JP2000044246A - PRODUCTION OF HIGH DENSITY SPINEL TYPE LiMn2O4 - Google Patents
PRODUCTION OF HIGH DENSITY SPINEL TYPE LiMn2O4Info
- Publication number
- JP2000044246A JP2000044246A JP10228515A JP22851598A JP2000044246A JP 2000044246 A JP2000044246 A JP 2000044246A JP 10228515 A JP10228515 A JP 10228515A JP 22851598 A JP22851598 A JP 22851598A JP 2000044246 A JP2000044246 A JP 2000044246A
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- Prior art keywords
- powder
- water
- limn
- spinel type
- aqueous solution
- Prior art date
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Classifications
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- 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)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する利用分野】本発明は、スピネル型 LiMn2
O4の製造方法に関し、特に、リチウム二次電池用正極材
として好適に用いられる高密度スピネル型 LiMn2O4の製
造方法についての提案である。The present invention relates to a spinel type LiMn 2
The present invention relates to a method for producing O 4 , and particularly to a method for producing a high-density spinel type LiMn 2 O 4 suitably used as a positive electrode material for a lithium secondary battery.
【０００２】[0002]
【従来の技術】LiMn2O4は、スピネルタイプのマンガン
化合物であり、資源量が豊富で価格面からも有利なマン
ガン化合物を原料とするので、高電圧・高エネルギー密
度型のリチウム二次電池用正極材であるLiCoO2の代替材
料として、最近注目を浴びている。 2. Description of the Related Art LiMn 2 O 4 is a spinel-type manganese compound, which is a raw material of a manganese compound which is abundant in resources and advantageous in terms of price. As a substitute for LiCoO 2 , which is a cathode material for automobiles, it has recently attracted attention.
【０００３】このようなスピネルタイプの LiMn2O4は、
従来、リチウム塩とマンガン塩，例えば炭酸リチウムと
Mn2O3 や炭酸リチウムと炭酸マンガンを、１：２の原子
比で乾式混合し、得られた混合粉を酸化性雰囲気中で焼
成することにより合成されている。しかし、かかる従来
の LiMn2O4製造プロセスでは、乾式の混合を固体−固体
間で行わせることから、原子あるいは分子レベルでのミ
クロ的な均一混合が不可能である。従って、結晶構造が
不安定となりやすく欠陥が生じやすいという欠点があっ
た。つまり、この技術では、充分な充放電サイクル特性
を有する材料を期待することはできない。[0003] Such spinel type LiMn 2 O 4 is
Conventionally, lithium salts and manganese salts, such as lithium carbonate
It is synthesized by dry-mixing Mn 2 O 3 or lithium carbonate and manganese carbonate at an atomic ratio of 1: 2, and firing the resulting mixed powder in an oxidizing atmosphere. However, in the conventional LiMn 2 O 4 production process, since dry mixing is performed between solids, it is impossible to perform microscopic uniform mixing at the atomic or molecular level. Therefore, there is a disadvantage that the crystal structure is likely to be unstable and defects are likely to occur. That is, with this technique, a material having sufficient charge / discharge cycle characteristics cannot be expected.
【０００４】これに対し、出願人は先に、水溶性リチウ
ム塩と硝酸マンガンを水に溶解することによって得られ
る混合水溶液中に、金属イオンを含まない非イオン水溶
性高分子をカチオン担持体として添加し、その後、前記
混合水溶液の水分を加熱除去することによって結晶性ス
ピネル型 LiMn2O4粉末を直接的に合成する方法を提案し
た（特開平８−208231公報、WO96／22943 公報参照）。[0004] On the other hand, the applicant has previously described a nonionic water-soluble polymer containing no metal ion as a cation carrier in a mixed aqueous solution obtained by dissolving a water-soluble lithium salt and manganese nitrate in water. A method of directly synthesizing crystalline spinel type LiMn 2 O 4 powder by adding and then removing the water content of the mixed aqueous solution by heating has been proposed (see JP-A-8-208231 and WO96 / 22943).
【０００５】[0005]
【発明が解決しようとする課題】出願人が先に提案した
上記合成方法によれば、高結晶質のスピネル型 LiMn2O4
粉末を得ることができ、これをリチウム二次電池の正極
材として用いると、サイクル寿命が長く、かつ、放電容
量の大きな二次電池を製造することができる。しかしな
がら、この合成方法によって得られた LiMn2O4は、見掛
け密度が 0.1ｇ／ccと極端に低く、合成反応後に高温
（約 700〜800 ℃）で再焼成しても、見掛け密度は 0.5
ｇ／cc程度、タップ密度では 1.2ｇ／cc程度、圧縮密度
でも 2.1ｇ／cc程度にしかならず、これを二次電池の正
極として実装した場合、正極板への充填密度が小さくな
るという課題が依然として残っていた。According to the above-mentioned synthesis method proposed by the applicant, a highly crystalline spinel type LiMn 2 O 4
When a powder can be obtained and used as a positive electrode material of a lithium secondary battery, a secondary battery having a long cycle life and a large discharge capacity can be manufactured. However, the apparent density of LiMn 2 O 4 obtained by this synthesis method is extremely low at 0.1 g / cc, and even if refired at a high temperature (about 700 to 800 ° C.) after the synthesis reaction, the apparent density is 0.5 g / cc.
g / cc, tap density is only about 1.2 g / cc, and compression density is only about 2.1 g / cc. When this is mounted as the positive electrode of a secondary battery, the problem that the packing density of the positive electrode plate becomes small still remains. Was left.
【０００６】本発明は、上述した従来技術の課題を解決
するためになされたものであり、その主たる目的は、充
填性および電池特性に優れるスピネル型 LiMn2O4を提供
することにある。具体的には、嵩密度を大きくして電池
の正極への充填密度を向上させることにより、初期放電
容量やサイクル寿命を低下させることなく、二次電池の
体積容量を向上させることにある。The present invention has been made to solve the above-mentioned problems of the prior art, and a main object of the present invention is to provide a spinel type LiMn 2 O 4 having excellent filling properties and battery characteristics. Specifically, it is to improve the volume capacity of the secondary battery without reducing the initial discharge capacity and the cycle life by increasing the bulk density to increase the filling density of the battery in the positive electrode.
【０００７】[0007]
【課題を解決するための手段】発明者らは、上掲の目的
の実現に向け鋭意研究を行った。その結果、水溶性リチ
ウム塩と硝酸マンガンとの混合水溶液に、カチオン担持
体を添加して加熱して得られる高結晶質のスピネル型 L
iMn2O4粉末を圧密，塊成化する際に、B2O3を微量添加
し、その後、粉砕，焼成すれば、スピネル型 LiMn2O4粉
末の充填性を改善できることを見出し、本発明に想到し
たのである。Means for Solving the Problems The present inventors have conducted intensive studies for realizing the above-mentioned object. As a result, a highly crystalline spinel-type L obtained by adding a cation carrier to a mixed aqueous solution of a water-soluble lithium salt and manganese nitrate and heating
The present inventors have found that, when the iMn 2 O 4 powder is compacted and agglomerated, a small amount of B 2 O 3 is added, followed by pulverization and firing, thereby improving the filling properties of the spinel-type LiMn 2 O 4 powder. It came to mind.
【０００８】すなわち、本発明は、水溶性リチウム塩と
硝酸マンガンとの混合水溶液中に、金属イオンを含まな
い非イオン水溶性高分子をカチオン担持体として添加
し、前記混合水溶液の水分を加熱除去することによって
結晶質スピネル型 LiMn2O4粉末を合成し、次いで、該結
晶質スピネル型 LiMn2O4粉末を圧密, 塊成化する際に、
濃度が10wt％以下の H3BO3水溶液を外枠量で３〜15wt％
添加し、塊成後、粉砕，焼成することを特徴とする高密
度スピネル型LiMn2O4 の製造方法である。That is, according to the present invention, a nonionic water-soluble polymer containing no metal ion is added as a cation carrier to a mixed aqueous solution of a water-soluble lithium salt and manganese nitrate, and the water content of the mixed aqueous solution is removed by heating. synthesizing a crystalline spinel LiMn 2 O 4 powder by, then the crystalline spinel LiMn 2 O 4 powder compaction, when agglomerated,
3 to 15% concentration of the to 10wt% of H 3 BO 3 aqueous solution border weight
This is a method for producing high-density spinel-type LiMn 2 O 4 , characterized by adding, agglomerating, pulverizing and firing.
【０００９】なお、圧密, 塊成化する方法は、ローラコ
ンパクタのような圧縮応力を与えて圧密化する方法、ま
たは前記粉末に必要により水分を供給しながら強制撹拌
して塊状もしくは粒状化して密度向上する方法、または
これらの組み合わせにより達成することが好ましい。The method of compacting and agglomerating may be performed by applying a compressive stress, such as a roller compactor, or may be performed by forcibly stirring the powder while supplying water as necessary to form a compact or a granular form. It is preferably achieved by an improved method or a combination of these.
【００１０】[0010]
【発明の実施の形態】本発明方法の基本は、水溶性リチ
ウム塩と硝酸マンガンの混合水溶液中に、金属イオンを
含まない非イオン水溶性高分子をカチオン担持体として
添加し、加熱脱水して結晶質スピネル型 LiMn2O4粉末を
合成し、これを圧密, 塊成化するとともに、B2O3を微量
添加した状態で焼成するところにある。DETAILED DESCRIPTION OF THE INVENTION The basic principle of the method of the present invention is to add a nonionic water-soluble polymer containing no metal ion as a cation carrier to a mixed aqueous solution of a water-soluble lithium salt and manganese nitrate, and to heat and dehydrate it. A crystalline spinel type LiMn 2 O 4 powder is synthesized, compacted and agglomerated, and fired with a small amount of B 2 O 3 added.
【００１１】これにより、B2O3を添加することで、焼結
が促進されて結晶性が向上し、かつ一次粒子どうしが強
固に焼結して二次粒子の緻密化が進む。その結果、焼成
時間を大幅に短縮でき、充填性および電池特性に優れた
結晶質スピネル型 LiMn2O4粉末を提供することができ
る。Thus, by adding B 2 O 3 , sintering is promoted and the crystallinity is improved, and the primary particles are strongly sintered and the secondary particles are densified. As a result, the firing time can be significantly reduced, and a crystalline spinel-type LiMn 2 O 4 powder having excellent filling properties and battery characteristics can be provided.
【００１２】本発明において、圧密, 塊成化の処理方法
としては、 二次元、三次元の圧力を加えて圧縮高密度化する方
法、例えば、LiMn2O4粉末をローラーまたは密閉容器内
で加圧する方法、 振動によって高密度化する方法、例えば、該LiMn2O
4 粉末に超音波振動等を付加する方法、 該LiMn2O4 粉末を、高速回転する撹拌器のような装
置にて高速撹拌しながら応力を与えて塊成化もしくは粒
状化する方法、 該LiMn2O4 粉末に、メカニカルアロイングによる粉
体剪断応力以上のパワーを与えて高密度・塊成化する方
法、 上記〜の方法の組み合わせにかかる方法、など
が採用される。なお、本発明の圧密・塊成化処理方法と
しては、スプレードライヤーのように、粉体に対して何
ら応力をかけないで密度を向上させる、いわゆる造粒の
みでの高密度化方法などは含まない。ただし、その造粒
と上記方法の組み合わせは何等妨げられるものではな
い。In the present invention, as a method of consolidation and agglomeration, a method of applying two-dimensional or three-dimensional pressure to increase the compression density, for example, adding LiMn 2 O 4 powder in a roller or a closed container. Pressing method, method of increasing density by vibration, for example, LiMn 2 O
4 a method of applying ultrasonic vibration or the like to the powder, a method of agglomerating or granulating the LiMn 2 O 4 powder by applying stress while stirring at a high speed with a device such as a stirrer rotating at a high speed, A method of applying a power equal to or more than the powder shearing stress by mechanical alloying to the 2 O 4 powder to achieve high density and agglomeration, a method involving a combination of the above-mentioned methods, and the like are employed. The consolidation / agglomeration method of the present invention includes a method of increasing the density without applying any stress to the powder, such as a spray dryer, a method of increasing the density only by granulation, and the like. Absent. However, the combination of the granulation and the above method is not hindered at all.
【００１３】ここで、B2O3を選択した理由は、B2O3は低
融点(450℃）であり、LiMn2O4 と反応しにくく、焼結助
剤として好適であると考えたからである。また、B2O3を
添加する手段として、本発明では、濃度が10wt％以下の
H3BO3水溶液を合成粉に対して外枠量で３〜15wt％添加
する方法が採用される。この理由は、 H3BO3水溶液の濃
度が10wt％超では、溶液粘度が高く、粉体に均一に混ぜ
ることが困難であり、一方、 H3BO3水溶液の添加量が３
wt％未満では粉体全体に行き渡らず、15wt％を超えると
乾燥時に H3BO3の偏析が生じるためである。The reason why B 2 O 3 was selected was that B 2 O 3 had a low melting point (450 ° C.), hardly reacted with LiMn 2 O 4 , and was considered to be suitable as a sintering aid. It is. As a means for adding B 2 O 3 , in the present invention, the concentration is 10 wt% or less.
A method of adding an H 3 BO 3 aqueous solution to the synthetic powder in an outer frame amount of 3 to 15 wt% is adopted. The reason for this is that if the concentration of the H 3 BO 3 aqueous solution exceeds 10 wt%, the solution viscosity is high and it is difficult to mix the H 3 BO 3 aqueous solution uniformly.
If the content is less than 15 wt%, H 3 BO 3 will segregate during drying if the content is less than 15 wt%.
【００１４】次に、本発明方法について各工程別に詳細
を説明する。本発明の方法は、まず、水溶性リチウム塩
と硝酸マンガンの混合水溶液中に、金属イオンを含まな
い非イオン水溶性高分子をカチオン担持体として添加し
て加熱する。ここで、金属イオンを含まない非イオン水
溶性高分子を、カチオン担持体として用いる理由は、高
分子に存在する金属イオンが LiMn2O4の構造中に入り結
晶構造欠陥を形成する、あるいは不純物として残留し、
電池特性を損なうおそれがあるからである。Next, the method of the present invention will be described in detail for each step. In the method of the present invention, first, a nonionic water-soluble polymer containing no metal ion is added as a cation carrier to a mixed aqueous solution of a water-soluble lithium salt and manganese nitrate and heated. Here, the reason why the nonionic water-soluble polymer containing no metal ion is used as the cation carrier is that the metal ion present in the polymer enters the structure of LiMn 2 O 4 to form a crystal structure defect or an impurity. Remains as
This is because battery characteristics may be impaired.
【００１５】まず、このような処理を行うことにより、
混合水溶液中のリチウムイオンとマンガンイオンはとも
に、水分の蒸発に伴い、カチオン担持体に固定されて反
応しやすい均一な状態となる一方で、硝酸イオンはカチ
オン担持体と加熱反応してニトロ化合物を生成する。そ
の結果、上記加熱を続けると、上記ニトロ化合物が分解
燃焼し、その熱エネルギーによってLiイオンとMnイオン
が反応して容易に LiMn2O4を合成することが可能にな
る。従って、このような方法によれば、LiMn2O4 の合成
が従来よりも低温度で可能となり、ひいては、比表面積
の大きな結晶質スピネル型 LiMn2O4粉末を、欠陥を生じ
ることなく安定して製造することができる。First, by performing such processing,
Both lithium ions and manganese ions in the mixed aqueous solution are fixed to the cation carrier and become a homogeneous state easily reacting with the evaporation of water, while nitrate ions are heated and reacted with the cation carrier to form the nitro compound. Generate. As a result, if the heating is continued, the nitro compound is decomposed and burned, and the thermal energy causes the Li ion and the Mn ion to react to easily synthesize LiMn 2 O 4 . Therefore, according to such a method, it is possible to synthesize LiMn 2 O 4 at a lower temperature than before, thereby stabilizing the crystalline spinel type LiMn 2 O 4 powder having a large specific surface area without generating defects. Can be manufactured.
【００１６】次に、このようにして得られたLiMn2O4 粉
末は、見掛け嵩密度が 0.1ｇ／cc以下である。つまり、
このようなLiMn2O4 粉末を高温で焼成したとしても、見
掛け嵩密度はせいぜい 0.5ｇ／cc程度にしかならない。
そこで、本発明では、このような合成方法によって得ら
れた LiMn2O4粉末にB2O3を微量添加して圧密, 塊成化処
理を施こしたのち、粉砕（顆粒化処理）し、その後、焼
成することにした。Next, the LiMn 2 O 4 powder thus obtained has an apparent bulk density of 0.1 g / cc or less. That is,
Even if such LiMn 2 O 4 powder is fired at a high temperature, the apparent bulk density is only about 0.5 g / cc at most.
Therefore, in the present invention, a very small amount of B 2 O 3 is added to the LiMn 2 O 4 powder obtained by such a synthesis method, followed by compaction and agglomeration, followed by pulverization (granulation), After that, firing was performed.
【００１７】その圧密, 塊成化の方法は、上述したとお
りであるが、特に、ローラコンパクタのように圧縮して
圧密化するタイプの装置、または攪拌器により強制撹拌
して前記粉末に応力を与えることにより、塊成化による
高密度化方法が好ましい。なお、上記圧密, 塊成化処理
は、ＨＩＰのような容器中で加熱しながら加圧する方法
によっても行うことができる。The method of consolidation and agglomeration is as described above. In particular, a device for compressing and consolidating, such as a roller compactor, or forcibly stirring with a stirrer to apply stress to the powder. By giving, the method of densification by agglomeration is preferable. The consolidation and agglomeration treatment can also be performed by a method of pressurizing while heating in a container such as HIP.
【００１８】その粉砕（顆粒化処理）の方法は、ペレタ
イザ、スプレードライヤのような一般的な造粒装置を用
いずに、ディスクミルまたは解砕機のような装置を用い
て上記圧密, 塊成化物を微粒子状に磨耗・顆粒化させる
ことが好ましい。The pulverization (granulation treatment) is performed by using a device such as a disk mill or a crusher without using a general granulating device such as a pelletizer or a spray dryer. Is preferably abraded and granulated into fine particles.
【００１９】また、結晶質スピネル型 LiMn2O4粉末を圧
密, 塊成化した後、顆粒化する前に、前記圧密, 塊成化
物を特定粒径以下, 即ち60mesh（250 μｍ) 以下の粉末
を分級して除去し、サイズ（粒径）の大きくなったもの
のみを顆粒化工程に移行し、サイズの小さいものは再び
圧密, 塊成化処理工程にまわすことができる。ただし、
この方法に限られることはない。Further, after compaction and agglomeration of the crystalline spinel type LiMn 2 O 4 powder, before compaction, the compacted and agglomerated material is powdered to a specific particle size or less, ie, 60 mesh (250 μm) or less. Is removed by classification, and only those having a large size (particle size) can be transferred to the granulation step, and those having a small size can be returned to the consolidation and agglomeration treatment steps. However,
It is not limited to this method.
【００２０】なお、圧密, 塊成化に先立ち、前処理とし
ての解砕処理および／または水分の添加は必要に応じて
行うものとし、さらに圧密, 塊成化処理に際しては、バ
インダーを添加してもよい。Prior to the consolidation and agglomeration, a crushing treatment and / or the addition of water as a pretreatment are performed as necessary. Further, in the consolidation and agglomeration treatment, a binder is added. Is also good.
【００２１】上記方法にて顆粒化処理した粉末は、その
後、 700〜800 ℃の温度にて焼成され、結晶欠陥のない
高結晶質で高密度のスピネル型LiMn2O4 粉末となる。従
来の方法では、 750℃×５時間程度の焼成が必要であっ
たが、本発明では、B2O3を微量添加した状態で焼成する
ので、 750℃×１時間程度で焼結が終了し、焼成時間を
大幅に短縮することができる。The powder granulated by the above method is then fired at a temperature of 700 to 800 ° C. to obtain a high-crystalline, high-density spinel-type LiMn 2 O 4 powder having no crystal defects. In the conventional method, sintering at 750 ° C. for about 5 hours was necessary. However, in the present invention, sintering was completed in about 750 ° C. for about 1 hour because sintering was performed with a small amount of B 2 O 3 added. In addition, the firing time can be greatly reduced.
【００２２】[0022]
【実施例】（実施例１）まず、LiNO3 １mol とMn(NO3)2
・6H2O 0.2molを純水200 mlに溶かし、混合水溶液とし
た。この混合水溶液を加熱し、カチオン担持体としてＰ
ＶＡを８ｇ添加した。その後、加熱を継続し、ある程度
の水分を蒸発させた後、150 ℃の乾燥器に移し、24時間
加熱乾燥した。その結果、黒色粉末が得られ、Ｘ線回折
による同定を行ったところ、LiMn2O4 スピネル単一相で
あることが確認できた。次に、得られたスピネル型 LiM
n2O4粉末に、 0.1〜1.0 wt％の範囲で濃度を変えた H3B
O3水溶液を外枠で10wt％添加した後、ローラコンパクタ
で複数回の圧密, 塊成化処理を行い、その後、ディスク
ミルでミクロンオーダの球状 (丸みをおびた) 微粒子と
し、750 ℃で１時間の焼成を行って本発明品を得た。EXAMPLES (Example 1) First, 1 mol of LiNO 3 and Mn (NO 3 ) 2
· Dissolve 6H 2 O 0.2 mol of pure water 200 ml, was mixed aqueous solution. This mixed aqueous solution is heated to form P as a cation carrier.
8 g of VA were added. Thereafter, the heating was continued to evaporate a certain amount of water, and then transferred to a dryer at 150 ° C. and dried by heating for 24 hours. As a result, a black powder was obtained. When the powder was identified by X-ray diffraction, it was confirmed that the powder was a single phase of LiMn 2 O 4 spinel. Next, the obtained spinel-type LiM
H 3 B with the concentration changed in the range of 0.1-1.0 wt% to n 2 O 4 powder
After adding 10 wt% of O 3 aqueous solution in the outer frame, compacting and agglomeration treatment are performed several times with a roller compactor, and then, it is made into spherical (rounded) fine particles of micron order by a disk mill, The product of the present invention was obtained by baking for a long time.
【００２３】（比較例１）比較材として、 H3BO3水溶液
を添加せずに、水のみを外枠で10wt％添加し、上述の塊
成化処理，粉砕を行い、750 ℃×５時間で焼成し、従来
品を得た。(Comparative Example 1) As a comparative material, without adding an aqueous solution of H 3 BO 3 , only water was added at 10 wt% in an outer frame, and the above-mentioned agglomeration treatment and pulverization were performed, and 750 ° C. × 5 hours And a conventional product was obtained.
【００２４】このようにして得られた本発明品と従来品
の特性を表１に示す。表１に示すように、本発明方法に
従って処理したものは、タップ密度と圧縮密度が共に向
上しているのがわかる。その結果、体積容量が330mAh／
cm3 程度にまで向上しており、二次電池の正極材として
充分な性能をもっていることが確認された。なお、本発
明品は、従来品と比較して、初期放電容量の低下は認め
られなかった。しかし、濃度が 0.5％超ではサイクル寿
命が低下しており、これは一次粒子が異常成長したため
と考えられる。これについては、焼成条件を最適化する
ことでサイクル寿命の劣化を抑えることができる。Table 1 shows the characteristics of the product of the present invention and the conventional product thus obtained. As shown in Table 1, it can be seen that those processed according to the method of the present invention have improved tap density and compressed density. As a result, the volume capacity is 330 mAh /
It has been improved to about cm 3, confirming that it has sufficient performance as a positive electrode material of a secondary battery. The product of the present invention did not show a decrease in the initial discharge capacity as compared with the conventional product. However, when the concentration was more than 0.5%, the cycle life was reduced, which is considered to be due to the abnormal growth of the primary particles. In this regard, deterioration of the cycle life can be suppressed by optimizing the firing conditions.
【００２５】[0025]
【表１】 [Table 1]
【００２６】また、本発明品と従来品のＸ線回析を行っ
た結果を図１および図２に示す。図１および図２に示す
Ｘ線回析チャートから明らかなように、B2O3の添加によ
り、ピークがシャープになって高角側でＫα1 とＫα2
によるスプリット（割れ）が出現し、スピネル型 LiMn2
O4粉末の結晶性が向上していることが確認できた。FIG. 1 and FIG. 2 show the results of X-ray diffraction of the product of the present invention and the conventional product. As is clear from the X-ray diffraction charts shown in FIGS. 1 and 2, the addition of B 2 O 3 sharpens the peak and increases Kα 1 and Kα 2 at the high angle side.
Split (split) due to spinel-type LiMn 2
It was confirmed that the crystallinity of the O 4 powder was improved.
【００２７】さらに、本発明品と従来品の二次粒子表面
を電子顕微鏡（ＳＥＭ）で観察した結果を、図３および
図４の写真に示す。図３および図４に示す写真から明ら
かなように、B2O3の添加により、一次粒子径が大きくな
って角張っていることから、結晶が成長していることが
わかった。Further, the results of observing the surfaces of the secondary particles of the product of the present invention and the conventional product by an electron microscope (SEM) are shown in the photographs of FIGS. As is clear from the photographs shown in FIG. 3 and FIG. 4, the addition of B 2 O 3 increased the primary particle diameter and made it angular, indicating that the crystal was growing.
【００２８】[0028]
【発明の効果】以上説明したように本発明によれば、B2
O3を添加することで、焼結が促進されて結晶性が向上
し、かつ一次粒子どうしが強固に焼結して二次粒子の緻
密化が進む結果、焼成時間を大幅に短縮でき、充填性お
よび電池特性に優れた結晶質スピネル型 LiMn2O4粉末を
提供することができる。As described above, according to the present invention, B 2
By adding O 3 , sintering is promoted, crystallinity is improved, and primary particles are strongly sintered and secondary particles are densified.As a result, firing time can be significantly reduced, and A crystalline spinel-type LiMn 2 O 4 powder having excellent properties and battery characteristics can be provided.
【図１】実施例１で得られたスピネル型 LiMn2O4のＸ線
回折チャート図である。FIG. 1 is an X-ray diffraction chart of a spinel type LiMn 2 O 4 obtained in Example 1.
【図２】比較例１で得られたスピネル型 LiMn2O4のＸ線
回折チャート図である。FIG. 2 is an X-ray diffraction chart of a spinel type LiMn 2 O 4 obtained in Comparative Example 1.
【図３】実施例１で得られたスピネル型 LiMn2O4の写真
である。FIG. 3 is a photograph of the spinel type LiMn 2 O 4 obtained in Example 1.
【図４】比較例１で得られたスピネル型 LiMn2O4の写真
である。FIG. 4 is a photograph of the spinel type LiMn 2 O 4 obtained in Comparative Example 1.
フロントページの続き (72)発明者 橋場 裕樹 茨城県つくば市東光台５丁目９番６号 日 本重化学工業株式会社筑波研究所内 (72)発明者 大谷 賢哉 富山県高岡市吉久１−１−１ 日本重化学 工業株式会社高岡工場内 Ｆターム(参考） 4G048 AA04 AB02 AB05 AC06 AD06 AE05 5H003 AA02 BA01 BA04 BA05 BB05 BC01 BC06 BD06 5H014 AA01 BB00 BB01 BB03 BB05 EE10 HH08 Continued on the front page (72) Inventor Hiroki Hashiba 5-9-6 Tokodai, Tsukuba-shi, Ibaraki Pref. Tsukuba Research Laboratories, Japan Heavy Industries, Ltd. (72) Inventor Kenya Otani 1-1-1 Yoshihisa, Takaoka-shi, Toyama Japan Japan F-term (reference) in the Takaoka Plant of Heavy Chemical Industry Co., Ltd. 4G048 AA04 AB02 AB05 AC06 AD06 AE05 5H003 AA02 BA01 BA04 BA05 BB05 BC01 BC06 BD06 5H014 AA01 BB00 BB01 BB03 BB05 EE10 HH08
Claims (1)
合水溶液中に、金属イオンを含まない非イオン水溶性高
分子をカチオン担持体として添加し、前記混合水溶液の
水分を加熱除去することによって結晶質スピネル型 LiM
n2O4粉末を合成し、次いで、該結晶質スピネル型 LiMn2
O4粉末を圧密, 塊成化する際に、濃度が10wt％以下の H
3BO3水溶液を外枠量で３〜15wt％添加し、その後、粉
砕，焼成することを特徴とする高密度スピネル型LiMn2O
4 の製造方法。1. A non-ionic water-soluble polymer containing no metal ion is added as a cation carrier to a mixed aqueous solution of a water-soluble lithium salt and manganese nitrate, and the water content of the mixed aqueous solution is removed by heating. Spinel LiM
n 2 O 4 powder was synthesized, and then the crystalline spinel type LiMn 2
When the O 4 powder is compacted and agglomerated, the concentration of H is 10 wt% or less.
High density spinel type LiMn 2 O characterized by adding 3 to 15 wt% of 3 BO 3 aqueous solution in outer frame amount, and then pulverizing and firing.
4. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22851598A JP3881111B2 (en) | 1998-07-30 | 1998-07-30 | Method for producing high density spinel type LiMn2O4 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22851598A JP3881111B2 (en) | 1998-07-30 | 1998-07-30 | Method for producing high density spinel type LiMn2O4 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000044246A true JP2000044246A (en) | 2000-02-15 |
| JP3881111B2 JP3881111B2 (en) | 2007-02-14 |
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ID=16877646
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| Application Number | Title | Priority Date | Filing Date |
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| JP22851598A Expired - Fee Related JP3881111B2 (en) | 1998-07-30 | 1998-07-30 | Method for producing high density spinel type LiMn2O4 |
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009152214A (en) * | 2000-09-25 | 2009-07-09 | Samsung Sdi Co Ltd | Positive electrode active material for lithium secondary battery, and manufacturing method therefor |
-
1998
- 1998-07-30 JP JP22851598A patent/JP3881111B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009152214A (en) * | 2000-09-25 | 2009-07-09 | Samsung Sdi Co Ltd | Positive electrode active material for lithium secondary battery, and manufacturing method therefor |
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| Publication number | Publication date |
|---|---|
| JP3881111B2 (en) | 2007-02-14 |
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