WO2013146300A1 - 非水電解質二次電池用負極活物質粒子粉末及びその製造方法、並びに非水電解質二次電池 - Google Patents
非水電解質二次電池用負極活物質粒子粉末及びその製造方法、並びに非水電解質二次電池 Download PDFInfo
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Definitions
- a negative electrode active material for a non-aqueous electrolyte secondary battery in which volume expansion accompanying Li storage is suppressed.
- graphitic carbon is widely used as a negative electrode material, but its capacity has already reached a value close to the theoretical value.
- Patent Document 1 a technique of coating the particle surface with a resin (Patent Document 1), a technique of fixing a negative electrode with a resin (Patent Documents 2 to 8), and the like are known.
- a negative electrode active material in which volume expansion due to Li occlusion is sufficiently suppressed has not been obtained yet.
- the metal negative electrode material replacing the carbon-based negative electrode material has the merit that the Li storage amount is large and the capacity is large, while the electrode structure is destroyed by volume expansion. There were disadvantages.
- thermosetting resin on Li active metal particles that expand in volume due to Li occlusion.
- the present invention relates to a negative electrode active material for a non-aqueous electrolyte secondary battery comprising a composite particle powder of metal particles and a thermosetting resin, wherein the composite particle powder has an average particle size of 5 to 100 ⁇ m. It is a characteristic negative electrode active material for nonaqueous electrolyte secondary batteries (Invention 1).
- the present invention also relates to a negative electrode active material for a non-aqueous electrolyte secondary battery according to the present invention 1 having a thermosetting resin content of 5.0 to 30 wt% (present invention 2).
- the present invention also relates to a negative electrode active material for a non-aqueous electrolyte secondary battery comprising a composite particle powder of metal particles and a thermosetting resin carbide, wherein the composite particle powder has an average particle size of 5 to 100 ⁇ m.
- This is a negative electrode active material for a nonaqueous electrolyte secondary battery (Invention 3).
- the present invention also relates to a negative electrode active material for a non-aqueous electrolyte secondary battery according to the present invention 1 or 2, wherein the carbide content is 0.1 to 20 wt% (Invention 4).
- the present invention is the negative electrode active material for a non-aqueous electrolyte secondary battery according to any one of the present invention 1 to 4, wherein the thermosetting resin is a thermosetting phenol resin or a thermosetting epoxy resin (the present invention). 5).
- the present invention provides the invention according to any one of the present inventions 1 to 5, wherein one or more carbons selected from crystalline carbon or carbon nanotubes are contained inside and on the surface of the negative electrode active material for a non-aqueous electrolyte secondary battery.
- Any one of the negative electrode active materials for nonaqueous electrolyte secondary batteries (this invention 6).
- the metal particles and thermosetting phenol resin or thermosetting epoxy resin are granulated to form a composite, and then the composite is heat-treated at 300 to 1200 ° C. in a reducing atmosphere. It is a manufacturing method of the negative electrode active material of the invention 3, (this invention 7).
- the present invention is a lithium ion secondary battery characterized in that the negative electrode active material for a non-aqueous electrolyte secondary battery according to any one of the present inventions 1 to 6 is used as a negative electrode material (Invention 8).
- Example 2 is an electron micrograph showing the particle shape of a negative electrode active material for a nonaqueous electrolyte secondary battery obtained in Example 1.
- the negative electrode active material particle powder for non-aqueous electrolyte secondary battery according to the present invention (hereinafter referred to as “negative electrode active material particle powder”) is composed of composite particles of metal particles and thermosetting resin.
- thermosetting resin it is preferable to use a thermosetting phenol resin or a thermosetting epoxy resin as the thermosetting resin.
- the content of the thermosetting resin in the negative electrode active material according to the present invention is preferably 5 to 30% by weight.
- the amount is less than 5% by weight, granulated particles by resin coating cannot be obtained, and when it exceeds 30% by weight, the filling property and dispersibility of the obtained negative electrode active material into the resin are insufficient.
- it is 5 to 20% by weight.
- the negative electrode active material according to the present invention may be in a state where the thermosetting resin is carbonized.
- the carbide content of the thermosetting resin is preferably 0.1 to 20% by weight. When it is less than 0.1% by weight, it is difficult to maintain the granulated state, and when it exceeds 20% by weight, the filling property and dispersibility of the obtained negative electrode active material into the resin are insufficient. Become. Preferably, it is 0.5 to 10% by weight.
- the negative electrode active material according to the present invention may contain one or more carbons selected from crystalline carbon such as ketjen black and acetylene black or carbon nanotubes inside or on the particle surface. By containing these carbon materials, conductivity is improved.
- the content of crystalline carbon or carbon nanotube in the negative electrode active material according to the present invention is preferably 0.1 to 70% by weight. When it is less than 0.1% by weight, the effect of increasing the electrical conductivity of the obtained negative electrode active material is insufficient. When it exceeds 70% by weight, the filling property and dispersibility of the obtained negative electrode active material into the resin are insufficient. Preferably, it is 1 to 50% by weight.
- the particle form of the negative electrode active material according to the present invention is preferably granular, spherical, or elliptical, and can reduce the viscosity of the paste when applied to the current collector.
- the average particle diameter (D50: average secondary particle diameter) of the negative electrode active material according to the present invention is 5 to 100 ⁇ m.
- An average particle size of less than 5 ⁇ m is not preferable because the packing density is lowered and the reactivity with the electrolyte is increased.
- the average particle diameter exceeds 100 ⁇ m it is not preferable because the dispersibility into the resin deteriorates when forming an electrode.
- the thickness is preferably 8 to 50 ⁇ m.
- the negative electrode active material according to the present invention is granulated into a composite using metal particles and a thermosetting phenol resin or a thermosetting epoxy resin by either a dry method or a wet method. If necessary, the obtained composite can be produced by heat treatment in a reducing atmosphere.
- the metal particles in the present invention are one or more selected from Si, Sn, Al, Mg, Na, Fe, Cd, Sb, Pb or Bi, and Si, Sn, Al, Fe, Cd, Sb, Pb. Or it is chosen from Bi, More preferably, they are Si and Sn.
- the average particle diameter of the metal particles in the present invention is preferably about 10 nm to 5 ⁇ m.
- the metal particles used in the present invention have a lipophilic surface in advance. By performing the oleophilic treatment, a negative electrode active material having a spherical shape can be obtained more easily.
- metal particles are dispersed in an aqueous solvent containing a surfactant or a method of treating metal particles with a coupling agent such as a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent.
- a coupling agent such as a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent.
- a method of adsorbing the surfactant on the surface is suitable.
- thermosetting phenol resin a thermosetting phenol resin
- silane coupling agent examples include those having a hydrophobic group, an amino group, and an epoxy group.
- examples of the silane coupling agent having a hydrophobic group include vinyl trichlorosilane, vinyl triethoxysilane, vinyl tris ( ⁇ - Methoxy) silane and the like.
- Examples of silane coupling agents having an amino group include ⁇ -aminopropyl triethoquinopran, N- ⁇ (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane.
- silane coupling agent having an epoxy group examples include ⁇ -glycidoxypropyl trimethylsilane, ⁇ -glycidoxypropyltrimethoxylane, ⁇ - (3,4-epoxycyclohexyl) trimethoxysilane and the like.
- titanate coupling agent isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate or the like may be used.
- surfactant commercially available surfactants can be used, and those having functional groups capable of binding to metal particles and hydroxyl groups on the surface of the particles are desirable, and the ionicity is cationic or anionic. Is preferred.
- the object of the present invention can be achieved by any of the above-mentioned treatment methods, but treatment with a silane coupling agent having an amino group or an epoxy group is preferable in consideration of adhesion with a phenol resin.
- the treatment amount of the coupling agent or surfactant is preferably 0.1 to 10% by weight with respect to the metal particles.
- a method for producing a composite comprising metal particles and a thermosetting phenol resin is as follows.
- alkylphenols such as m-cresol, p-cresol, p-tert-butylphenol, o-propylphenol, and a part or all of alkyl groups are chlorine atoms or bromine atoms.
- compounds having a phenolic hydroxyl group, such as halogenated phenols substituted with are chlorine atoms or bromine atoms.
- aldehydes used in the present invention include formaldehyde, acetaldehyde, furfural, glyoxal, acrolein, crotonaldehyde, salicylaldehyde, and glutaraldehyde in the form of either formalin or paraaldehyde, with formaldehyde being most preferred.
- the molar ratio of aldehydes to phenols is preferably 1.0 to 4.0.
- the molar ratio of aldehydes to phenols is less than 1.0, it is difficult to form particles, Since curing is difficult to proceed, the strength of the resulting particles tends to be weak.
- it exceeds 4.0 there is a tendency that unreacted aldehydes remaining in the aqueous medium after the reaction increase. More preferably, it is 1.2 to 3.0.
- a basic catalyst used in the production of ordinary resol resins can be used.
- ammonia water, hexamethylenetetramine, alkylamines such as dimethylamine, diethyltriamine, and polyethyleneimine can be mentioned, and ammonia water is particularly preferable.
- the basic catalyst is preferably in a molar ratio of 0.05 to 1.50 with respect to phenols. If it is less than 0.05, curing does not proceed sufficiently and granulation becomes difficult. If it exceeds 1.50, the structure of the phenol resin is affected, so that the granulation property is deteriorated and it is difficult to obtain particles having a large particle size.
- the reaction in the present invention is carried out in an aqueous medium, but the solid content concentration in the aqueous medium is preferably 30 to 95% by weight, particularly preferably 60 to 90% by weight. .
- the reaction solution to which the basic catalyst has been added is heated to a temperature range of 60 to 95 ° C., and reacted at this temperature for 30 to 300 minutes, preferably 60 to 240 minutes, followed by a polycondensation reaction of a phenol resin and curing.
- the heating rate is preferably 0.5 to 1.5 ° C./min, more preferably 0.8 to 1.2 ° C./min.
- the stirring speed is preferably 100 to 1000 rpm.
- the solid dispersion is separated from the aqueous dispersion containing the complex according to conventional methods such as filtration and centrifugation, and then washed and dried to obtain a complex.
- thermosetting epoxy resin a thermosetting epoxy resin
- titanate-based, silane-based coupling agents having a lipophilic group, silylating agents, silicone oils, etc. can be used, and in particular, functional groups capable of reacting with epoxy resins. Those having (—NH 2 or the like) are preferable because they have effects such as increasing the strength of the composite itself.
- Titanate coupling agents having a lipophilic group include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ) Ethylene titanate and the like
- silane coupling agents having a lipophilic group include N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldimethoxysilane, ⁇ -Aminopropyltriethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysi
- the treatment amount of the lipophilic agent is preferably 0.1 to 10% by weight with respect to the metal particles.
- thermosetting epoxy resin a method for producing a composite comprising metal particles and a thermosetting epoxy resin is as follows.
- bisphenols compounds having two or more phenolic hydrogen groups such as bisphenol A, bisphenol F, bisphenol S, resorcin and the like can be used.
- Bisphenol A is preferred from the economical aspect.
- epihalohydrin epichlorohydrin, epibromohydrin, epiiodohydrin and the like can be used, and epichlorohydrin is preferable.
- the use ratio of bisphenols and epihalohydrin is 0.5 to 1.0: 1.0 in molar ratio.
- 0.5 When it is less than 0.5, granulation becomes difficult due to the influence of reaction by-products and the like caused by excess epihalohydrin. If it exceeds 1.0, the curing rate becomes high, and it is difficult to obtain a composite, and even if it is obtained, the spread of the particle size distribution becomes large.
- An alkaline aqueous medium can be obtained by adding an alkali such as sodium hydroxide or potassium hydroxide to water.
- an alkaline aqueous medium containing metal particles, bisphenols and epihalohydrin is heated to a temperature in the range of 60 to 90 ° C. while stirring in the presence of a curing agent, and the polymerization reaction is allowed to proceed for about 1 to 5 hours.
- the temperature is raised to a temperature in the range of 60 to 90 ° C. while stirring in the presence of a curing agent in an aqueous medium containing metal particles and an uncured epoxy resin, and the curing reaction is allowed to proceed for about 1 to 8 hours. Is done.
- the reaction in the present invention is carried out in an aqueous medium, but the solid content concentration in the aqueous medium is preferably 30 to 95% by weight, particularly preferably 60 to 90% by weight. .
- curing agent acid anhydrides, amines and the like that are generally known as curing agents for epoxy resins can be used.
- an epoxy compound having two or more epoxy groups in the molecule such as bisphenol A both-terminal glycidyl ether and polyethylene glycol both-terminal glycidyl ether can be used.
- the heating rate is preferably 0.5 to 1.5 ° C./min, more preferably 0.8 to 1.2 ° C./min.
- the stirring speed is preferably 100 to 1000 rpm.
- the alkaline aqueous medium or the complex formed in the aqueous medium may be subjected to solid-liquid separation by ordinary methods such as filtration and centrifugation, and then washed with water and dried by heating.
- the total content of metal particles in the composite is preferably 70 to 95% by weight with respect to the composite, and if it is less than 70% by weight, the resin content increases and large particles are easily formed. If it exceeds 95% by weight, the resin content is insufficient and sufficient strength cannot be obtained. More preferably, it is 80 to 90% by weight.
- crystalline carbon or carbon nanotube When crystalline carbon or carbon nanotube is contained, it may be added at the time of dispersion before curing the resin, or a catalyst made of nickel or iron may be supported on the carbon nanotube and generated by decomposition reaction of gas containing carbon. .
- the heat treatment of the composite in the present invention in a reducing atmosphere may be performed at a temperature necessary for decomposition and carbonization of the phenol resin or epoxy resin, that is, 300 ° C. or more.
- the treatment is preferably performed at 400 to 1200 ° C, more preferably at 500 to 1000 ° C.
- the treatment temperature is less than 400 ° C., the carbonization of the phenol resin or epoxy resin does not proceed.
- it exceeds 1000 ° C., the pore diameter is not in the preferred range.
- the heat treatment temperature may be maintained at an appropriate temperature for a certain period of time, and further raised to the desired heat treatment temperature.
- the reducing atmosphere in the heat treatment include nitrogen, hydrogen, or a mixed gas thereof.
- a conductive agent and a binder are added and mixed according to a conventional method.
- the conductive agent acetylene black, carbon black, graphite and the like are preferable
- the binder polytetrafluoroethylene, polyvinylidene fluoride and the like are preferable.
- the secondary battery manufactured using the negative electrode containing the negative electrode active material particle powder according to the present invention includes the negative electrode, the positive electrode, and an electrolyte.
- the positive electrode active material various positive electrode active materials such as LiCoO 2 , LiNiO 2 , LiMn 2 O 4, and LiFePO 4 can be used.
- the positive electrode active material may contain various different elements.
- an organic solvent containing at least one of carbonates such as propylene carbonate and dimethyl carbonate and ethers such as dimethoxyethane can be used as the solvent for the electrolytic solution.
- At least one lithium salt such as lithium perchlorate and lithium tetrafluoroborate can be dissolved in the above solvent and used.
- a typical embodiment of the present invention is as follows.
- the average particle diameter of the negative electrode active material was measured using a scanning electron microscope (SEM).
- a CR2032-type coin cell was manufactured using a lithium mixed with EC and DMC in a volume ratio of 1: 2 in which 1 mol / l LiPF 6 was dissolved as a positive electrode and metallic lithium punched into 16 mm ⁇ .
- charging was performed at a current density of 0.05 C up to 1.6 V in an environment set to 25 ° C. in a thermostat, and then discharging was performed at a current density of 0.1 C up to 0.01 V.
- a level equal to or lower than that of Comparative Example 1 was determined to be “bad”, and a value exceeding that level was determined to be “good”.
- Example 1 Into a 1 liter flask was charged 67.8 g of phenol, 53.9 g of formalin, 200 g of the above powder whose particle surface was treated with a silane coupling agent having an epoxy group, 24.2 g of aqueous ammonia and 6 g of water, and the mixture was stirred for 30. After raising the temperature to 85 ° C. for 1 minute, the composite of the silicon particle powder and the phenol resin was produced by reacting and curing at the same temperature for 120 minutes. Next, the contents in the flask are cooled to 30 ° C., 1.5 liters of water is added, the supernatant is removed, and the lower layer precipitate is washed with water, in a dryer set at 80 ° C. After drying for 12 hours, spherical composite particles composed of a silicon particle powder having an average particle diameter (D50) of 15.2 ⁇ m and a phenol resin were obtained.
- D50 average particle diameter
- the obtained composite particles had an average particle size of 20 ⁇ m and a resin content of 25 wt%.
- the sheet surface was “good” and the electrode density was “high”.
- FIGS. 1 and 2 it can be seen that the metal active material is encapsulated in a resin, is spherical, is hardened, and has high density.
- Example 2 The composite particles obtained in Example 1 were heat-treated at 1000 ° C. for 2 hours in a reducing atmosphere (N 2 ) to obtain a negative electrode active material composed of silicon powder and carbon. Various characteristics of the obtained negative electrode active material particle powder are shown in Table 1.
- Examples 3-7, Comparative Examples 1-3 Various conditions were changed with respect to Example 2, and heat treatment was performed at a temperature of 300 to 1200 ° C. to obtain negative electrode active material particle powder.
- Table 1 shows the production conditions of the negative electrode active material particle powder and various characteristics of the obtained negative electrode active material particle powder.
- the negative electrode active material particle powder according to the present invention was excellent in initial charge / discharge characteristics. This is presumably due to the fact that the volume expansion accompanying the storage of Li was suppressed. Moreover, it was confirmed that the negative electrode active material according to the present invention has a high electrode density.
- the negative electrode active material according to the present invention is excellent in initial charge / discharge capacity, it is suitable as a negative electrode active material particle powder for a non-aqueous electrolyte secondary battery.
Abstract
Description
負極活物質の体積膨張を抑制するため、樹脂で活物質を覆うことが有効であると考え、Li活性な金属粒子を熱硬化性樹脂で被覆すること、被覆した樹脂をグラファイト化することで活物質に導電性を持たせることによって、負極活物質として特性向上することができた。体積膨張を抑制する理由として、金属粒子の周りに樹脂及び/又はその炭化物が存在することで、金属活物質のLi吸蔵による膨張に伴う体積変化を吸収することができることによるものと推定している。
電極密度(g/cm3)=(打ち抜きシート重量―アルミ箔重量)
/(打ち抜きシート面積×(打ち抜きシート厚さーアルミ箔の厚さ))
高:1.3g/cm3以上
低:1.3g/cm3未満
本発明における実施例で得られた負極活物質を用い、活物質:アセチレンブラック:PVdF=9:1:1(wt%)になるよう調整して、ギャップ150μmのドクターブレードで電極スラリーをAl箔集電体上に塗布した。シート乾燥後、3t/cm2に加圧しシート表面を目視で観察し、下記2段階で評価した。
良:シート表面に塗布ムラが確認されない
悪:シート表面に塗布ムラが確認される
本発明における実施例で得られた負極活物質を用い、活物質:アセチレンブラック:PVdF=9:1:1(wt%)になるよう調整して、Cu箔上に塗工し、110℃で3時間乾燥した。このシートを16mmφに打ち抜いた後、1t/cm2で圧着し、集電体上の電極膜厚を20μmとしたものを負極に用いた。
正極は16mmφに打ち抜いた金属リチウムとし、電解液は1mol/lのLiPF6を溶解したECとDMCを体積比で1:2で混合した溶液を用いてCR2032型コインセルを作製した。
1リットルフラスコ内にフェノール67.8g、ホルマリン53.9g、粒子表面がエポキシ基を有するシランカップリング剤で処理されている上記粉末200g、アンモニア水24.2g及び水6gを仕込み、撹拌しながら30分間で85℃に上昇させた後、同温度で120分間反応・硬化させることにより、シリコン粒子粉末とフェノール樹脂とからなる複合体の生成を行った。
次に、フラスコ内の内容物を30℃に冷却し、1.5リットルの水を添加した後、上澄み液を除去し、さらに下層の沈殿物を水洗し、80℃に設定した乾燥機中で12時間乾燥させ、平均粒径(D50)が15.2μmであるシリコン粒子粉末とフェノール樹脂とからなる球状の複合体の粒子を得た。
図1、2に示すように金属活物質が樹脂に内包され球状であり、且つ固められていて密度の高い粒子であることがわかる。
上記実施例1で得られた複合体粒子を還元性雰囲気中(N2)、1000℃で2時間熱処理を行って、シリコン粉末と炭素とからなる負極活物質を得た。得られた負極活物質粒子粉末の諸特性を表1に示す。
前記実施例2に対して種々条件を変更し、300~1200℃の間の温度で熱処理を行って、負極活物質粒子粉末を得た。
Claims (8)
- 金属粒子と熱硬化性樹脂との複合粒子粉末からなる非水電解質二次電池用負極活物質であって、前記複合粒子粉末の平均粒径が5~100μmであることを特徴とする非水電解質二次電池用負極活物質。
- 熱硬化性樹脂の含有量が5.0~30wt%である請求項1記載の非水電解質二次電池用負極活物質。
- 金属粒子と熱硬化性樹脂の炭化物との複合粒子粉末からなる非水電解質二次電池用負極活物質であって、前記複合粒子粉末の平均粒径が5~100μmであることを特徴とする非水電解質二次電池用負極活物質。
- 炭化物の含有量が0.1~20wt%である請求項3記載の非水電解質二次電池用負極活物質。
- 熱硬化性樹脂が熱硬化性フェノール樹脂又は熱硬化性エポキシ樹脂からなる請求項1~4のいずれかに記載の非水電解質二次電池用負極活物質。
- 非水電解質二次電池用負極活物質の粒子内部及び粒子表面に、結晶性炭素又はカーボンナノチューブから選ばれる1種または2種類以上の炭素を含有する請求項1~5のいずれかに記載の非水電解質二次電池用負極活物質。
- 金属粒子と熱硬化性フェノール樹脂又は熱硬化性エポキシ樹脂とを造粒して複合体とした後、当該複合体を還元性雰囲気中で300~1200℃で加熱処理する請求項3記載の負極活物質の製造方法。
- 負極材として請求項1~6のいずれかに記載の非水電解質二次電池用負極活物質を用いることを特徴とするリチウムイオン二次電池。
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KR1020147026934A KR20140148395A (ko) | 2012-03-30 | 2013-03-14 | 비수전해질 이차 전지용 부극 활물질 입자 분말 및 그의 제조 방법 및 비수전해질 이차 전지 |
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JP2015118871A (ja) * | 2013-12-19 | 2015-06-25 | 凸版印刷株式会社 | 非水電解質二次電池用負極、及び非水電解質二次電池 |
JP2016207635A (ja) * | 2015-04-24 | 2016-12-08 | 住友金属鉱山株式会社 | 非水系電解質二次電池用正極活物質とその製造方法、および該正極活物質を用いた非水系電解質二次電池 |
JP2019033094A (ja) * | 2014-04-25 | 2019-02-28 | サウス ダコタ ボード オブ リージェンツ | 大容量電極 |
US11824189B2 (en) | 2018-01-09 | 2023-11-21 | South Dakota Board Of Regents | Layered high capacity electrodes |
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CN103474666B (zh) * | 2013-07-23 | 2016-03-02 | 江苏华东锂电技术研究院有限公司 | 锂离子电池负极活性材料的制备方法 |
KR102237829B1 (ko) * | 2013-12-30 | 2021-04-08 | 삼성전자주식회사 | 리튬 이차 전지용 음극재, 그 제조방법, 이를 음극으로 포함하는 리튬 이차 전지 |
CN106469814B (zh) * | 2016-04-14 | 2019-11-29 | 山东圣泉新能源科技有限公司 | 一种包覆剂、负极材料、锂离子电池及其制备方法 |
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US11824189B2 (en) | 2018-01-09 | 2023-11-21 | South Dakota Board Of Regents | Layered high capacity electrodes |
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US20150064553A1 (en) | 2015-03-05 |
EP2833444A4 (en) | 2015-10-21 |
KR20140148395A (ko) | 2014-12-31 |
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