package was sealed.
  • a battery (A1-1) which is a non-aqueous electrolyte secondary battery, was produced.
  • the design capacity of this battery was 360 mAh.
  • a battery (A1-2) was produced under the same conditions as the battery (A1-1) except that the negative electrode active material (a1-2) was used instead of the negative electrode active material (a1-1).
  • a battery (A2-1) was fabricated under the same conditions as those for the battery (A1-1), except that the negative electrode active material (a2-1) was used instead of the negative electrode active material (a1-1).
  • Charge-discharge cycle characteristics A total of 400 charging/discharging cycles were performed at a temperature of 25° C. for the non-aqueous electrolyte secondary battery. Charge-discharge cycles were performed by repeating a set of charge-discharge cycles consisting of 100 charge-discharge cycles four times. One set of charge-discharge cycles includes one charge-discharge cycle under charge-discharge condition 1, one charge-discharge cycle under charge-discharge condition 2, and then 98 charge-discharge cycles under charge-discharge condition 3. It was done by repeating
  • Capacity retention rate (%) after 400 cycles (discharge capacity at 400th cycle/discharge capacity at 3rd cycle) x 100
  • the battery B is a battery of a comparative example, and the others are batteries according to the present disclosure.
  • Batteries A1-1 to A2-2 according to the present disclosure were able to suppress a decrease in capacity retention rate due to charge-discharge cycles as compared with battery B of the comparative example.
  • the surfaces of the negative electrode active materials (a1-1) to (a2-2) are protected by the reaction product of compound (1). Therefore, it is considered that the reaction (side reaction) between Si and the electrolytic solution was suppressed, and the decrease in the capacity retention rate was suppressed.

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PCT/JP2022/019359 2021-04-30 2022-04-28 非水電解質二次電池用の負極活物質、それを用いた非水電解質二次電池、および非水電解質二次電池用の負極活物質の製造方法 Ceased WO2022230993A1 (ja)

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CN202280031443.XA CN117223125A (zh) 2021-04-30 2022-04-28 非水电解质二次电池用的负极活性物质、使用了其的非水电解质二次电池、和非水电解质二次电池用的负极活性物质的制造方法
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EP22795906.1A EP4332062A4 (en) 2021-04-30 2022-04-28 NEGATIVE ELECTRODE ACTIVE MATERIAL FOR NONAQUEOUS ELECTROLYTE SECONDARY BATTERY AND METHOD FOR PRODUCING SAME, AND NONAQUEOUS ELECTROLYTE SECONDARY BATTERY USING THIS NEGATIVE ELECTRODE ACTIVE MATERIAL

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