JP2018110076A - Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery - Google Patents
Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery Download PDFInfo
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- JP2018110076A JP2018110076A JP2017000169A JP2017000169A JP2018110076A JP 2018110076 A JP2018110076 A JP 2018110076A JP 2017000169 A JP2017000169 A JP 2017000169A JP 2017000169 A JP2017000169 A JP 2017000169A JP 2018110076 A JP2018110076 A JP 2018110076A
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- negative electrode
- lithium ion
- ion secondary
- secondary battery
- electrode material
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Classifications
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明はリチウムイオン二次電池用負極材、リチウムイオン二次電池用負極及びリチウムイオン二次電池に関する。 The present invention relates to a negative electrode material for a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery.
リチウムイオン二次電池用負極材には、リチウムイオンを吸蔵放出する炭素材料が広く使用されている。炭素材料としては、黒鉛が挙げられる。黒鉛を炭素材料として用いると、充放電におけるリチウムイオンの吸蔵放出反応が可逆性に優れるため、サイクル特性が良好なリチウムイオン二次電池が得られる。しかしながら、黒鉛のリチウムイオンの吸蔵放出容量は、ＬｉＣ６を形成した場合の３７２ｍＡｈ／ｇが理論値であり、さらなる高容量化には限界がある。 Carbon materials that occlude and release lithium ions are widely used as negative electrode materials for lithium ion secondary batteries. An example of the carbon material is graphite. When graphite is used as a carbon material, a lithium ion secondary battery having good cycle characteristics can be obtained because the lithium ion occlusion and release reaction during charge and discharge is excellent in reversibility. However, the lithium ion storage / release capacity of graphite is 372 mAh / g when LiC 6 is formed, and there is a limit to further increase in capacity.
シリコン（Ｓｉ）は、リチウムと合金（金属間化合物）を形成するため、電気化学的にリチウムイオンを吸蔵放出することが可能である。リチウムイオンの吸蔵放出容量は、Ｌｉ２２Ｓｉ５を形成した場合の４１９７ｍＡｈ／ｇが理論値であり、黒鉛負極よりも高容量化することが可能である。 Since silicon (Si) forms an alloy (intermetallic compound) with lithium, it is possible to occlude and release lithium ions electrochemically. The lithium ion storage / release capacity has a theoretical value of 4197 mAh / g when Li 22 Si 5 is formed, and can have a higher capacity than the graphite negative electrode.
一方で、シリコンはリチウムイオンの吸蔵放出にともない３倍〜４倍の大きな体積変化を生じる。このため、充放電サイクルを行った場合、膨張収縮が繰り返されることによりシリコンが崩壊して微細化してしまい、良好なサイクル寿命が得られないという課題があった。そこで、黒鉛粒子、シリコン微粒子及び非晶質炭素を含む複合粒子の表面に、黒鉛又はカーボンブラックから選ばれる少なくとも１種類以上の物質である炭素質物質が配置されるとともに、該炭素質物質が非晶質炭素によって被覆された構造を有するリチウムイオン二次電池材料が開示されている（例えば、特許文献１参照）。 On the other hand, silicon causes a large volume change of 3 to 4 times with insertion and extraction of lithium ions. For this reason, when a charge / discharge cycle is performed, there is a problem that silicon is collapsed and refined by repeated expansion and contraction, and a good cycle life cannot be obtained. Therefore, a carbonaceous material which is at least one kind of material selected from graphite or carbon black is disposed on the surface of the composite particles containing graphite particles, silicon fine particles and amorphous carbon, and the carbonaceous material is non-coated. A lithium ion secondary battery material having a structure covered with crystalline carbon is disclosed (for example, see Patent Document 1).
リチウムイオン二次電池の高容量化に対する要求が高まっているなか、さらに高容量であるリチウムイオン二次電池を作製可能な負極材が求められている。そこで本発明は、高容量であるリチウムイオン二次電池を作製可能なリチウムイオン二次電池用負極材、ならびにこれを用いたリチウムイオン二次電池用負極及びリチウムイオン二次電池を提供することを課題とする。 Along with the increasing demand for higher capacity of lithium ion secondary batteries, negative electrode materials capable of producing lithium ion secondary batteries having higher capacities have been demanded. Accordingly, the present invention provides a negative electrode material for a lithium ion secondary battery capable of producing a high capacity lithium ion secondary battery, and a negative electrode for a lithium ion secondary battery and a lithium ion secondary battery using the same. Let it be an issue.
上記課題を解決するための手段は、以下の通りである。 Means for solving the above problems are as follows.
＜１＞ アスペクト比が１〜２０であり、かつ、厚みが０．５μｍ以下の扁平なシリコン粒子であるリチウムイオン二次電池用負極材。
＜２＞ アスペクト比が１〜２０、かつ、厚みが０．５μｍ以下の扁平なシリコン粒子と、前記シリコン粒子の表面上の少なくとも一部に形成された炭素層と、を備えるリチウムイオン二次電池用負極材。
＜３＞ 前記シリコン粒子に対する前記炭素層の質量比が、０．００１〜０．３である、＜２＞に記載のリチウムイオン二次電池用負極材。
＜４＞ Ｒ値が、０．５〜２．５である＜２＞又は＜３＞に記載のリチウムイオン二次電池用負極材。
＜５＞ 体積平均粒子径（Ｄ５０）が０．５μｍ〜２０μｍである＜１＞〜＜４＞のいずれか１つに記載のリチウムイオン二次電池用負極材。
＜６＞ ７７Ｋでの窒素吸着測定より求めた比表面積が０．５ｍ２／ｇ〜３０ｍ２／ｇである＜１＞〜＜５＞のいずれか１つに記載のリチウムイオン二次電池用負極材。
<1> A negative electrode material for a lithium ion secondary battery, which is flat silicon particles having an aspect ratio of 1 to 20 and a thickness of 0.5 μm or less.
<2> A lithium ion secondary battery comprising: flat silicon particles having an aspect ratio of 1 to 20 and a thickness of 0.5 μm or less; and a carbon layer formed on at least a part of the surface of the silicon particles. Negative electrode material.
<3> The negative electrode material for a lithium ion secondary battery according to <2>, wherein a mass ratio of the carbon layer to the silicon particles is 0.001 to 0.3.
<4> The negative electrode material for a lithium ion secondary battery according to <2> or <3>, wherein the R value is 0.5 to 2.5.
<5> The volume average particle diameter (D 50) is 0.5μm~20μm <1> ~ <4> The negative electrode material for lithium ion secondary battery according to any one of.
<6> The specific surface area determined from nitrogen adsorption measurements at 77K is 0.5m 2 / g~30m 2 / g < 1> ~ <5> The negative electrode for a lithium ion secondary battery according to any one of Wood.
＜７＞ ＜１＞〜＜６＞のいずれか１つに記載のリチウムイオン二次電池用負極材を含む、リチウムイオン二次電池用負極。 <7> A negative electrode for a lithium ion secondary battery, comprising the negative electrode material for a lithium ion secondary battery according to any one of <1> to <6>.
＜８＞ ＜７＞に記載のリチウムイオン二次電池用負極と、正極と、電解質とを含むリチウムイオン二次電池。 <8> A lithium ion secondary battery comprising the negative electrode for lithium ion secondary batteries according to <7>, a positive electrode, and an electrolyte.
本発明によれば、高容量であるリチウムイオン二次電池を作製可能なリチウムイオン二次電池用負極材、ならびにこれを用いたリチウムイオン二次電池用負極及びリチウムイオン二次電池が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the negative electrode material for lithium ion secondary batteries which can produce a high capacity | capacitance lithium ion secondary battery, the negative electrode for lithium ion secondary batteries, and a lithium ion secondary battery using the same are provided. .
以下、本発明を実施するための形態について詳細に説明する。但し、本発明は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合を除き、必須ではない。数値及びその範囲についても同様であり、本発明を制限するものではない。また、本明細書に開示される技術的思想の範囲内において、様々な変更及び修正が可能である。 Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and the present invention is not limited thereto. Various changes and modifications can be made within the scope of the technical idea disclosed in this specification.
本明細書において「工程」との語には、他の工程から独立した工程に加え、他の工程と明確に区別できない場合であってもその工程の目的が達成されれば、当該工程も含まれる。
本明細書において「〜」を用いて示された数値範囲には、「〜」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
本明細書中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本明細書においてスラリー中の各成分の含有量は、スラリー中に各成分に該当する物質が複数種存在する場合、特に断らない限り、スラリー中に存在する当該複数種の物質の合計の含有量を意味する。
本明細書において「層」との語は、平面図として観察したときに、全面に形成されている形状の構成に加え、一部に形成されている形状の構成も包含される。
本明細書において各成分の粒子径は、各成分に該当する粒子が複数種存在する場合、特に断らない限り、当該複数種の粒子の混合物についての値を意味する。
In this specification, the term “process” includes a process that is independent of other processes and includes the process if the purpose of the process is achieved even if it cannot be clearly distinguished from the other processes. It is.
In the present specification, the numerical ranges indicated by using “to” include numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range. Good. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
In the present specification, the content of each component in the slurry is the total content of the plurality of materials present in the slurry unless there is a specific indication when there are a plurality of materials corresponding to each component in the slurry. Means.
In this specification, the term “layer” includes a configuration formed in a part in addition to a configuration formed in the entire surface when observed as a plan view.
In the present specification, the particle diameter of each component means a value for a mixture of the plurality of types of particles when there are a plurality of types of particles corresponding to each component, unless otherwise specified.
［第１実施形態］
＜リチウムイオン二次電池用負極材＞
第１実施形態のリチウムイオン二次電池用負極材（以下、単に負極材とも称する）は、アスペクト比が１〜２０であり、かつ、厚みが０．５μｍ以下の扁平なシリコン粒子である。このような負極材は、黒鉛粒子を用いる従来の負極材と比較して高容量であるリチウムイオン二次電池を作製可能である。さらに、このような負極材は、シリコン粒子を用いる従来の負極材と比較して高効率かつ高寿命であるリチウムイオン二次電池を作製可能である。また、このようなシリコン粒子としては、鱗状、鱗片状、一部塊状等の形状を有するものが挙げられる。
[First Embodiment]
<Anode material for lithium ion secondary battery>
The negative electrode material for lithium ion secondary batteries of the first embodiment (hereinafter also simply referred to as negative electrode material) is flat silicon particles having an aspect ratio of 1 to 20 and a thickness of 0.5 μm or less. Such a negative electrode material can produce a lithium ion secondary battery having a higher capacity than a conventional negative electrode material using graphite particles. Furthermore, such a negative electrode material can produce a lithium ion secondary battery that is more efficient and has a longer life than conventional negative electrode materials that use silicon particles. Examples of such silicon particles include those having a scale shape, a scale shape, a partial lump shape, and the like.
シリコン粒子は、長軸方向の長さをＡ、短軸方向の長さをＢとしたときに、Ａ／Ｂで表されるアスペクト比が１〜２０であり、３〜１５であってもよく、５〜１０であってもよい。アスペクト比が１以上であることにより、粒子間の接触面積が増加して、導電性がより向上する傾向にあり、アスペクト比が２０以下であることにより、充放電サイクルを行う際のシリコンの崩壊が抑制され、リチウムイオン二次電池が長寿命となる傾向にある。 The silicon particles have an aspect ratio represented by A / B of 1 to 20, and 3 to 15 when the length in the major axis direction is A and the length in the minor axis direction is B. 5-10 may be sufficient. When the aspect ratio is 1 or more, the contact area between the particles increases and the conductivity tends to be further improved. When the aspect ratio is 20 or less, the silicon collapses during the charge / discharge cycle. Is suppressed, and the lithium ion secondary battery tends to have a long life.
シリコン粒子のアスペクト比は、図１に示すように、シリコン粒子の長軸方向の長さをＡ、短軸方向の長さをＢとしたとき、Ａ／Ｂで表される。本明細書において、アスペクト比は、顕微鏡でシリコン粒子を拡大し、任意に１０個のシリコン粒子を選択してＡ／Ｂを測定して、その測定値の算術平均値をとったものである。なお、図１は、本実施形態に係るリチウムイオン二次電池用負極材である扁平なシリコン粒子を示す概略図であり、ＡとＢ及びＢ’、ならびにＡ’とＢ及びＢ’とはそれぞれ直交している。
ここで、長軸方向の長さは、観察されるシリコン粒子を二本の平行線Ａ、Ａ’で接するように挟んだとき、その間隔が最も大きくなる場合のＡ、Ａ’間の距離であり、短軸方向の長さは、前記長軸方向の長さを決める二本の平行線Ａ、Ａ’に対して垂直な二本の平行線Ｂ、Ｂ’で前記シリコン粒子を接するよう挟んだときのそのＢ、Ｂ’間の距離である。なお、シリコン粒子の短軸方向の長さは、シリコン粒子の厚みよりも長く、０．５μｍ以上となる。
As shown in FIG. 1, the aspect ratio of silicon particles is represented by A / B, where A is the length in the major axis direction of the silicon particles and B is the length in the minor axis direction. In this specification, the aspect ratio is obtained by enlarging silicon particles with a microscope, arbitrarily selecting 10 silicon particles, measuring A / B, and taking the arithmetic average value of the measured values. FIG. 1 is a schematic view showing flat silicon particles that are negative electrode materials for a lithium ion secondary battery according to the present embodiment, and A, B, and B ′, and A ′, B, and B ′ are respectively shown. Orthogonal.
Here, the length in the major axis direction is the distance between A and A ′ when the distance between the silicon particles to be observed is the largest when the silicon particles are sandwiched by two parallel lines A and A ′. Yes, the length in the minor axis direction is such that the silicon particles are in contact with the two parallel lines B and B ′ perpendicular to the two parallel lines A and A ′ that determine the length in the major axis direction. This is the distance between B and B ′. In addition, the length of the minor axis direction of the silicon particles is longer than the thickness of the silicon particles and is 0.5 μm or more.
さらに、シリコン粒子の厚みは、０．５μｍ以下であり、好ましくは０．０１μｍ〜０．４μｍであり、より好ましくは０．０５μｍ〜０．３μｍ以下である。シリコン粒子の厚みが０．５μｍ以下であることにより、充放電サイクルを行う際のシリコンの崩壊が抑制され、リチウムイオン二次電池が長寿命となる傾向にある。 Furthermore, the thickness of the silicon particles is 0.5 μm or less, preferably 0.01 μm to 0.4 μm, more preferably 0.05 μm to 0.3 μm. When the thickness of the silicon particles is 0.5 μm or less, the collapse of silicon during the charge / discharge cycle is suppressed, and the lithium ion secondary battery tends to have a long life.
シリコン粒子の厚みは、シリコン粒子を顕微鏡で観察し、任意に１０個のシリコン粒子を選択して厚みを測定して、その測定値の算術平均値をとったものである。
ここで、シリコン粒子の厚みは、長軸方向及び短軸方向に直交する方向において、観察されるシリコン粒子を二本の平行線Ｃ、Ｃ’で接するように挟んだとき、その間隔が最も大きくなる場合のＣ、Ｃ’間の距離である。
The thickness of the silicon particles is obtained by observing the silicon particles with a microscope, arbitrarily selecting 10 silicon particles, measuring the thickness, and taking the arithmetic average value of the measured values.
Here, the thickness of the silicon particles is the largest when the observed silicon particles are sandwiched by two parallel lines C and C ′ in the direction perpendicular to the major axis direction and the minor axis direction. Is the distance between C and C ′.
負極材の体積平均粒子径（Ｄ５０）は、０．５μｍ〜２０μｍであることが好ましく、０．６μｍ〜１０μｍであることがより好ましく、０．７μｍ〜５μｍであることが更に好ましい。負極材の体積平均粒子径が０．５μｍ以上であると、充分なタップ密度と、負極材スラリーとしたときの良好な塗工性が得られる傾向にある。一方、負極材の体積平均粒子径が２０μｍ以下であると、負極材の表面から内部へのリチウムの拡散距離が長くなりすぎず、リチウムイオン二次電池の入出力特性が良好に維持される傾向にある。 The volume average particle diameter (D 50 ) of the negative electrode material is preferably 0.5 μm to 20 μm, more preferably 0.6 μm to 10 μm, and still more preferably 0.7 μm to 5 μm. When the volume average particle diameter of the negative electrode material is 0.5 μm or more, a sufficient tap density and good coatability when a negative electrode material slurry is obtained tend to be obtained. On the other hand, when the volume average particle diameter of the negative electrode material is 20 μm or less, the diffusion distance of lithium from the surface of the negative electrode material to the inside does not become too long, and the input / output characteristics of the lithium ion secondary battery tend to be maintained well. It is in.
負極材の体積平均粒子径（Ｄ５０）は、負極材の粒子径分布において、小径側から体積累積分布曲線を描いた場合に、累積５０％となるときの粒子径である。体積平均粒子径（Ｄ５０）は、例えば、精製水に界面活性剤とともに負極材を分散させ、レーザー回折式粒度分布測定装置（例えば、株式会社島津製作所製、ＳＡＬＤ−３０００Ｊ）で測定することができる。 The volume average particle diameter (D 50 ) of the negative electrode material is the particle diameter when the cumulative volume distribution curve is drawn from the small diameter side in the particle diameter distribution of the negative electrode material, and the cumulative 50%. The volume average particle diameter (D 50 ) can be measured, for example, by dispersing a negative electrode material together with a surfactant in purified water and measuring with a laser diffraction particle size distribution analyzer (for example, SALD-3000J, manufactured by Shimadzu Corporation). it can.
負極材の７７Ｋでの窒素吸着測定より求められる比表面積（以下、Ｎ２比表面積とも称する）は、０．５ｍ２／ｇ〜３０ｍ２／ｇであることが好ましく、５ｍ２／ｇ〜２５ｍ２／ｇであることがより好ましく、１０ｍ２／ｇ〜２５ｍ２／ｇであることが更に好ましい。Ｎ２比表面積が上記範囲内であれば、入出力特性と初回充放電効率の良好なバランスが得られる傾向にある。Ｎ２比表面積は、具体的には、後述する実施例の方法により求めることができる。 Specific surface area determined from nitrogen adsorption measurements at 77K of negative electrode material (hereinafter, also referred to as N 2 specific surface area) is preferably 0.5m 2 / g~30m 2 / g, 5m 2 / g~25m 2 / G is more preferable, and 10 m 2 / g to 25 m 2 / g is still more preferable. If the N 2 specific surface area is within the above range, a good balance between input / output characteristics and initial charge / discharge efficiency tends to be obtained. Specifically, the N 2 specific surface area can be determined by the method of Examples described later.
アスペクト比が１〜２０であり、かつ、厚みが０．５μｍ以下の扁平なシリコン粒子としては、例えば、純シリコンを機械的研磨した際に発生したシリコン粉が挙げられる。 Examples of the flat silicon particles having an aspect ratio of 1 to 20 and a thickness of 0.5 μm or less include silicon powder generated when mechanically polishing pure silicon.
［第２実施形態］
＜リチウムイオン二次電池用負極材＞
第２実施形態のリチウムイオン二次電池用負極材（以下、単に負極材とも称する）は、アスペクト比が１〜２０、かつ、厚みが０．５μｍ以下の扁平なシリコン粒子と、シリコン粒子の表面上の少なくとも一部に形成された炭素層と、を備える。第２実施形態の負極材は、シリコン粒子の表面上の少なくとも一部に炭素層が形成されている点で、第１実施形態の負極材と相違する。
[Second Embodiment]
<Anode material for lithium ion secondary battery>
The negative electrode material for a lithium ion secondary battery of the second embodiment (hereinafter also simply referred to as a negative electrode material) has flat silicon particles having an aspect ratio of 1 to 20 and a thickness of 0.5 μm or less, and the surface of the silicon particles A carbon layer formed on at least a part of the upper surface. The negative electrode material of the second embodiment is different from the negative electrode material of the first embodiment in that a carbon layer is formed on at least a part of the surface of the silicon particles.
さらに、負極材は、シリコン粒子の表面上の少なくとも一部に炭素層が形成されているため、比表面積を下げ、ＳＥＩ（Ｓｏｌｉｄ Ｅｌｅｃｔｒｏｌｙｔｅ Ｉｎｔｅｒｐｈａｓｅ）膜の生成量を下げることができる傾向にある。なお、ＳＥＩ膜が生成されると電池の初期特性（例えば、充放電効率）の低下につながる。
また、シリコン粒子の表面上の少なくとも一部に炭素層が形成されていることにより、シリコン粒子と、シリコンと反応性が高い電解液との接触が抑制され、電解液の分解が抑制される傾向にある。これにより、初期特性低下が抑制される傾向にある。
また、シリコン粒子の表面上の少なくとも一部に炭素層を形成させて導電性を付与することにより、粒子表面の導電性が向上し、かつリチウムの吸蔵及び放出に伴う体積変化に対して安定な構造となる傾向にある。その結果として、リチウムイオン二次電池における長期安定性及び初期効率が改善される傾向にある。
なお、負極材は、シリコン粒子の表面上の少なくとも一部に炭素層が形成されていればよく、シリコン粒子の表面の一部に炭素層が形成されていてもよく、シリコン粒子の表面の全部に炭素層が形成されていてもよい。
Further, since the carbon layer is formed on at least a part of the surface of the silicon particle, the negative electrode material tends to reduce the specific surface area and reduce the generation amount of SEI (Solid Electrolyte Interface) film. In addition, when an SEI film | membrane is produced, it will lead to the fall of the initial characteristic (for example, charging / discharging efficiency) of a battery.
In addition, since the carbon layer is formed on at least a part of the surface of the silicon particles, the contact between the silicon particles and the electrolyte having high reactivity with silicon is suppressed, and the decomposition of the electrolyte tends to be suppressed. It is in. Thereby, there exists a tendency for the initial characteristic fall to be suppressed.
Moreover, by providing a conductivity by forming a carbon layer on at least a part of the surface of the silicon particle, the conductivity of the particle surface is improved and stable against a volume change caused by insertion and extraction of lithium. It tends to be a structure. As a result, long-term stability and initial efficiency in lithium ion secondary batteries tend to be improved.
The negative electrode material only needs to have a carbon layer formed on at least a part of the surface of the silicon particles, and a carbon layer may be formed on a part of the surface of the silicon particles. A carbon layer may be formed.
シリコン粒子に対する炭素層の質量比は０．００１〜０．３であることが好ましく、０．００２〜０．２５であることがより好ましく、０．００５〜０．２であることが更に好ましい。炭素層の質量比が０．００１以上であることにより、炭素層を設けたことによる前述の効果をより好適に奏する傾向にあり、炭素層の質量比が０．３以下であることにより、シリコン割合の低下を抑制してより高容量のリチウムイオン二次電池とすることができる傾向にある。 The mass ratio of the carbon layer to the silicon particles is preferably 0.001 to 0.3, more preferably 0.002 to 0.25, and still more preferably 0.005 to 0.2. When the mass ratio of the carbon layer is 0.001 or more, the above-described effects due to the provision of the carbon layer tend to be more suitably achieved. When the mass ratio of the carbon layer is 0.3 or less, silicon It tends to be possible to obtain a higher-capacity lithium ion secondary battery by suppressing the decrease in the ratio.
シリコン粒子の表面上の少なくとも一部に炭素層を形成する方法は、特に限定されない。例えば、以下のような湿式混合方式、乾式混合方式、気相方式等の方法が挙げられる。 The method for forming the carbon layer on at least a part of the surface of the silicon particle is not particularly limited. For example, methods such as the following wet mixing method, dry mixing method, and gas phase method are exemplified.
湿式混合方式の方法としては、炭素層を構成する炭素質材料又はその前駆体となる物質（有機化合物等）を溶媒に溶解又は分散させた混合液に、シリコン粒子を分散して混合した後、溶媒を除去する方法が挙げられる。前駆体を用いた場合、前駆体を付着させた状態のシリコン粒子を熱処理して前駆体を炭素化することにより、シリコン粒子を炭素質材料で被覆することができる。 As a method of the wet mixing method, after dispersing and mixing silicon particles in a mixed solution in which a carbonaceous material constituting a carbon layer or a precursor substance (organic compound or the like) is dissolved or dispersed in a solvent, The method of removing a solvent is mentioned. When a precursor is used, the silicon particles can be coated with a carbonaceous material by heat-treating the silicon particles with the precursor attached thereto to carbonize the precursor.
乾式混合方式の方法としては、シリコン粒子と有機化合物とをそれぞれ固体の状態で混合し、得られた混合物に力学的エネルギーを加えることでシリコン粒子の表面に有機化合物を付着させ、有機化合物を付着させた状態のシリコン粒子を熱処理して有機化合物を炭素化することにより、シリコン粒子を炭素質材料で被覆することができる。 As a dry mixing method, silicon particles and an organic compound are mixed in a solid state, and mechanical energy is applied to the resulting mixture to attach the organic compound to the surface of the silicon particles. The silicon particles can be coated with a carbonaceous material by carbonizing the organic compound by heat-treating the silicon particles thus formed.
気相方式の方法としては、ＣＶＤ法等の、アセチレン、プロピレン等のガス分解反応によってシリコン粒子の表面を炭素質材料で被覆する方法が挙げられる。 Examples of the vapor phase method include a method of coating the surface of silicon particles with a carbonaceous material by a gas decomposition reaction such as acetylene or propylene, such as a CVD method.
有機化合物の具体例としては、エチレンヘビーエンドピッチ、原油ピッチ、コールタールピッチ、アスファルト分解ピッチ、ポリ塩化ビニル等を熱分解して生成するピッチ、ナフタレン等を超強酸存在下で重合させて作製される合成ピッチなどが挙げられる。また、ポリ塩化ビニル、ポリビニルアルコール、ポリ酢酸ビニル、ポリビニルブチラール等の熱可塑性合成樹脂を有機化合物として用いることもできる。また、デンプン、セルロース等の天然物を有機化合物として用いることもできる。 Specific examples of organic compounds are prepared by polymerizing ethylene heavy end pitch, crude oil pitch, coal tar pitch, asphalt cracking pitch, pitch generated by pyrolyzing polyvinyl chloride, naphthalene, etc. in the presence of a super strong acid. Synthesis pitch and the like. In addition, thermoplastic synthetic resins such as polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, and polyvinyl butyral can also be used as the organic compound. Natural products such as starch and cellulose can also be used as the organic compound.
熱処理の温度は６００℃〜１１００℃であることが好ましく、６５０℃〜１０００℃であることがより好ましく、７００℃〜９００℃であることがさらに好ましい。熱処理時の雰囲気は、負極材が酸化し難い雰囲気であれば特に制限はなく、窒素ガス雰囲気、アルゴンガス雰囲気、自己分解ガス雰囲気等が適用できる。使用する炉の形式は特に制限はないが、電気又はガスを熱源としたバッチ炉、連続炉等が好ましい。 The temperature of the heat treatment is preferably 600 ° C to 1100 ° C, more preferably 650 ° C to 1000 ° C, and further preferably 700 ° C to 900 ° C. The atmosphere during the heat treatment is not particularly limited as long as the negative electrode material is not easily oxidized, and a nitrogen gas atmosphere, an argon gas atmosphere, a self-decomposing gas atmosphere, or the like can be applied. The type of furnace to be used is not particularly limited, but a batch furnace, a continuous furnace or the like using electricity or gas as a heat source is preferable.
（ラマン分光測定のＲ値）
負極材のラマン分光測定のＲ値は０．５〜２．５であることが好ましく、０．７〜２．０であることがより好ましく、０．８〜１．５であることが更に好ましい。Ｒ値が０．５以上であると、リチウムイオンの挿入及び脱離に用いられる黒鉛格子欠陥が充分存在し、入出力特性の低下が抑制される傾向にある。Ｒ値が２．５以下であると、電解液の分解反応が充分に抑制され、初回効率の低下が抑制される傾向にある。
(R value of Raman spectroscopic measurement)
The R value of the Raman spectroscopic measurement of the negative electrode material is preferably 0.5 to 2.5, more preferably 0.7 to 2.0, and still more preferably 0.8 to 1.5. . When the R value is 0.5 or more, there are sufficient graphite lattice defects used for insertion and desorption of lithium ions, and the input / output characteristics tend to be prevented from deteriorating. When the R value is 2.5 or less, the decomposition reaction of the electrolytic solution is sufficiently suppressed, and the decrease in the initial efficiency tends to be suppressed.
Ｒ値は、ラマン分光測定において得られたラマン分光スペクトルにおいて、１５８０ｃｍ−１付近に現れるピークの強度Ｉｇと、１３６０ｃｍ−１付近に現れるピークの強度Ｉｄの強度比（Ｉｄ／Ｉｇ）と定義する。ここで、１５８０ｃｍ−１付近に現れるピークとは、通常、黒鉛結晶構造に対応すると同定されるピークであり、例えば１５３０ｃｍ−１〜１６３０ｃｍ−１に観測されるピークを意味する。また１３６０ｃｍ−１付近に現れるピークとは、通常、炭素の非晶質構造に対応すると同定されるピークであり、例えば１３００ｃｍ−１〜１４００ｃｍ−１に観測されるピークを意味する。 R value, in the Raman spectrum obtained in the Raman spectrometry, to define the intensity Ig of the peak appearing near 1580 cm -1, the intensity ratio of the intensity Id of the peak appearing near 1360 cm -1 and (Id / Ig). Here, the peak appearing near 1580 cm -1, generally a peak identified as corresponding to the graphite crystal structure, means a peak observed for example 1530cm -1 ~1630cm -1. Moreover, the peak appearing in the vicinity of 1360 cm −1 is a peak usually identified as corresponding to the amorphous structure of carbon, for example, a peak observed at 1300 cm −1 to 1400 cm −1 .
本明細書においてラマン分光測定は、レーザーラマン分光光度計（日本分光株式会社製、ＮＲＳ−２１００）を用い、リチウムイオン二次電池用負極材を平らになるようにセットした試料板にアルゴンレーザー光を照射して測定を行う。測定条件は例えば以下の通りである。
レーザー出力１０ｍＷ
分光器Ｆシングル
入射スリット幅８００μｍ
積算回数３回
露光時間６０秒
In this specification, the Raman spectroscopic measurement is performed by using a laser Raman spectrophotometer (NRS-2100, manufactured by JASCO Corporation), and argon laser light on a sample plate in which a negative electrode material for a lithium ion secondary battery is set flat. To measure. Measurement conditions are as follows, for example.
Laser power 10mW
Spectrometer F single entrance slit width 800μm
Integration times 3 times Exposure time 60 seconds
負極材の体積平均粒子径（Ｄ５０）は、０．５μｍ〜２０μｍであることが好ましく、０．６μｍ〜１０μｍであることがより好ましく、０．７μｍ〜５μｍであることが更に好ましい。負極材の体積平均粒子径が０．５μｍ以上であると、充分なタップ密度と、負極材スラリーとしたときの良好な塗工性が得られる傾向にある。一方、負極材の体積平均粒子径が２０μｍ以下であると、負極材の表面から内部へのリチウムの拡散距離が長くなりすぎず、リチウムイオン二次電池の入出力特性が良好に維持される傾向にある。 The volume average particle diameter (D 50 ) of the negative electrode material is preferably 0.5 μm to 20 μm, more preferably 0.6 μm to 10 μm, and still more preferably 0.7 μm to 5 μm. When the volume average particle diameter of the negative electrode material is 0.5 μm or more, a sufficient tap density and good coatability when a negative electrode material slurry is obtained tend to be obtained. On the other hand, when the volume average particle diameter of the negative electrode material is 20 μm or less, the diffusion distance of lithium from the surface of the negative electrode material to the inside does not become too long, and the input / output characteristics of the lithium ion secondary battery tend to be maintained well. It is in.
負極材の体積平均粒子径（Ｄ５０）は、前述の第１実施形態に記載の方法にて測定することができる。 The volume average particle diameter (D 50 ) of the negative electrode material can be measured by the method described in the first embodiment.
負極材の７７Ｋでの窒素吸着測定より求められる比表面積（以下、Ｎ２比表面積とも称する）は、０．５ｍ２／ｇ〜３０ｍ２／ｇであることが好ましく、５ｍ２／ｇ〜２５ｍ２／ｇであることがより好ましく、１０ｍ２／ｇ〜２５ｍ２／ｇであることが更に好ましい。Ｎ２比表面積が上記範囲内であれば、入出力特性と初回充放電効率の良好なバランスが得られる傾向にある。Ｎ２比表面積は、前述の第１実施形態に記載の方法を用いて求めることができる。 Specific surface area determined from nitrogen adsorption measurements at 77K of negative electrode material (hereinafter, also referred to as N 2 specific surface area) is preferably 0.5m 2 / g~30m 2 / g, 5m 2 / g~25m 2 / G is more preferable, and 10 m 2 / g to 25 m 2 / g is still more preferable. If the N 2 specific surface area is within the above range, a good balance between input / output characteristics and initial charge / discharge efficiency tends to be obtained. The N 2 specific surface area can be obtained using the method described in the first embodiment.
＜リチウムイオン二次電池用負極＞
本実施形態のリチウムイオン二次電池用負極（以下、単に負極とも称する）は、本実施形態のリチウムイオン二次電池用負極材を含む。これにより、高容量であるリチウムイオン二次電池を構成することが可能となる。また、リチウムイオン二次電池用負極は、リチウムイオン二次電池用負極材を含む負極層と、集電体と、を含んでいてもよい。リチウムイオン二次電池用負極は、必要に応じて他の構成要素を含んでもよい。
<Anode for lithium ion secondary battery>
The negative electrode for a lithium ion secondary battery (hereinafter also simply referred to as a negative electrode) of the present embodiment includes the negative electrode material for a lithium ion secondary battery of the present embodiment. This makes it possible to configure a high-capacity lithium ion secondary battery. Moreover, the negative electrode for lithium ion secondary batteries may contain the negative electrode layer containing the negative electrode material for lithium ion secondary batteries, and a collector. The negative electrode for a lithium ion secondary battery may include other components as necessary.
リチウムイオン二次電池用負極は、例えば、リチウムイオン二次電池用負極材及び有機系結着剤を溶剤とともに撹拌機、ボールミル、スーパーサンドミル、加圧ニーダー等の分散装置により混練し、負極材スラリーを調製し、これを集電体に塗布して負極層を形成する、又は、ペースト状の負極材スラリーをシート状、ペレット状等の形状に成形し、これを集電体と一体化することで得ることができる。 The negative electrode for a lithium ion secondary battery is prepared by, for example, kneading a negative electrode material for a lithium ion secondary battery and an organic binder together with a solvent by a dispersing device such as a stirrer, a ball mill, a super sand mill, or a pressure kneader. And applying this to a current collector to form a negative electrode layer, or forming a paste-like negative electrode material slurry into a sheet shape, pellet shape, etc., and integrating this with the current collector Can be obtained at
有機系結着剤としては、特に限定されず、スチレン−ブタジエン共重合体、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、（メタ）アクリロニトリル、ヒドロキシエチル（メタ）アクリレート等のエチレン性不飽和カルボン酸エステルの重合体；アクリル酸、メタクリル酸、イタコン酸、フマル酸、マレイン酸等のエチレン性不飽和カルボン酸の重合体；ポリフッ化ビニリデン、ポリエチレンオキサイド、ポリエピクロヒドリン、ポリフォスファゼン、ポリアクリロニトリル等のイオン導電性の大きな高分子化合物などが挙げられる。この有機系結着剤の含有量は、リチウムイオン二次電池用負極材と有機系結着剤の合計１００質量部に対して０．５質量部〜２０質量部であることが好ましい。有機系結着剤は１種を単独で用いても、２種以上を組み合わせて用いてもよい。（メタ）アクリレートは、アクリレート又はメタクリレートを意味し、（メタ）アクリロニトリルはアクリロニトリル又はメタクリロニトリルを意味する。 The organic binder is not particularly limited, and is a styrene-butadiene copolymer, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylonitrile, hydroxyethyl (meth) acrylate, or the like. Polymer of ethylenically unsaturated carboxylic acid ester; Polymer of ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid; polyvinylidene fluoride, polyethylene oxide, polyepichlorohydrin , High ionic conductive polymer compounds such as polyphosphazene and polyacrylonitrile. The content of the organic binder is preferably 0.5 parts by mass to 20 parts by mass with respect to a total of 100 parts by mass of the negative electrode material for a lithium ion secondary battery and the organic binder. One organic binder may be used alone, or two or more organic binders may be used in combination. (Meth) acrylate means acrylate or methacrylate, and (meth) acrylonitrile means acrylonitrile or methacrylonitrile.
溶剤は、有機系結着剤を溶解又は分散可能な溶剤であれば特に制限されない。具体的には、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、γ−ブチロラクトン等の有機溶剤が挙げられる。溶剤の使用量は、負極材スラリーをペースト等の所望の状態にできれば特に制限されない。例えば、負極材１００質量部に対して６０質量部以上１５０質量部未満であることが好ましい。 The solvent is not particularly limited as long as it can dissolve or disperse the organic binder. Specific examples include organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and γ-butyrolactone. The usage-amount of a solvent will not be restrict | limited especially if a negative electrode material slurry can be made into desired states, such as a paste. For example, the amount is preferably 60 parts by mass or more and less than 150 parts by mass with respect to 100 parts by mass of the negative electrode material.
負極材スラリーには、粘度を調整するための増粘剤を添加してもよい。増粘剤としては、カルボキシメチルセルロース、カルボキシメチルセルロースのナトリウム塩、メチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、エチルセルロース、ポリビニルアルコール、ポリアクリル酸、ポリアクリル酸のナトリウム塩、アルギン酸、アルギン酸のナトリウム塩、酸化スターチ、リン酸化スターチ、カゼイン等が挙げられる。増粘剤は１種単独で用いても、２種以上を組み合わせて用いてもよい。負極材スラリーが増粘剤を含む場合、その量は特に制限されない。増粘剤の含有量は、例えば、負極材１００質量部に対して０．１質量部〜５質量部であることが好ましい。 A thickener for adjusting the viscosity may be added to the negative electrode material slurry. Thickeners include: carboxymethylcellulose, sodium salt of carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, ethylcellulose, polyvinyl alcohol, polyacrylic acid, sodium salt of polyacrylic acid, alginic acid, sodium salt of alginic acid, oxidized starch, phosphorus Examples thereof include oxidized starch and casein. A thickener may be used individually by 1 type, or may be used in combination of 2 or more type. When the negative electrode material slurry contains a thickener, the amount is not particularly limited. It is preferable that content of a thickener is 0.1-5 mass parts with respect to 100 mass parts of negative electrode materials, for example.
負極材スラリーには、導電補助剤を添加してもよい。導電補助剤としては、天然黒鉛、人造黒鉛、カーボンブラック（アセチレンブラック、サーマルブラック、ファーネスブラック等）、導電性を示す酸化物、導電性を示す窒化物などが挙げられる。導電補助剤を含むことで、電極としての導電性をより向上させることができる。導電補助剤は１種単独で用いても、２種以上を組み合わせて用いてもよい。負極材スラリーが導電補助剤を含む場合、その量は特に制限されない。導電補助剤の含有量は、例えば、負極材１００質量部に対して０．５質量部〜１５質量部であることが好ましい。 A conductive additive may be added to the negative electrode material slurry. Examples of the conductive aid include natural graphite, artificial graphite, carbon black (acetylene black, thermal black, furnace black, etc.), conductive oxide, conductive nitride, and the like. By including a conductive auxiliary agent, the conductivity as an electrode can be further improved. A conductive support agent may be used individually by 1 type, or may be used in combination of 2 or more type. When the negative electrode material slurry contains a conductive additive, the amount is not particularly limited. It is preferable that content of a conductive support agent is 0.5-15 mass parts with respect to 100 mass parts of negative electrode materials, for example.
集電体の材質及び形状については、特に限定されず、例えば、アルミニウム、銅、ニッケル、チタン、ステンレス鋼等を、箔状、穴開け箔状、メッシュ状等にした帯状のものを用いればよい。また、ポーラスメタル（発泡メタル）、カーボンペーパー等の多孔性材料も使用可能である。 The material and shape of the current collector are not particularly limited, and for example, a belt-like material in which aluminum, copper, nickel, titanium, stainless steel, or the like is formed into a foil shape, a punched foil shape, a mesh shape, or the like may be used. . Also, porous materials such as porous metal (foamed metal) and carbon paper can be used.
負極材スラリーを集電体に塗布する方法は特に限定されず、公知の方法を適宜選択することができる。具体的には、メタルマスク印刷法、静電塗装法、ディップコート法、スプレーコート法、ロールコート法、ドクターブレード法、コンマコート法、グラビアコート法、スクリーン印刷法等が挙げられる。 The method for applying the negative electrode material slurry to the current collector is not particularly limited, and a known method can be appropriately selected. Specific examples include a metal mask printing method, an electrostatic coating method, a dip coating method, a spray coating method, a roll coating method, a doctor blade method, a comma coating method, a gravure coating method, and a screen printing method.
負極の作製方法は特に制限されない。例えば、負極材と、結着剤と、必要に応じて添加される増粘剤、導電補助剤等と、溶剤とを含むペースト状の負極材スラリーを作製し、得られた負極材スラリーを集電体の上に塗布し、乾燥し、必要に応じてロールプレス等の成形法により圧縮成形することで作製することができる。その他、ペースト状の負極材スラリーをシート状、ペレット状等に成形し、これをロールプレス等の成形法により集電体と一体化することで作製することもできる。 The method for producing the negative electrode is not particularly limited. For example, a paste-like negative electrode material slurry containing a negative electrode material, a binder, a thickener added as necessary, a conductive auxiliary agent, etc., and a solvent is prepared, and the obtained negative electrode material slurry is collected. It can be produced by coating on an electric body, drying, and compression molding by a molding method such as a roll press if necessary. In addition, the paste-like negative electrode material slurry can be formed into a sheet shape, a pellet shape, or the like, and can be produced by integrating it with a current collector by a forming method such as a roll press.
＜リチウムイオン二次電池＞
本実施形態のリチウムイオン二次電池は、本実施形態のリチウムイオン二次電池用負極と、正極と、電解質とを含む。本実施形態のリチウムイオン二次電池は、高容量である。
<Lithium ion secondary battery>
The lithium ion secondary battery of this embodiment includes the negative electrode for a lithium ion secondary battery of this embodiment, a positive electrode, and an electrolyte. The lithium ion secondary battery of this embodiment has a high capacity.
リチウムイオン二次電池は、例えば、リチウムイオン二次電池用負極と正極とをセパレータを介して対向して配置し、電解液を注入することにより得ることができる。 A lithium ion secondary battery can be obtained, for example, by disposing a negative electrode for a lithium ion secondary battery and a positive electrode facing each other with a separator interposed therebetween and injecting an electrolytic solution.
正極は、上述した負極と同様にして、集電体上に正極材料及び必要に応じて含まれる増粘剤、導電補助剤等を含む正極層を形成することで作製される。集電体としては、アルミニウム、チタン、ステンレス鋼等の金属又は合金を、箔状、穴開け箔状、メッシュ状等にしたものを用いることができる。 The positive electrode is produced by forming a positive electrode layer containing a positive electrode material and, if necessary, a thickener, a conductive auxiliary agent and the like on the current collector in the same manner as the negative electrode described above. As the current collector, a metal or alloy such as aluminum, titanium, stainless steel or the like made into a foil shape, a punched foil shape, a mesh shape, or the like can be used.
正極層の形成に用いる正極材料は、特に制限されない。例えば、リチウムイオンをドーピング又はインターカレーション可能な金属化合物（金属酸化物、金属硫化物等）及び導電性高分子材料が挙げられる。より具体的には、コバルト酸リチウム（ＬｉＣｏＯ２）、ニッケル酸リチウム（ＬｉＮｉＯ２）、マンガン酸リチウム（ＬｉＭｎＯ２）、これらの複酸化物（ＬｉＣｏｘＮｉｙＭｎｚＯ２、ｘ＋ｙ＋ｚ＝１）、添加元素Ｍ’を含む複酸化物（ＬｉＣｏａＮｉｂＭｎｃＭ’ｄＯ２、ａ＋ｂ＋ｃ＋ｄ＝１、Ｍ’：Ａｌ、Ｍｇ、Ｔｉ、Ｚｒ又はＧｅ）、スピネル型リチウムマンガン酸化物（ＬｉＭｎ２Ｏ４）、リチウムバナジウム化合物、Ｖ２Ｏ５、Ｖ６Ｏ１３、ＶＯ２、ＭｎＯ２、ＴｉＯ２、ＭｏＶ２Ｏ８、ＴｉＳ２、Ｖ２Ｓ５、ＶＳ２、ＭｏＳ２、ＭｏＳ３、Ｃｒ３Ｏ８、Ｃｒ２Ｏ５、オリビン型ＬｉＭＰＯ４（Ｍ：Ｃｏ、Ｎｉ、Ｍｎ、Ｆｅ）等のリチウム含有化合物、ポリアセチレン、ポリアニリン、ポリピロール、ポリチオフェン、ポリアセン等の導電性ポリマー、多孔質炭素などが挙げられる。正極材料は１種を単独で用いても、２種以上を組み合わせて用いてもよい。 The positive electrode material used for forming the positive electrode layer is not particularly limited. For example, a metal compound (metal oxide, metal sulfide, etc.) capable of doping or intercalating lithium ions and a conductive polymer material can be given. More specifically, lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganate (LiMnO 2 ), double oxides thereof (LiCo x Ni y Mn z O 2 , x + y + z = 1), Double oxide containing additive element M ′ (LiCo a Ni b Mn c M ′ d O 2 , a + b + c + d = 1, M ′: Al, Mg, Ti, Zr or Ge), spinel type lithium manganese oxide (LiMn 2 O 4 ), lithium vanadium compound, V 2 O 5 , V 6 O 13 , VO 2 , MnO 2 , TiO 2 , MoV 2 O 8 , TiS 2 , V 2 S 5 , VS 2 , MoS 2 , MoS 3 , Cr 3 O 8, Cr 2 O 5, olivine-type LiMPO 4 (M: Co, Ni , Mn, Fe) lithium-containing compounds such as polyacetylene, Poriani Emissions, polypyrrole, polythiophene, electrically conductive polymers such as polyacene, a porous carbon and the like. The positive electrode material may be used alone or in combination of two or more.
正極は、正極材料と、結着剤と、結着剤を溶解又は分散可能な溶剤と、必要に応じて添加される増粘剤、導電補助剤等とを含む正極材スラリーを集電体の少なくとも一方の面に塗布し、次いで溶剤を乾燥して除去し、必要に応じて圧延して作製することができる。 The positive electrode comprises a positive electrode material slurry containing a positive electrode material, a binder, a solvent capable of dissolving or dispersing the binder, a thickener added as necessary, a conductive auxiliary agent, and the like. It can be produced by applying to at least one surface, then drying to remove the solvent, and rolling if necessary.
結着剤、溶剤、増粘剤及び導電補助剤としては、リチウムイオン二次電池用負極の項で例示したものを同様に用いることができる。 As the binder, the solvent, the thickener, and the conductive auxiliary agent, those exemplified in the section of the negative electrode for a lithium ion secondary battery can be similarly used.
リチウムイオン二次電池に用いられる電解質は特に制限されず、公知のものを用いることができる。例えば、電解質を有機溶剤に溶解させた電解液を用いることにより、非水系リチウムイオン二次電池を製造することができる。 The electrolyte used for the lithium ion secondary battery is not particularly limited, and a known one can be used. For example, a non-aqueous lithium ion secondary battery can be manufactured by using an electrolytic solution in which an electrolyte is dissolved in an organic solvent.
電解質としては、ＬｉＰＦ６、ＬｉＣｌＯ４、ＬｉＢＦ４、ＬｉＣｌＦ４、ＬｉＡｓＦ６、ＬｉＳｂＦ６、ＬｉＡｌＯ４、ＬｉＡｌＣｌ４、ＬｉＮ（ＣＦ３ＳＯ２）２、ＬｉＮ（Ｃ２Ｆ５ＳＯ２）２、ＬｉＣ（ＣＦ３ＳＯ２）３、ＬｉＣｌ、ＬｉＩ等が挙げられる。電解質は１種を単独で用いても、２種以上を組み合わせて用いてもよい。 As the electrolyte, LiPF 6, LiClO 4, LiBF 4, LiClF 4, LiAsF 6, LiSbF 6, LiAlO 4, LiAlCl 4, LiN (CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) 2, LiC ( CF 3 SO 2 ) 3 , LiCl, LiI and the like. One electrolyte may be used alone, or two or more electrolytes may be used in combination.
有機溶剤としては、プロピレンカーボネート、エチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、メチルプロピルカーボネート、ブチルメチルカーボネート、エチルプロピルカーボネート、ブチルエチルカーボネート、ジプロピルカーボネート、フルオロエチレンカーボネート、クロロエチレンカーボネート、ブチレンカーボネート、ビニレンカーボネート等のカーボネート系溶剤；γ−ブチロラクトン等のラクトン系溶剤；酢酸メチル、酢酸エチル、トリメチルリン酸エステル、トリエチルリン酸エステル等のエステル系溶剤：１，２−ジメトキシエタン、ジメチルエーテル、ジエチルエーテル等の鎖状エーテル系溶剤；テトラヒドロフラン、２−メチルテトラヒドロフラン、１，３−ジオキソラン、４−メチルジオキソラン等の環状エーテル系溶剤；スルホラン、３−メチルスルホラン、２，４−ジメチルスルホラン等のスルホラン系溶剤；ジメチルスルホキシド等のスルホキシド系溶剤；アセトニトリル、プロピオニトリル、ベンゾニトリル等のニトリル系溶剤；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等のアミド系溶剤；ジエチレングリコール等のポリオキシアルキレングリコール系溶剤；シクロペンタノン等のケトン系溶剤；シクロヘキシルベンゼン等の芳香族系溶剤；プロパンスルトン等の含硫黄系溶剤；３−メチル−１，３−オキサゾリジン−２−オン等のオキサゾリドン系溶剤などが挙げられる。有機溶剤は、１種を単独で用いても、２種以上を組み合わせて用いてもよい。 Organic solvents include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, butyl methyl carbonate, ethyl propyl carbonate, butyl ethyl carbonate, dipropyl carbonate, fluoroethylene carbonate, chloroethylene carbonate, butylene Carbonate solvents such as carbonate and vinylene carbonate; lactone solvents such as γ-butyrolactone; ester solvents such as methyl acetate, ethyl acetate, trimethyl phosphate and triethyl phosphate: 1,2-dimethoxyethane, dimethyl ether, diethyl Chain ether solvents such as ether; tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-di Cyclic ether solvents such as xoxolane and 4-methyldioxolane; sulfolane solvents such as sulfolane, 3-methylsulfolane and 2,4-dimethylsulfolane; sulfoxide solvents such as dimethyl sulfoxide; acetonitrile, propionitrile, benzonitrile and the like Nitrile solvents; Amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide; Polyoxyalkylene glycol solvents such as diethylene glycol; Ketone solvents such as cyclopentanone; Aromatic solvents such as cyclohexylbenzene A sulfur-containing solvent such as propane sultone; an oxazolidone-based solvent such as 3-methyl-1,3-oxazolidine-2-one, and the like. An organic solvent may be used individually by 1 type, or may be used in combination of 2 or more type.
セパレータは特に制限されず、例えば、樹脂製の不織布、クロス、微孔フィルム又はそれらを組み合わせたものを使用することができる。樹脂としては、ポリエチレン、ポリプロピレン等のポリオレフィンを主成分とするものが挙げられる。リチウムイオン二次電池の構造上、正極と負極が直接接触しない場合は、セパレータは使用しなくてもよい。 The separator is not particularly limited, and for example, a resin nonwoven fabric, cloth, microporous film, or a combination thereof can be used. Examples of the resin include those mainly composed of polyolefin such as polyethylene and polypropylene. When the positive electrode and the negative electrode are not in direct contact due to the structure of the lithium ion secondary battery, the separator may not be used.
本実施形態のリチウムイオン二次電池の作製方法は、本実施形態のリチウムイオン二次電池用負極を用いること以外は特に制限はなく、公知の正極、リチウムイオン二次電池用電解液、セパレータ等の材料を用いて、公知の方法により作製することができる。 The method for producing the lithium ion secondary battery according to the present embodiment is not particularly limited except that the negative electrode for the lithium ion secondary battery according to the present embodiment is used. Known positive electrodes, electrolyte solutions for lithium ion secondary batteries, separators, and the like This material can be used to make a known method.
リチウムイオン二次電池における正極及び負極の状態は、特に限定されない。例えば、正極及び負極と、必要に応じて正極及び負極の間に配置されるセパレータとを、渦巻状に巻回した状態であっても、これらを平板状として積層した状態であってもよい。 The state of the positive electrode and the negative electrode in the lithium ion secondary battery is not particularly limited. For example, the positive electrode and the negative electrode and a separator disposed between the positive electrode and the negative electrode as necessary may be wound in a spiral shape or may be stacked in a flat plate shape.
リチウムイオン二次電池の形状は、特に制限されない。具体的には、ラミネート型電池、ペーパー型電池、ボタン型電池、コイン型電池、積層型電池、円筒型電池、角型電池等が挙げられる。 The shape of the lithium ion secondary battery is not particularly limited. Specifically, a laminate type battery, a paper type battery, a button type battery, a coin type battery, a laminated type battery, a cylindrical type battery, a square type battery, and the like can be given.
本実施形態のリチウムイオン二次電池は、高容量であるため、電気自動車、パワーツール、電力貯蔵装置等に使用されるリチウムイオン二次電池として好適である。特に、加速性能及びブレーキ回生性能の向上のために大電流での充放電が求められている電気自動車（ＥＶ）、ハイブリッド電気自動車（ＨＥＶ）、プラグインハイブリッド電気自動車（ＰＨＥＶ）等に使用されるリチウムイオン二次電池として好適である。 Since the lithium ion secondary battery of this embodiment has a high capacity, it is suitable as a lithium ion secondary battery used in electric vehicles, power tools, power storage devices, and the like. In particular, it is used for electric vehicles (EV), hybrid electric vehicles (HEV), plug-in hybrid electric vehicles (PHEV), etc. that are required to be charged and discharged with a large current to improve acceleration performance and brake regeneration performance. It is suitable as a lithium ion secondary battery.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
（実施例１）
アスペクト比が１〜２０で、かつ、厚みが０．５μｍ以下の扁平なシリコン粒子を用意した。このシリコン粒子を超音波処理によって解砕後、乾燥し、２５０メッシュの標準篩にて粗粉を除去して負極材試料１を得た。
Example 1
Flat silicon particles having an aspect ratio of 1 to 20 and a thickness of 0.5 μm or less were prepared. The silicon particles were pulverized by ultrasonic treatment, dried, and coarse powder was removed with a 250 mesh standard sieve to obtain a negative electrode material sample 1.
（実施例２）
上記の実施例１で得られた負極材試料１を１００ｇとコールタールピッチ１０ｇを、それぞれ室温（２５℃）で混合し、次いで窒素流通下、３００℃／時間の昇温速度で９００℃まで昇温し、１時間保持して炭素層被覆シリコン粒子とした。得られた炭素被覆シリコン粒子を解砕後、２５０メッシュの標準篩を通し、負極材試料２を得た。
(Example 2)
100 g of the negative electrode material sample 1 obtained in Example 1 and 10 g of coal tar pitch were mixed at room temperature (25 ° C.), respectively, and then increased to 900 ° C. at a temperature increase rate of 300 ° C./hour under a nitrogen flow. Warm and hold for 1 hour to obtain carbon layer coated silicon particles. The obtained carbon-coated silicon particles were crushed and then passed through a 250 mesh standard sieve to obtain a negative electrode material sample 2.
（実施例３）
上記の実施例２において、使用したコールタールピッチの量を２０ｇに代えた以外は、同様にして、負極材試料３を得た。
(Example 3)
A negative electrode material sample 3 was obtained in the same manner as in Example 2, except that the amount of coal tar pitch used was changed to 20 g.
（比較例１、２）
従来品である黒鉛系負極材試料（アスペクト比が１．１）を比較例１とし、従来品であるシリコン系負極材試料（アスペクト比が１．２又は１．７、厚みが０．５μｍ超）を比較例２とした。
(Comparative Examples 1 and 2)
A conventional graphite-based negative electrode material sample (aspect ratio is 1.1) is Comparative Example 1, and a conventional silicon-based negative electrode material sample (aspect ratio is 1.2 or 1.7, thickness is more than 0.5 μm). ) As Comparative Example 2.
上記の実施例１〜３で得られた負極材試料１〜３、比較例１の黒鉛系負極材及び比較例２のシリコン系負極材の物性値、及び電気的特性を以下の方法で測定した。
測定結果を表１に示す。
The physical property values and electrical characteristics of the negative electrode material samples 1 to 3 obtained in Examples 1 to 3, the graphite negative electrode material of Comparative Example 1 and the silicon negative electrode material of Comparative Example 2 were measured by the following methods. .
The measurement results are shown in Table 1.
［アスペクト比］
アスペクト比は、図１に示すように、シリコン粒子の長軸方向の長さをＡ、短軸方向の長さをＢとしたとき、Ａ／Ｂで表される。本明細書において、アスペクト比は、顕微鏡でシリコン粒子を拡大し、任意に１０個のシリコン粒子を選択してＡ／Ｂを測定して、その測定値の算術平均値をとったものである。
ここで、長軸方向の長さは、観察されるシリコン粒子を二本の平行線Ａ、Ａ’で接するように挟んだとき、その間隔が最も大きくなる場合のＡ、Ａ’間の距離であり、短軸方向の長さは、前記長軸方向の長さを決める二本の平行線Ａ、Ａ’に対して垂直な二本の平行線Ｂ、Ｂ’で前記シリコン粒子を接するよう挟んだときのそのＢ、Ｂ’間の距離である。
[aspect ratio]
As shown in FIG. 1, the aspect ratio is represented by A / B, where A is the length in the major axis direction of the silicon particles and B is the length in the minor axis direction. In this specification, the aspect ratio is obtained by enlarging silicon particles with a microscope, arbitrarily selecting 10 silicon particles, measuring A / B, and taking the arithmetic average value of the measured values.
Here, the length in the major axis direction is the distance between A and A ′ when the distance between the silicon particles to be observed is the largest when the silicon particles are sandwiched by two parallel lines A and A ′. Yes, the length in the minor axis direction is such that the silicon particles are in contact with the two parallel lines B and B ′ perpendicular to the two parallel lines A and A ′ that determine the length in the major axis direction. This is the distance between B and B ′.
［ラマンスペクトルピーク強度比（Ｒ値）］
レーザーラマン分光光度計（日本分光株式会社製、ＮＲＳ−２１００）を用い、レーザー出力１０ｍＷ、分光器Ｆシングル、入射スリット幅８００μｍ、積算回数３回及び露光時間６０秒の条件にて測定を行った。
[Raman spectral peak intensity ratio (R value)]
Using a laser Raman spectrophotometer (NRS-2100, manufactured by JASCO Corporation), the measurement was performed under the conditions of a laser output of 10 mW, a spectroscope F single, an incident slit width of 800 μm, an integration number of 3 times, and an exposure time of 60 seconds. .
［平均粒子径］
負極材試料２ｇを界面活性剤と共に精製水中に分散させた溶液を分取し、レーザー回折式粒度分布測定装置（株式会社島津製作所製、ＳＡＬＤ−３０００Ｊ）の試料水槽に入れた。次いで、超音波をかけながらポンプで循環させながら、レーザー回折式で測定した。得られた粒度分布の累積５０％粒子径（Ｄ５０）を平均粒子径とした。
[Average particle size]
A solution in which 2 g of a negative electrode material sample was dispersed in purified water together with a surfactant was fractionated and placed in a sample water tank of a laser diffraction particle size distribution measuring apparatus (SALD-3000J, manufactured by Shimadzu Corporation). Subsequently, it measured by the laser diffraction type, circulating with a pump, applying an ultrasonic wave. The cumulative 50% particle size (D 50 ) of the obtained particle size distribution was defined as the average particle size.
［比表面積］
負極材試料１ｇを２００℃で２時間真空乾燥した後、Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製ＡＳＡＰ２０１０を用い、液体窒素温度（７７Ｋ）での窒素吸着を多点法で測定、ＢＥＴ法に従って算出した。
[Specific surface area]
After 1 g of a negative electrode material sample was vacuum dried at 200 ° C. for 2 hours, nitrogen adsorption at a liquid nitrogen temperature (77 K) was measured by a multipoint method using ASAP2010 manufactured by Micromeritics, and calculated according to the BET method.
［初回充電容量及び初回効率］
負極材試料５質量％に対し、黒鉛系負極材料、スチレンブタジエンゴム（ＳＢＲ）、及び、カルボキシメチルセルロース（ＣＭＣ）を固形分でそれぞれ９２．６質量％、１．２質量％及び１．２質量％となるよう加え、混練してペースト状の負極材スラリーを作製した。このスラリーを厚さ１０μｍの電解銅箔に厚さ１００ μｍのクオーターを用いて塗布し、さらに、１０５℃で乾燥して水分を除去し、試料電極（負極）を作製した。
次いで、上記試料電極、セパレータ、対極（正極）の順に積層した後、ＬｉＰＦ６をエチレンカーボネート（ＥＣ）及びメチルエチルカーボネート（ＭＥＣ）（ＥＣとＭＥＣは体積比で３：７）の混合溶媒にビニレンカーボネート（ＶＣ）０．５ｍｏｌ／Ｌの濃度になるように溶解した電解液溶液を注入し、コイン電池を作製した。対極には金属リチウムを使用し、セパレータには厚み２０μｍのポリエチレン微孔膜を使用した。
得られたコイン電池の試料電極と対極の間に、０．２ｍＡ／ｃｍ２の定電流で０．０２Ｖ（Ｖ ｖｓ. Ｌｉ／Ｌｉ＋）まで充電し、次いで０．２Ｖの定電圧で電流が０．０２ｍＡになるまで充電した。次に３０分の休止時間後に０．２ｍＡ／ｃｍ２の定電流で１．５Ｖ（Ｖ ｖｓ. Ｌｉ／Ｌｉ＋）まで放電する１サイクル試験を行い、初回充電容量を測定した。さらに、得られた初回充電容量と初回放電容量の差から、初回効率を算出した。
[Initial charge capacity and initial efficiency]
92.6% by mass, 1.2% by mass and 1.2% by mass, respectively, in terms of solid content of graphite-based negative electrode material, styrene butadiene rubber (SBR), and carboxymethyl cellulose (CMC) with respect to 5% by mass of the negative electrode material sample And kneaded to prepare a paste-like negative electrode material slurry. This slurry was applied to an electrolytic copper foil having a thickness of 10 μm using a quarter having a thickness of 100 μm, and further dried at 105 ° C. to remove moisture, thereby preparing a sample electrode (negative electrode).
Next, after laminating the sample electrode, separator, and counter electrode (positive electrode) in this order, LiPF 6 was mixed with vinylene in a mixed solvent of ethylene carbonate (EC) and methyl ethyl carbonate (MEC) (EC and MEC are in a volume ratio of 3: 7). An electrolyte solution dissolved to a concentration of 0.5 mol / L of carbonate (VC) was injected to produce a coin battery. Metal lithium was used for the counter electrode, and a polyethylene microporous film having a thickness of 20 μm was used for the separator.
Between the sample electrode and the counter electrode of the obtained coin battery, it was charged to 0.02 V (V vs. Li / Li + ) at a constant current of 0.2 mA / cm 2 , and then the current was applied at a constant voltage of 0.2 V. The battery was charged until it reached 0.02 mA. Next, after a 30-minute rest period, a one-cycle test was performed to discharge to 1.5 V (V vs. Li / Li + ) at a constant current of 0.2 mA / cm 2 , and the initial charge capacity was measured. Furthermore, the initial efficiency was calculated from the difference between the obtained initial charge capacity and the initial discharge capacity.
［充電容量維持率（１０回）］
負極材試料５質量％に対し、黒鉛系負極材料、スチレンブタジエンゴム（ＳＢＲ）、及び、カルボキシメチルセルロース（ＣＭＣ）を固形分でそれぞれ９２．６質量％、１．２質量％、及び、１．２質量％となるよう加え、混練してペースト状の負極材スラリーを作製した。このスラリーを厚さ１０μｍの電解銅箔に厚さ１００μｍのクオーターを用いて塗布し、さらに、１０５℃で乾燥して水分を除去し、試料電極（負極）を作製した。
次いで、上記試料電極、セパレータ、及び対極（正極）の順に積層した後、ＬｉＰＦ６をエチレンカーボネート（ＥＣ）及びメチルエチルカーボネート（ＭＥＣ）（ＥＣとＭＥＣは体積比で３：７）の混合溶媒にビニレンカーボネート（ＶＣ）０．５ ｍｏｌ／Ｌの濃度になるように溶解した電解液溶液を注入し、コイン電池を作製した。対極には金属リチウムを使用し、セパレータには厚み２０μｍのポリエチレン微孔膜を使用した。
得られたコイン電池の試料電極と対極の間に、０．２ｍＡ／ｃｍ２の定電流で０．０２Ｖ（Ｖ ｖｓ. Ｌｉ／Ｌｉ＋）まで充電し、次いで０．２Ｖの定電圧で電流が０．０２ｍＡになるまで充電した。次に３０ 分の休止時間後に０．２ｍＡ／ｃｍ２の定電流で１．５Ｖ（Ｖ ｖｓ. Ｌｉ／Ｌｉ＋）まで放電するサイクル試験を３回繰り返し行った。
その後、得られたコイン電池の試料電極と対極の間に、０．５ｍＡ／ｃｍ２の定電流で０．０２Ｖ（Ｖ ｖｓ. Ｌｉ／Ｌｉ＋）まで充電し、次いで０．５Ｖの定電圧で電流が０．０２ｍＡになるまで充電した。次に３０分の休止時間後に０．５ｍＡ／ｃｍ２の定電流で１．５Ｖ（Ｖ ｖｓ. Ｌｉ／Ｌｉ＋）まで放電するサイクル試験を７回繰り返し行った。
１サイクル目の充電容量を１００％とし、１０回目の充電容量から、充電容量維持率（１０回）を算出した。
[Charge capacity maintenance rate (10 times)]
92.6% by mass, 1.2% by mass, and 1.2% by mass of the graphite-based negative electrode material, styrene butadiene rubber (SBR), and carboxymethyl cellulose (CMC), respectively, with respect to 5% by mass of the negative electrode material sample. It added so that it might become mass%, and it knead | mixed and produced the paste-form negative electrode material slurry. This slurry was applied to an electrolytic copper foil with a thickness of 10 μm using a quarter with a thickness of 100 μm, and further dried at 105 ° C. to remove moisture, thereby preparing a sample electrode (negative electrode).
Next, after laminating the sample electrode, separator, and counter electrode (positive electrode) in this order, LiPF 6 is mixed into a mixed solvent of ethylene carbonate (EC) and methyl ethyl carbonate (MEC) (EC and MEC are in a volume ratio of 3: 7). An electrolyte solution dissolved to a concentration of 0.5 mol / L of vinylene carbonate (VC) was injected to prepare a coin battery. Metal lithium was used for the counter electrode, and a polyethylene microporous film having a thickness of 20 μm was used for the separator.
Between the sample electrode and the counter electrode of the obtained coin battery, it was charged to 0.02 V (V vs. Li / Li + ) at a constant current of 0.2 mA / cm 2 , and then the current was applied at a constant voltage of 0.2 V. The battery was charged until it reached 0.02 mA. Next, a cycle test in which the battery was discharged to 1.5 V (V vs. Li / Li + ) at a constant current of 0.2 mA / cm 2 after a 30-minute rest period was repeated three times.
Thereafter, between the sample electrode and the counter electrode of the obtained coin battery, it was charged to 0.02 V (V vs. Li / Li + ) with a constant current of 0.5 mA / cm 2 , and then with a constant voltage of 0.5 V. The battery was charged until the current reached 0.02 mA. Next, after a rest time of 30 minutes, a cycle test for discharging to 1.5 V (V vs. Li / Li + ) at a constant current of 0.5 mA / cm 2 was repeated seven times.
The charge capacity maintenance rate (10 times) was calculated from the 10th charge capacity, assuming that the charge capacity at the first cycle was 100%.
表１から明らかなように、実施例１〜３のリチウムイオン二次電池用負極材を用いたリチウムイオン二次電池は、比較例１及び比較例２のリチウムイオン二次電池用負極材を用いたリチウムイオン二次電池と比較して、初回充電容量に優れる。また、実施例１〜３のリチウムイオン二次電池用負極材を用いたリチウムイオン二次電池は、比較例２のシリコン系負極材料と比較し、初回効率及び充電容量維持率（１０回）に優れる。 As is clear from Table 1, the lithium ion secondary batteries using the negative electrode materials for lithium ion secondary batteries of Examples 1 to 3 use the negative electrode materials for lithium ion secondary batteries of Comparative Examples 1 and 2. Compared to a conventional lithium ion secondary battery, the initial charge capacity is excellent. Moreover, the lithium ion secondary battery using the negative electrode material for lithium ion secondary batteries of Examples 1 to 3 has an initial efficiency and a charge capacity maintenance rate (10 times) compared with the silicon-based negative electrode material of Comparative Example 2. Excellent.
［初回充電容量と負極材試料中のシリコン粒子含有率との関係］
０〜５５質量％の負極材試料１に対し、スチレンブタジエンゴム（ＳＢＲ）、及び、カルボキシメチルセルロース（ＣＭＣ）を固形分でそれぞれ１．２質量％、残りが黒鉛系負極材料となるよう加え、混練してペースト状の負極材スラリーを作製した。このスラリーを厚さ１０μｍの電解銅箔に厚さ１００μｍのクオーターを用いて塗布し、さらに、１０５℃で乾燥して水分を除去し、試料電極（負極）を作製した。
次いで、上記試料電極、セパレータ及び対極（正極）の順に積層した後、ＬｉＰＦ６をエチレンカーボネート（ＥＣ）及びメチルエチルカーボネート（ＭＥＣ）（ＥＣとＭＥＣは体積比で３：７）の混合溶媒にビニレンカーボネート（ＶＣ）０．５ ｍｏｌ／Ｌの濃度になるように溶解した電解液溶液を注入し、コイン電池を作製した。対極には金属リチウムを使用し、セパレータには厚み２０μｍのポリエチレン微孔膜を使用した。
得られたコイン電池の試料電極と対極の間に、０．２ｍＡ／ｃｍ２の定電流で０．０２Ｖ（Ｖ ｖｓ. Ｌｉ／Ｌｉ＋）まで充電し、次いで０．２Ｖの定電圧で電流が０．０２ｍＡになるまで充電した。次に３０分の休止時間後に０．２ｍＡ／ｃｍ２の定電流で１．５Ｖ（Ｖ ｖｓ. Ｌｉ／Ｌｉ＋）まで放電する１サイクル試験を行い、初回充電容量を測定した。
[Relationship between initial charge capacity and silicon particle content in negative electrode material sample]
Styrene butadiene rubber (SBR) and carboxymethylcellulose (CMC) are each added in a solid content of 1.2% by mass to the negative electrode material sample 1 of 0 to 55% by mass, and the remainder is a graphite-based negative electrode material. Thus, a paste-like negative electrode material slurry was produced. This slurry was applied to an electrolytic copper foil with a thickness of 10 μm using a quarter with a thickness of 100 μm, and further dried at 105 ° C. to remove moisture, thereby preparing a sample electrode (negative electrode).
Next, after laminating the sample electrode, separator, and counter electrode (positive electrode) in this order, LiPF 6 was mixed with vinylene in a mixed solvent of ethylene carbonate (EC) and methyl ethyl carbonate (MEC) (EC and MEC are in a volume ratio of 3: 7). An electrolyte solution dissolved so as to have a concentration of carbonate (VC) of 0.5 mol / L was injected to produce a coin battery. Metal lithium was used for the counter electrode, and a polyethylene microporous film having a thickness of 20 μm was used for the separator.
Between the sample electrode and the counter electrode of the obtained coin battery, it was charged to 0.02 V (V vs. Li / Li + ) at a constant current of 0.2 mA / cm 2 , and then the current was applied at a constant voltage of 0.2 V. The battery was charged until it reached 0.02 mA. Next, after a 30-minute rest period, a one-cycle test was performed to discharge to 1.5 V (V vs. Li / Li + ) at a constant current of 0.2 mA / cm 2 , and the initial charge capacity was measured.
負極材試料中のシリコン粒子含有率と初回充電容量との関係を表２及び図２に示す。 The relationship between the silicon particle content in the negative electrode material sample and the initial charge capacity is shown in Table 2 and FIG.
表２及び図２から明らかなように、実施例１のリチウムイオン二次電池用負極材を用いたリチウムイオン二次電池は、シリコン粒子含有率の増加に伴い、初回充電容量が増加する。また、実施例２、３のリチウムイオン二次電池用負極材を用いたリチウムイオン二次電池についても同様の結果が得られると推測される。 As is apparent from Table 2 and FIG. 2, the initial charge capacity of the lithium ion secondary battery using the negative electrode material for the lithium ion secondary battery of Example 1 increases as the silicon particle content increases. Moreover, it is estimated that the same result is obtained also about the lithium ion secondary battery using the negative electrode material for lithium ion secondary batteries of Example 2, 3.
シリコン粒子のアスペクト比と初回充電容量との関係を表３及び図３に示す。なお、各実施例及び各比較例では、前述の［初回充電容量及び初回効率］と同様の方法により試料電極（負極）を形成し、かつ同様の方法で初回充電容量を測定した。 The relationship between the aspect ratio of the silicon particles and the initial charge capacity is shown in Table 3 and FIG. In each example and each comparative example, the sample electrode (negative electrode) was formed by the same method as the above-mentioned [initial charge capacity and initial efficiency], and the initial charge capacity was measured by the same method.
表３及び図３から明らかなように、実施例１〜３のリチウムイオン二次電池用負極材を用いたリチウムイオン二次電池は、負極材中のシリコン粒子のアスペクト比が２０以下であることにより、初回充電容量が増加する。 As is apparent from Table 3 and FIG. 3, in the lithium ion secondary battery using the negative electrode materials for lithium ion secondary batteries of Examples 1 to 3, the aspect ratio of silicon particles in the negative electrode material is 20 or less. As a result, the initial charge capacity increases.
以上より、アスペクト比が１〜２０で、かつ、厚みが０．５μｍ以下の扁平なシリコン粒子を適用した負極を有するリチウムイオン二次電池は、充電容量に優れる。さらに、比較例２のシリコン系負極材を用いたリチウムイオン二次電池よりも、高効率かつ長寿命である。 From the above, a lithium ion secondary battery having a negative electrode to which flat silicon particles having an aspect ratio of 1 to 20 and a thickness of 0.5 μm or less are excellent in charge capacity. Furthermore, it is more efficient and has a longer life than the lithium ion secondary battery using the silicon-based negative electrode material of Comparative Example 2.
Claims (8)
前記シリコン粒子の表面上の少なくとも一部に形成された炭素層と、
を備えるリチウムイオン二次電池用負極材。 Flat silicon particles having an aspect ratio of 1 to 20 and a thickness of 0.5 μm or less;
A carbon layer formed on at least a part of the surface of the silicon particles;
A negative electrode material for a lithium ion secondary battery.
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| WO2020129467A1 (en) | 2018-12-19 | 2020-06-25 | Dic株式会社 | Silicon nanoparticles, non-aqueous secondary battery negative electrode active material using said silicon nanoparticles, and secondary battery |
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