JP2000090917A - Manufacture of positive electrode plate for lithium ion secondary battery - Google Patents
Manufacture of positive electrode plate for lithium ion secondary batteryInfo
- Publication number
- JP2000090917A JP2000090917A JP10264092A JP26409298A JP2000090917A JP 2000090917 A JP2000090917 A JP 2000090917A JP 10264092 A JP10264092 A JP 10264092A JP 26409298 A JP26409298 A JP 26409298A JP 2000090917 A JP2000090917 A JP 2000090917A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- dispersion
- lithium
- composite oxide
- secondary battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はリチウムイオン二次
電池用正極板の製造方法に関するものである。The present invention relates to a method for manufacturing a positive electrode plate for a lithium ion secondary battery.
【０００２】[0002]
【従来の技術】ＬｉＣｏＯ2 等からなるリチウム複合酸
化物を正極材として用いる正極板と、リチウムイオンを
吸蔵、放出する炭素材料等を負極材として用いる負極板
とが非水電解質を介して積層されたリチウムイオン二次
電池が知られている。一般にリチウムイオン二次電池の
正極板は、前述のリチウム複合酸化物（正極材）と、バ
インダと、有機溶媒とを含む正極材スラリーを集電体上
に塗布してからこの正極材スラリーを乾燥して製造す
る。リチウムイオン二次電池は、エネルギー密度が高
く、主にＶＴＲカメラ，ノートパソコン，携帯電話等の
ポータブル機器に使用されている。最近では、このリチ
ウムイオン二次電池のエネルギー密度を更に高めること
が求められている。そこでＬｉＣｏＯ2 に代えて、Ｌｉ
ＮｉＯ2 ，ＬｉＮｉx Ｃｏy Ｏ2 等の少なくともリチウ
ム元素及びニッケル元素を含むリチウムニッケル複合酸
化物を主成分とする正極材を用いるリチウムイオン二次
電池が開発された。リチウムニッケル複合酸化物の単位
重量あたりの容量（１８０〜２００ mAh/g）は、ＬｉＣ
ｏＯ2 の単位重量あたりの容量（１４５〜１５０ mAh/
g）に比べて大幅に高い。 2. Description of the Related Art A positive electrode plate using a lithium composite oxide made of LiCoO 2 or the like as a positive electrode material and a negative electrode plate using a carbon material or the like that occludes and releases lithium ions as a negative electrode material are laminated via a non-aqueous electrolyte. Lithium ion secondary batteries are known. Generally, a positive electrode plate of a lithium ion secondary battery is formed by applying a positive electrode material slurry containing the above-described lithium composite oxide (positive electrode material), a binder, and an organic solvent onto a current collector, and then drying the positive electrode material slurry. To manufacture. Lithium ion secondary batteries have a high energy density and are mainly used for portable devices such as VTR cameras, notebook computers, and mobile phones. Recently, it has been required to further increase the energy density of the lithium ion secondary battery. Therefore, instead of LiCoO 2 , Li
A lithium-ion secondary battery using a positive electrode material mainly composed of a lithium-nickel composite oxide containing at least a lithium element and a nickel element such as NiO 2 and LiNix Coy O 2 has been developed. The capacity per unit weight (180-200 mAh / g) of the lithium nickel composite oxide is LiC
Capacity per unit weight of oO 2 (145 to 150 mAh /
significantly higher than g).
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、このよ
うなリチウムニッケル複合酸化物を用いて正極材スラリ
ーを作ると正極材スラリーが流動性を失いゲル化すると
いう問題が生じる。これは次のような理由によると考え
られる。他のリチウム含有複合酸化物に比べて、少なく
ともリチウム元素及びニッケル元素を含むリチウムニッ
ケル複合酸化物は、生成された段階において、Ｌｉ2 Ｏ
等のフリーのリチウムが不純物として残留しやすい。こ
のＬｉ2 Ｏがスラリー中に微量に含まれる水分と反応す
ると、Ｌｉ2 Ｏ＋Ｈ2 Ｏ→２ＬｉＯＨの反応式で水酸化
リチウム（ＬｉＯＨ）を生成し、スラリーが比較的強い
アルカリ性になる。例えば、この種のリチウムニッケル
複合酸化物を水に対して約１１重量％分散させて分散液
を作ると、分散液のｐＨは約１２になる。これにより、
スラリー中のバインダが三次元化して正極材スラリーが
ゲル化すると考えられる。特にバインダとして、ポリフ
ッ化ビニリデン（ＰＶＤＦ）を用い、有機溶媒としてＮ
−メチル−２−ピロリドン（ＮＭＰ）を用いるとバイン
ダの三次元化が著しい。そこで、正極材スラリー生成時
に除湿等の雰囲気対策を講じることも考えられるが、こ
のような対策を講じると、製造コストが高くなる。ま
た、このような対策を講じても活物質中にＬｉ2 Ｏが存
在するので、活物質中にＬｉＯＨやＬｉ2 ＣＯ3 が生成
され、電池の充放電が阻害されて高負荷時の放電容量が
低くなる。However, when a positive electrode material slurry is prepared using such a lithium nickel composite oxide, there is a problem that the positive electrode material slurry loses fluidity and gels. This is considered for the following reasons. Compared with other lithium-containing composite oxides, a lithium-nickel composite oxide containing at least a lithium element and a nickel element is Li 2 O
Free lithium such as is likely to remain as impurities. When this Li 2 O reacts with a small amount of water contained in the slurry, lithium hydroxide (LiOH) is generated by a reaction formula of Li 2 O + H 2 O → 2LiOH, and the slurry becomes relatively strongly alkaline. For example, when this kind of lithium nickel composite oxide is dispersed in water by about 11% by weight to form a dispersion, the pH of the dispersion becomes about 12. This allows
It is considered that the binder in the slurry becomes three-dimensional and the positive electrode material slurry gels. In particular, polyvinylidene fluoride (PVDF) is used as a binder, and N is used as an organic solvent.
When -methyl-2-pyrrolidone (NMP) is used, the binder is significantly three-dimensional. Therefore, it is conceivable to take measures against the atmosphere, such as dehumidification, when the positive electrode material slurry is generated. However, if such measures are taken, the manufacturing cost increases. In addition, even if such measures are taken, since Li 2 O is present in the active material, LiOH and Li 2 CO 3 are generated in the active material, charging and discharging of the battery are hindered, and the discharge capacity at high load is reduced. Becomes lower.
【０００４】本発明の目的は、製造コストを高めたり、
電池の高負荷時の放電容量を低下させることなく、正極
材スラリーがゲル化するのを防止できるリチウムイオン
二次電池用正極板の製造方法を提供することにある。It is an object of the present invention to increase manufacturing costs,
An object of the present invention is to provide a method for manufacturing a positive electrode plate for a lithium ion secondary battery, which can prevent the positive electrode material slurry from gelling without lowering the discharge capacity of the battery under a high load.
【０００５】[0005]
【課題を解決するための手段】本発明は、少なくともリ
チウム元素及びニッケル元素を含むリチウムニッケル複
合酸化物を主成分とする正極材と、バインダと、有機溶
媒とを含むスラリーを集電体上に塗布してリチウムイオ
ン二次電池用正極板を製造する方法を改良の対象にす
る。ここでいう、少なくともリチウム元素及びニッケル
元素を含むリチウムニッケル複合酸化物とは、ＬｉＮｉ
Ｏ2 のようにＬｉ及びＮｉを含むリチウムニッケル複合
酸化物、またはＬｉＮｉx Ｃｏy Ｏ2 （x ＋y ＝１）の
ようにＬｉ及びＮｉに加えて、Ｌｉ及びＮｉ以外の元素
も少なくとも１つ有するリチウムニッケル複合酸化物で
ある。本発明では、正極材を水に対して８〜１２重量％
分散させて分散液を作った場合に、分散液のｐＨが７．
１〜１１．２になるものを正極材として用いる。SUMMARY OF THE INVENTION According to the present invention, there is provided a slurry comprising a positive electrode material containing a lithium-nickel composite oxide containing at least a lithium element and a nickel element as a main component, a binder and an organic solvent. A method for producing a positive electrode plate for a lithium ion secondary battery by coating is intended to be improved. Here, the lithium-nickel composite oxide containing at least the lithium element and the nickel element is LiNi
Lithium nickel composite oxide containing Li and Ni such as O 2 , or lithium nickel having at least one element other than Li and Ni in addition to Li and Ni such as LiNix Coy O 2 (x + y = 1) It is a composite oxide. In the present invention, the cathode material is 8 to 12% by weight based on water.
When a dispersion is prepared by dispersing, the pH of the dispersion is adjusted to 7.
A material that becomes 1 to 11.2 is used as a positive electrode material.
【０００６】このようにして水に分散しても強いアルカ
リ性にならないリチウムニッケル複合酸化物を作れば、
正極材スラリーに微量に水分が含まれていても、正極材
スラリーは、ほぼ中性または弱アルカリ性になり、バイ
ンダの三次元化を抑制して、正極材スラリーがゲル化す
るのを防ぐことができる。なお、分散液のｐＨが７．１
を下回ると、活物質が電解液に溶解しやすくなるため、
放電容量が低くなる。このような正極材は、種々の方法
で生成できる。例えば、Ｌｉ2 Ｏとリチウムニッケル複
合酸化物とを含むリチウムニッケル複合酸化物材料を水
に対して８〜１２重量％分散させて分散液を作り、この
分散液のｐＨが７．１〜１１．２になるまで分散液を撹
拌する。次にこの分散液を濾過して、残渣を取出してか
ら、乾燥して正極材を生成する。このようにすれば、分
散液を撹拌する際に空気中のＣＯ2 が分散液に溶け込ん
でＨ2 ＣＯ3 になる。このＨ2 ＣＯ3 は次の式により、
Ｌｉ2 Ｏと水とが反応して生成された分散液中のＬｉＯ
Ｈと反応する。In this way, if a lithium nickel composite oxide which does not become strongly alkaline even when dispersed in water is produced,
Even if a slight amount of water is contained in the positive electrode material slurry, the positive electrode material slurry becomes almost neutral or weakly alkaline, suppressing the three-dimensional formation of the binder and preventing the positive electrode material slurry from gelling. it can. The pH of the dispersion was 7.1.
If the value is lower than the range, the active material is easily dissolved in the electrolytic solution.
The discharge capacity decreases. Such a positive electrode material can be produced by various methods. For example, a lithium-nickel composite oxide material containing Li 2 O and a lithium-nickel composite oxide is dispersed in water in an amount of 8 to 12% by weight to prepare a dispersion, and the pH of the dispersion is 7.1 to 11. Stir the dispersion until 2. Next, the dispersion is filtered to remove the residue, and then dried to produce a positive electrode material. In this way, when the dispersion is stirred, CO 2 in the air dissolves into the dispersion to become H 2 CO 3 . This H 2 CO 3 is given by the following equation:
LiO in the dispersion formed by the reaction of Li 2 O and water
Reacts with H.
【０００７】[0007]
【化１】 これにより、分散液のｐＨは小さくなり、分散液が中性
化する。この時のｐＨは、分散液の撹拌速度または撹拌
時間等により調整すればよい。Embedded image As a result, the pH of the dispersion is reduced, and the dispersion is neutralized. The pH at this time may be adjusted by the stirring speed or the stirring time of the dispersion.
【０００８】本方法で製造された正極板の正極材は、上
記式で生成されたＬｉ2 ＣＯ3 が分散液濾過後に残留す
ることになる。即ち、リチウムニッケル複合酸化物に加
えてＬｉ2 ＣＯ3 を含むことになる。[0008] In the positive electrode material of the positive electrode plate manufactured by the present method, Li 2 CO 3 produced by the above formula remains after filtration of the dispersion. That is, Li 2 CO 3 is included in addition to the lithium nickel composite oxide.
【０００９】また他の方法では、Ｌｉ2 Ｏとリチウムニ
ッケル複合酸化物とを含むリチウムニッケル複合酸化物
材料を水に対して８〜１２重量％分散させて分散液を作
り、分散液のｐＨが７．１〜１１．２になるまで分散液
に燐酸（Ｈ3 ＰＯ4 ）を加える。次にこの分散液を濾過
して、残渣を取出してから、乾燥して正極材を生成す
る。このようにすれば、Ｈ3 ＰＯ4 は次の式によりＬｉ
2 Ｏと水とが反応して生成された分散液中のＬｉＯＨと
反応する。In another method, a lithium-nickel composite oxide material containing Li 2 O and a lithium-nickel composite oxide is dispersed in water in an amount of 8 to 12% by weight to form a dispersion. until 7.1 to 11.2 is added phosphoric acid (H 3 PO 4) to the dispersion. Next, the dispersion is filtered to remove the residue, and then dried to produce a positive electrode material. In this way, H 3 PO 4 is Li by the following equation:
The reaction between 2 O and water reacts with LiOH in the dispersion produced.
【００１０】[0010]
【化２】 これにより、分散液のｐＨは小さくなり、分散液が中性
化する。Embedded image As a result, the pH of the dispersion is reduced, and the dispersion is neutralized.
【００１１】なお、本発明者が試験したところ、分散液
のｐＨを低下させるために、塩酸、硫酸、硝酸、硼酸、
塩素酸等の燐酸以外の無機酸または有機酸を用いても十
分な放電容量を得ることはできなかった。Incidentally, when the present inventor tested, in order to lower the pH of the dispersion, hydrochloric acid, sulfuric acid, nitric acid, boric acid,
Even if an inorganic or organic acid other than phosphoric acid such as chloric acid was used, a sufficient discharge capacity could not be obtained.
【００１２】本方法で製造された正極板の正極材は、上
記式で生成されたＬｉ3 ＰＯ4 が分散液濾過後に残留す
ることになる。即ち、リチウムニッケル複合酸化物に加
えてＬｉ3 ＰＯ4 を含むことになる。In the positive electrode material of the positive electrode plate manufactured by the present method, Li 3 PO 4 produced by the above formula remains after filtration of the dispersion. That is, Li 3 PO 4 is included in addition to the lithium nickel composite oxide.
【００１３】前述したように、バインダとしてポリフッ
化ビニリデン（ＰＶＤＦ）を用い、有機溶媒としてＮ−
メチル−２−ピロリドン（ＮＭＰ）を用いた場合に、ス
ラリーが比較的強いアルカリ性になった際のバインダの
三次元化が著しい。そこで、このようなバインダ（ＰＶ
ＤＦ）及び有機溶媒（ＮＭＰ）を用いた場合には、本発
明の効果は著しく高くなる。As described above, polyvinylidene fluoride (PVDF) is used as a binder, and N-
When methyl-2-pyrrolidone (NMP) is used, the binder becomes remarkably three-dimensional when the slurry becomes relatively strongly alkaline. Therefore, such a binder (PV
When DF) and an organic solvent (NMP) are used, the effect of the present invention is significantly enhanced.
【００１４】[0014]
【発明の実施の形態】試験に用いた各リチウムイオン二
次電池用正極板の正極材スラリーを次のようにして作っ
た。まず、Ｌｉ2 ＯとＬｉＮｉ0.8 Ｃｏ0.2 Ｏ2 とを含
むリチウムニッケル複合酸化物材料５ｇを水４５ｇに分
散して（リチウムニッケル複合酸化物材料を水に対して
１１重量％分散させて）分散液を作る。本例では、本莊
ＦＭＣエナジー株式会社から販売されているリチウムニ
ッケル複合酸化物材料を用いた。このリチウムニッケル
複合酸化物材料に含まれるＬｉ2 Ｏの量は定かではな
い。しかしながら、下記の表１の比較例１に示される撹
拌時間が０分のときのｐＨ値は、リチウムニッケル複合
酸化物材料に含まれるＬｉ2 Ｏの量に比例している。即
ち、Ｌｉ2 Ｏの含有量が多ければ撹拌時間が０分のとき
のｐＨ値は大きくなり、Ｌｉ2 Ｏの含有量が少ないとき
にはこのｐＨ値は小さくなる。したがってこのｐＨ値よ
りＬｉ2 Ｏの含有量は、計算によりある程度求めること
は可能である。Ｌｉ2 Ｏの含有量が不明であっても、撹
拌時間によってｐＨ値の調整ができるため、Ｌｉ2 Ｏの
含有量は不明であっても問題にはならない。次にマグネ
ットスターラーを用いて表１に示す時間の撹拌を分散液
にそれぞれ行って、ｐＨ値の異なる各分散液を作った。
このように分散液を撹拌すると空気中のＣＯ2 が分散液
に溶け込む。そのため、撹拌時間が長いほど分散液のｐ
Ｈ値は小さくなる。なお、本試験では、ｐＨ測定器を汚
さないために、分散液を撹拌後６０分間静止してから、
分散液の上澄液のｐＨ値を測定した。次に分散液をそれ
ぞれ濾過してリチウムニッケル複合酸化物を取出した。
次にこれらを９０℃の温度で２４時間加熱して乾燥し、
平均粒径２０μｍの各リチウムニッケル複合酸化物を得
た。BEST MODE FOR CARRYING OUT THE INVENTION The positive electrode material slurry of each positive electrode plate for a lithium ion secondary battery used in the test was prepared as follows. First, 5 g of a lithium-nickel composite oxide material containing Li 2 O and LiNi 0.8 Co 0.2 O 2 was dispersed in 45 g of water (by dispersing the lithium-nickel composite oxide material by 11% by weight with respect to water). make. In this example, a lithium nickel composite oxide material sold by Honjo FMC Energy Co., Ltd. was used. The amount of Li 2 O contained in this lithium nickel composite oxide material is not certain. However, the pH value when the stirring time is 0 minutes shown in Comparative Example 1 in Table 1 below is proportional to the amount of Li 2 O contained in the lithium nickel composite oxide material. That, pH value when the stirring time The greater the content of Li 2 O is 0 minutes increases, the pH value when a small content of Li 2 O is small. Therefore, the Li 2 O content can be determined to some extent by calculation from the pH value. Even if the content of Li 2 O is unknown, since the pH value can be adjusted by the stirring time, there is no problem even if the content of Li 2 O is unknown. Next, each of the dispersion liquids was stirred for the time shown in Table 1 using a magnetic stirrer to prepare dispersion liquids having different pH values.
When the dispersion is stirred in this manner, CO 2 in the air dissolves in the dispersion. Therefore, the longer the stirring time, the higher the p
The H value decreases. In addition, in this test, in order not to contaminate the pH meter, after the dispersion liquid was left stationary for 60 minutes after stirring,
The pH value of the supernatant of the dispersion was measured. Next, each dispersion was filtered to take out a lithium nickel composite oxide.
Next, they are dried by heating at a temperature of 90 ° C. for 24 hours,
Each lithium nickel composite oxide having an average particle size of 20 μm was obtained.
【００１５】また、これらのリチウムニッケル複合酸化
物とは別にＬｉ2 ＯとＬｉＮｉ0.8Ｃｏ0.2 Ｏ2 とを含
むリチウムニッケル複合酸化物５ｇを水４５ｇに分散し
て（リチウムニッケル複合酸化物材料を水に対して１１
重量％分散させて）分散液を作った。次に濃度８．５重
量％の燐酸（Ｈ3 ＰＯ4 ）を表２に示す量だけ分散液に
それぞれ滴下してから、マグネットスターラーを用いて
５分間撹拌した。そして、分散液を６０分間静止して、
分散液の上澄液のｐＨ値を測定した。次に分散液をそれ
ぞれ濾過してリチウムニッケル複合酸化物を取出した。
次にこれらを９０℃の温度で２４時間加熱して乾燥し、
平均粒径２０μｍの各リチウムニッケル複合酸化物を得
た。Further, separately from these lithium-nickel composite oxides, 5 g of a lithium-nickel composite oxide containing Li 2 O and LiNi 0.8 Co 0.2 O 2 is dispersed in 45 g of water (the lithium-nickel composite oxide material is 11 for
A dispersion was made (by weight percent dispersion). Next, phosphoric acid (H 3 PO 4 ) having a concentration of 8.5% by weight was added dropwise to the dispersion in an amount shown in Table 2, and the mixture was stirred for 5 minutes using a magnetic stirrer. Then, the dispersion is allowed to stand for 60 minutes,
The pH value of the supernatant of the dispersion was measured. Next, each dispersion was filtered to take out a lithium nickel composite oxide.
Next, they are dried by heating at a temperature of 90 ° C. for 24 hours,
Each lithium nickel composite oxide having an average particle size of 20 μm was obtained.
【００１６】次に上記各リチウムニッケル複合酸化物８
０重量％を、平均粒径０．５μｍの黒鉛からなる導電剤
１０重量％と、ポリフッ化ビニリデン（ＰＶＤＦ）から
なるバインダ１０重量％とにそれぞれ混合した。次にこ
れにＮ−メチル−２−ピロリドン（ＮＭＰ）からなる有
機溶媒を適量加えて十分に混練して各正極材スラリーを
作った。なお、正極材スラリー作成時の雰囲気は５０％
ＲＨとした。次に２０μｍ×５０ｍｍ×４５０ｍｍの帯
状のアルミニウム箔からなる正極集電体の両面にロール
トゥロール転写により正極材スラリーを塗布してから乾
燥、プレスして両面にそれぞれ厚み８０μｍの正極材層
を形成して、表１及び２に示す比較例１Ａ，１Ｂ及び実
施例１Ａ〜１Ｅ並びに比較例２Ａ〜２Ｃ及び実施例２Ａ
〜２Ｄの各正極板を作った。表１及び２には、各正極板
の製造時の正極材スラリーの流動性の有無が示されてい
る。Next, each of the above lithium nickel composite oxides 8
0% by weight was mixed with 10% by weight of a conductive agent composed of graphite having an average particle size of 0.5 μm and 10% by weight of a binder composed of polyvinylidene fluoride (PVDF). Next, an appropriate amount of an organic solvent composed of N-methyl-2-pyrrolidone (NMP) was added thereto and sufficiently kneaded to prepare each positive electrode material slurry. The atmosphere during the preparation of the positive electrode material slurry was 50%
RH. Next, a positive electrode material slurry is applied by roll-to-roll transfer to both surfaces of a positive electrode current collector made of a 20 μm × 50 mm × 450 mm strip-shaped aluminum foil, dried and pressed to form a positive electrode material layer having a thickness of 80 μm on both surfaces. Then, Comparative Examples 1A and 1B and Examples 1A to 1E and Comparative Examples 2A to 2C and Example 2A shown in Tables 1 and 2
~ 2D positive electrode plates were made. Tables 1 and 2 show the presence or absence of fluidity of the positive electrode material slurry at the time of manufacturing each positive electrode plate.
【００１７】[0017]
【表１】 [Table 1]
【表２】 表１及び２より分散液のｐＨ値が１１．２を上回る比較
例１Ａ，１Ｂ，２Ａ，２Ｂでは、正極材スラリーの流動
性がなく電池として有効に機能する正極板を形成するこ
とができなかった。[Table 2] According to Comparative Examples 1A, 1B, 2A, and 2B in which the pH value of the dispersion liquid exceeds 11.2 from Tables 1 and 2, the positive electrode material slurry did not have fluidity, and a positive electrode plate that effectively functions as a battery could not be formed. Was.
【００１８】次に比較例１Ａ，１Ｂ，２Ａ，２Ｂを除く
各正極板を用いて図１に示す試験用のリチウムイオン二
次電池を作った。本図に示すように、リチウムイオン二
次電池は、巻回式極板群１が電池缶２内に収納された構
造を有している。そして、巻回式極板群１は、正極板３
と負極板４とが電解質層（セパレータ）５を介して積層
するように巻回された構造を有している。正極板３は正
極集電体６の両面に正極材層７が形成された構造を有し
ている。また、負極板４は負極集電体８の両面に負極材
層９が形成された構造を有している。リチウムイオン二
次電池は次のように製造した。まず、負極板４を製造し
た。最初に、平均粒子径１５μｍの黒鉛の炭素材料から
なる負極材９０重量％と、ポリフッ化ビニリデンからな
るバインダ１０重量％とを混合した。なお、負極材とし
ては非晶質炭素を用いることもできる。これにＮ−メチ
ル−２−ピロリドン（ＮＭＰ）からなる溶媒を適量加え
て十分に混練して負極スラリーを作った。次に１０μｍ
×５０ｍｍ×４９０ｍｍの帯状の銅箔からなる負極集電
体８の両面にロールトゥロール転写により負極材スラリ
ーを塗布してから乾燥、プレスして両面にそれぞれ厚み
１０５μｍの負極材層９を形成して負板４を作った。な
お、この負極材層９の密度は１．３〜１．４５ｇ／ｃｍ
3 である。Next, a test lithium ion secondary battery shown in FIG. 1 was prepared using each positive electrode plate except Comparative Examples 1A, 1B, 2A and 2B. As shown in the figure, the lithium ion secondary battery has a structure in which a wound electrode group 1 is housed in a battery can 2. Then, the wound electrode group 1 includes the positive electrode plate 3
And a negative electrode plate 4 are wound so as to be laminated with an electrolyte layer (separator) 5 interposed therebetween. The positive electrode plate 3 has a structure in which a positive electrode material layer 7 is formed on both surfaces of a positive electrode current collector 6. The negative electrode plate 4 has a structure in which a negative electrode material layer 9 is formed on both surfaces of a negative electrode current collector 8. The lithium ion secondary battery was manufactured as follows. First, the negative electrode plate 4 was manufactured. First, 90% by weight of a negative electrode material made of a graphite carbon material having an average particle diameter of 15 μm and 10% by weight of a binder made of polyvinylidene fluoride were mixed. Note that amorphous carbon can also be used as the negative electrode material. An appropriate amount of a solvent composed of N-methyl-2-pyrrolidone (NMP) was added thereto, and the mixture was sufficiently kneaded to prepare a negative electrode slurry. Next, 10 μm
A negative electrode material slurry is applied to both surfaces of a negative electrode current collector 8 made of a strip-shaped copper foil of × 50 mm × 490 mm by roll-to-roll transfer, dried and pressed to form a negative electrode material layer 9 having a thickness of 105 μm on both surfaces. To make a negative plate 4. The density of the negative electrode material layer 9 is 1.3 to 1.45 g / cm.
3
【００１９】次に、前述の各正極板３と負極板４とを厚
み２５μｍのポリエチレン微多孔膜からなる帯状のセパ
レータ５を介してそれぞれ巻回して極板群１を作った。
次に、極板群１をＮｉめっき鉄からなる円筒形の電池缶
２内に配置してから、予め負極集電体８に溶接してある
ニッケルタブ端子１１を電池缶２の底部２ａに溶接し
た。次に炭酸エチレンと炭酸ジメチルと炭酸ジエチルと
を体積比３０：５０：２０で混合した溶媒にＬｉＰＦ6
からなるリチウム塩を１モル／ｌの濃度で溶解した有機
電解液（非水電解液）を電池缶２内に５ｍｌ注入した。
次に予め正極集電体６に溶接してあるアルミニウムタブ
端子１０を電流遮断機構（圧力スイッチ）及び弁（図示
せず）を備える電池蓋１２に溶接した。なお、この弁は
電流遮断機構（圧力スイッチ）が作動する圧力より高い
圧力で開放作動を行う。そして、電池蓋１２を絶縁性の
ポリプロピレンからなるガスケット１３を介して電池缶
２の上部に配置してから、これをかしめて電池缶２内を
密閉して円筒形の各リチウムイオン二次電池を作った。Next, each of the positive electrode plate 3 and the negative electrode plate 4 was wound around a strip-shaped separator 5 made of a 25 μm-thick polyethylene microporous film to form an electrode plate group 1.
Next, after disposing the electrode plate group 1 in the cylindrical battery can 2 made of Ni-plated iron, the nickel tab terminal 11 previously welded to the negative electrode current collector 8 is welded to the bottom 2 a of the battery can 2. did. Next, LiPF 6 was added to a solvent in which ethylene carbonate, dimethyl carbonate, and diethyl carbonate were mixed at a volume ratio of 30:50:20.
5 ml of an organic electrolyte solution (non-aqueous electrolyte solution) in which a lithium salt of 1 mol / l was dissolved was injected into the battery can 2.
Next, the aluminum tab terminal 10 previously welded to the positive electrode current collector 6 was welded to a battery lid 12 provided with a current cutoff mechanism (pressure switch) and a valve (not shown). This valve opens at a pressure higher than the pressure at which the current cutoff mechanism (pressure switch) operates. Then, after the battery lid 12 is arranged on the upper portion of the battery can 2 via the gasket 13 made of insulating polypropylene, this is caulked and the inside of the battery can 2 is sealed, and each of the cylindrical lithium ion secondary batteries is sealed. Had made.
【００２０】次に各リチウムイオン二次電池を２５℃の
雰囲気中において４．２１Ｖの低電圧（制限電流３２０
ｍＡｈ）で８時間充電してから、１．６Ａで終止電圧
２．５Ｖまで放電して正極材（リチウムニッケル複合酸
化物）１ｇあたりの放電容量を求めた。表１及び２に
は、各正極板を用いて作った電池の放電容量が示されて
いる。表２よりｐＨ値が７．１を下回る比較例２Ｃで
は、活物質が電解液に溶解するため、放電容量が低くな
るのが分かる。Next, each lithium ion secondary battery was placed in a 25 ° C. atmosphere at a low voltage of 4.21 V (with a limiting current of 320
mAh) for 8 hours, and then discharged to a final voltage of 2.5 V at 1.6 A to obtain a discharge capacity per 1 g of the positive electrode material (lithium nickel composite oxide). Tables 1 and 2 show the discharge capacities of the batteries made using each positive electrode plate. From Table 2, it can be seen that in Comparative Example 2C where the pH value was lower than 7.1, the active material was dissolved in the electrolytic solution, so that the discharge capacity was low.
【００２１】次に、表３に示すように、分散液の撹拌時
間または燐酸の添加量を変えて、ｐＨ値が１１．２を上
回る値でそれぞれ異なるリチウムニッケル複合酸化物を
得た。そして、各リチウムニッケル複合酸化物を用い
て、除湿装置による３％ＲＨの雰囲気中で正極材スラリ
ー作成し、リチウムイオン二次電池を作った。なお、正
極材スラリー及びリチウムイオン二次電池は、雰囲気の
湿度を除いては、前述の試験と同じ条件で製造した。そ
して、正極材スラリーの流動性の有無及びリチウムイオ
ン二次電池の正極材（リチウムニッケル複合酸化物）１
ｇあたりの放電容量を調べた。表３はその測定結果を示
している。Next, as shown in Table 3, by changing the stirring time of the dispersion or the added amount of phosphoric acid, different lithium nickel composite oxides having different pH values exceeding 11.2 were obtained. Then, using each lithium nickel composite oxide, a positive electrode material slurry was prepared in an atmosphere of 3% RH by a dehumidifier to prepare a lithium ion secondary battery. The positive electrode material slurry and the lithium ion secondary battery were manufactured under the same conditions as the above-mentioned test except for the humidity of the atmosphere. Then, the presence or absence of fluidity of the positive electrode material slurry and the positive electrode material (lithium nickel composite oxide) 1 of the lithium ion secondary battery
The discharge capacity per g was examined. Table 3 shows the measurement results.
【００２２】[0022]
【表３】 表３より、３％ＲＨの雰囲気中で作成した各正極材スラ
リーは流動性を有しているのが分かる。しかしながら、
各正極材スラリーを用いて製造した電池は、高負荷時の
放電容量が１５４〜１５８ｍＡｈ／ｇと低く、十分な容
量を得ることができないのが分る。したがって、正極材
スラリー生成時に除湿の雰囲気対策を講じても、高負荷
時の放電容量は低いままであるのが分る。[Table 3] Table 3 shows that each positive electrode material slurry prepared in an atmosphere of 3% RH has fluidity. However,
It can be seen that the batteries manufactured using each of the positive electrode material slurries have a low discharge capacity at a high load of 154 to 158 mAh / g, and a sufficient capacity cannot be obtained. Therefore, it can be seen that the discharge capacity under a high load remains low even if countermeasures against dehumidification are taken when the positive electrode material slurry is generated.
【００２３】[0023]
【発明の効果】本発明によれば、水に分散しても強いア
ルカリ性にならないリチウムニッケル複合酸化物を用い
て正極材スラリーを作るので、正極材スラリーに微量に
水分が含まれていても、正極材スラリーは、ほぼ中性ま
たは弱アルカリ性になり、バインダの三次元化を抑制し
て、正極材スラリーがゲル化するのを防ぐことができ
る。According to the present invention, a positive electrode material slurry is prepared using a lithium nickel composite oxide which does not become strongly alkaline even when dispersed in water. Therefore, even if a slight amount of water is contained in the positive electrode material slurry, The positive electrode material slurry becomes substantially neutral or weakly alkaline, thereby suppressing the three-dimensional formation of the binder and preventing the positive electrode material slurry from being gelled.
【図１】本発明の実施例の方法で製造したリチウムイオ
ン二次電池の端面図である。FIG. 1 is an end view of a lithium ion secondary battery manufactured by a method according to an embodiment of the present invention.
１ 巻回式極板群 ２ 電池缶 ３ 正極板 ４ 負極板 ５ 電解質層（セパレータ） ６ 正極集電体 ７ 正極材層 ８ 負極集電体 ９ 負極材層 DESCRIPTION OF SYMBOLS 1 Wound type electrode group 2 Battery can 3 Positive electrode plate 4 Negative electrode plate 5 Electrolyte layer (separator) 6 Positive electrode collector 7 Positive electrode layer 8 Negative electrode collector 9 Negative electrode layer
───────────────────────────────────────────────────── フロントページの続き (72)発明者 鈴木 克典 東京都中央区日本橋本町２丁目８番７号 新神戸電機株式会社内 Ｆターム(参考） 5H029 AJ00 AJ14 AK03 AL06 AM02 AM03 AM07 BJ02 BJ14 CJ07 CJ08 CJ12 CJ22 DJ07 DJ08 EJ12 HJ01 HJ02 HJ10 ────────────────────────────────────────────────── ─── Continued on the front page (72) Katsunori Suzuki 2-8-7 Nihonbashi Honcho, Chuo-ku, Tokyo F-term in Shin-Kobe Electric Co., Ltd. 5H029 AJ00 AJ14 AK03 AL06 AM02 AM03 AM07 BJ02 BJ14 CJ07 CJ08 CJ12 CJ22 DJ07 DJ08 EJ12 HJ01 HJ02 HJ10
Claims (6)
素を含むリチウムニッケル複合酸化物を主成分とする正
極材と、バインダと、有機溶媒とを含むスラリーを集電
体上に塗布してリチウムイオン二次電池用正極板を製造
する方法において、 前記正極材として、前記正極材を水に対して８〜１２重
量％分散させて分散液を作った場合に、前記分散液のｐ
Ｈが７．１〜１１．２になるものを用いることを特徴と
するリチウムイオン二次電池用正極板の製造方法。1. A lithium ion secondary battery comprising: applying a slurry containing a positive electrode material containing a lithium nickel composite oxide containing at least a lithium element and a nickel element as a main component, a binder, and an organic solvent on a current collector; In the method of manufacturing a positive electrode plate for use, when the positive electrode material is dispersed in water by 8 to 12% by weight to form a dispersion,
A method for producing a positive electrode plate for a lithium ion secondary battery, wherein a material having H of 7.1 to 11.2 is used.
とを含むリチウムニッケル複合酸化物材料を水に対して
８〜１２重量％分散させて分散液を作り、 前記分散液のｐＨが７．１〜１１．２になるまで前記分
散液を撹拌し、 次に前記分散液を濾過して、残渣を取出し、 前記残渣を乾燥したものを前記正極材として用いること
を特徴とする請求項１に記載のリチウムイオン二次電池
用正極板の製造方法。2. A dispersion is prepared by dispersing a lithium nickel composite oxide material containing Li 2 O and lithium nickel composite oxide in water in an amount of 8 to 12% by weight, and the dispersion has a pH of 7.1. The dispersion is stirred until the dispersion becomes about 11.2, and then the dispersion is filtered to take out a residue, and the residue is dried and used as the positive electrode material. The method for producing a positive electrode plate for a lithium ion secondary battery according to the above.
とを含むリチウムニッケル複合酸化物材料を水に対して
８〜１２重量％分散させて分散液を作り、 前記分散液のｐＨが７．１〜１１．２になるまで前記分
散液に燐酸を加え、 次に前記分散液を濾過して、残渣を取出し、 前記残渣を乾燥したものを前記正極材として用いること
を特徴とする請求項１に記載のリチウムイオン二次電池
用正極板の製造方法。3. A dispersion is prepared by dispersing a lithium nickel composite oxide material containing Li 2 O and lithium nickel composite oxide in water in an amount of 8 to 12% by weight, and the dispersion has a pH of 7.1. The phosphoric acid is added to the dispersion until the solution reaches ~ 11.2, the dispersion is filtered to remove a residue, and the residue is dried to be used as the positive electrode material. A method for producing a positive electrode plate for a lithium ion secondary battery according to the above.
デンを用い、前記有機溶媒としてＮ−メチル−２−ピロ
リドンを用いることを特徴とする請求項２または３に記
載のリチウムイオン二次電池用正極板の製造方法。4. The positive electrode plate for a lithium ion secondary battery according to claim 2, wherein polyvinylidene fluoride is used as the binder, and N-methyl-2-pyrrolidone is used as the organic solvent. Production method.
素を含むリチウムニッケル複合酸化物を主成分とする正
極材と、バインダと、有機溶媒とを含むスラリーが集電
体上に塗布されて形成されるリチウムイオン二次電池用
正極板において、 前記正極材は、Ｌｉ2 ＣＯ3 を含んでいるリチウムイオ
ン二次電池用正極板。5. A lithium ion formed by applying a slurry containing a cathode material mainly containing a lithium nickel composite oxide containing at least a lithium element and a nickel element, a binder, and an organic solvent onto a current collector. In the positive electrode plate for a secondary battery, the positive electrode material includes Li 2 CO 3, and the positive electrode plate for a lithium ion secondary battery.
素を含むリチウムニッケル複合酸化物を主成分とする正
極材と、バインダと、有機溶媒とを含むスラリーが集電
体上に塗布されて形成されるリチウムイオン二次電池用
正極板において、 前記正極材は、Ｌｉ3 ＰＯ4 を含んでいるリチウムイオ
ン二次電池用正極板。6. A lithium ion formed by applying a slurry containing a positive electrode material mainly composed of a lithium nickel composite oxide containing at least a lithium element and a nickel element, a binder, and an organic solvent onto a current collector. A positive electrode plate for a lithium ion secondary battery, wherein the positive electrode material contains Li 3 PO 4 .
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26409298A JP3654005B2 (en) | 1998-09-18 | 1998-09-18 | Method for producing positive electrode plate for lithium ion secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26409298A JP3654005B2 (en) | 1998-09-18 | 1998-09-18 | Method for producing positive electrode plate for lithium ion secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000090917A true JP2000090917A (en) | 2000-03-31 |
| JP3654005B2 JP3654005B2 (en) | 2005-06-02 |
Family
ID=17398407
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|---|---|---|---|
| JP26409298A Expired - Fee Related JP3654005B2 (en) | 1998-09-18 | 1998-09-18 | Method for producing positive electrode plate for lithium ion secondary battery |
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| Country | Link |
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