JP2724350B2 - Lithium battery - Google Patents
Lithium batteryInfo
- Publication number
- JP2724350B2 JP2724350B2 JP63057662A JP5766288A JP2724350B2 JP 2724350 B2 JP2724350 B2 JP 2724350B2 JP 63057662 A JP63057662 A JP 63057662A JP 5766288 A JP5766288 A JP 5766288A JP 2724350 B2 JP2724350 B2 JP 2724350B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode active
- active material
- lithium
- negative electrode
- positive electrode
- 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.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、リチウム電池に関する。更に詳しくは、本
発明は、エネルギー密度が高く、且つ長期に亙って優れ
た充放電特性を有するリチウム二次電池に関する。Description: TECHNICAL FIELD The present invention relates to a lithium battery. More specifically, the present invention relates to a lithium secondary battery having a high energy density and excellent charge / discharge characteristics over a long period of time.
従来の技術 従来から負極にリチウムを使用し、電解液に有機電解
液を使用する、所謂リチウム電池は、小型、軽量であ
り、しかも高いエネルギー密度を有することから近年種
々の用途に使われている。しかしながら、これらの電池
は一次電池であり、充電できないという欠点を有してい
る。2. Description of the Related Art Conventionally, lithium batteries, which use lithium for the negative electrode and organic electrolyte for the electrolyte, have been used in various applications in recent years because of their small size, light weight, and high energy density. . However, these batteries are primary batteries and have the drawback that they cannot be charged.
一方、二次電池の分野では、その高いエネルギー密度
を活かしつつ多数回の充放電が可能なものは未だ実用化
されておらず、各方面で盛んに研究されているが、充分
なものは未だ完成されていないのが実情である。このよ
うな中で非晶質V2O5を正極に使用した電池が、高エネル
ギー密度で充放電特性を有するリチウム二次電池として
開発されている（例えば特開昭61−200667号広報参
照）。On the other hand, in the field of secondary batteries, a battery that can be charged and discharged a number of times while utilizing its high energy density has not yet been put to practical use, and has been actively studied in various fields, but not enough. The fact is that it has not been completed. Under such circumstances, a battery using amorphous V 2 O 5 as a positive electrode has been developed as a lithium secondary battery having a high energy density and charge / discharge characteristics (for example, see JP-A-61-200667). .
発明が解決しようとする問題点 しかしながら、このようなリチウム二次電池にも下記
に示す欠点がある。Problems to be Solved by the Invention However, such lithium secondary batteries also have the following disadvantages.
一般に非晶質物質は、熱力学的に準安定な物質であ
り、経時的に安定な結晶相へと変化するものであり、特
に加熱によりこの変化は促進される。非晶質V2O5も同様
であり、経時的に結晶質V2O5に変化する。而して非晶質
V2O5を正極に用いたリチウム二次電池が経時的に変化
し、結晶質V2O5になった場合、その電池性能、特に充放
電のサイクル特性が劣化するを避け得なくなり、これが
実用上の障害となっているのが現状である。Generally, an amorphous substance is a metastable substance that is thermodynamically stable and changes into a stable crystalline phase over time. In particular, this change is accelerated by heating. The same applies to amorphous V 2 O 5 , which changes to crystalline V 2 O 5 over time. Thus amorphous
When a lithium secondary battery using V 2 O 5 as the positive electrode changes over time and becomes crystalline V 2 O 5 , it is inevitable that the battery performance, especially the charge / discharge cycle characteristics, deteriorates. At present, it is a practical obstacle.
問題点を解決するための手段 本発明の目的は、上記現状を改良し、高エネルギー密
度で長期に亙って充放電特性の良好なリチウム二次電池
を提供することにある。Means for Solving the Problems An object of the present invention is to improve the above-mentioned current situation and to provide a lithium secondary battery having a high energy density and good charge / discharge characteristics over a long period of time.
即ち、本発明は、V2O5にNa2O、K2O、Rb2O、Cs2O、Be
O、MgO、CaO、SrO、ZrO2、Nb2O5、Ta2O5、Cr2O3、Mn
O2、Fe2O3、Co2O3、NiO、ZnO、CdO、Ag2O、Al2O3、Ga2O
3、As2O3、PbO、Tl2O3、CeO2、Nd2O3、Y2O3及びSc2O3か
らなる群より選ばれた酸化物の少なくとも１種又は加熱
・溶融によりこれらの酸化物を生成し得る化合物を１〜
30モル％の割合で添加した混合物を加熱溶融後に急冷し
て得られる非晶物質を正極活物質とし、金属リチウム、
リチウム合金又はリチウムイオンを電気化学的に電解液
中へ生成及び電解液中から消費せしめる物質を負極活物
質とし、前記正極活物質及び負極活物質に対して化学的
に安定であり且つリチウムイオンが前記正極活物質又は
負極活物質と電気化学反応をするための移動を行ない得
る物質を電解質物質としたことを特徴とするリチウム電
池に係る。That is, the present invention, Na 2 O to V 2 O 5, K 2 O , Rb 2 O, Cs 2 O, Be
O, MgO, CaO, SrO, ZrO 2, Nb 2 O 5, Ta 2 O 5, Cr 2 O 3, Mn
O 2 , Fe 2 O 3 , Co 2 O 3 , NiO, ZnO, CdO, Ag 2 O, Al 2 O 3 , Ga 2 O
3 , As 2 O 3 , PbO, Tl 2 O 3 , CeO 2 , Nd 2 O 3 , Y 2 O 3 and at least one oxide selected from the group consisting of Sc 2 O 3 or by heating and melting Compounds capable of forming an oxide of
Amorphous material obtained by heating and melting the mixture added at a ratio of 30 mol% and then rapidly cooling is used as a positive electrode active material, metallic lithium,
A material which electrochemically generates lithium alloy or lithium ion in the electrolytic solution and consumes it from the electrolytic solution is used as the negative electrode active material, and is chemically stable with respect to the positive electrode active material and the negative electrode active material and lithium ion is used. The present invention relates to a lithium battery, wherein a substance which can move to perform an electrochemical reaction with the positive electrode active material or the negative electrode active material is used as an electrolyte material.
本発明のリチウム電池に用いられる正極活物質は、V2
O5に上記特定の酸化物の少なくとも１種を添加した混合
物を加熱溶融後、急冷して得られる非晶質物質である。
斬かる非晶質物質は、従来公知の方法により製造され
る。例えば溶融物を高速回転ロール面又は冷却板上に吹
き出す方法、溶融物を高圧ガスにてアトマイズ化して急
冷する方法等を有効に利用することができる。また、原
料として用いられる上記酸化物の代りに、加熱・溶融に
よって酸化物を生成する化合物（例えば炭酸塩、硝酸
塩、塩酸塩等）を使用しても本質的に同じである。The positive electrode active material used in the lithium battery of the present invention is V 2
An amorphous substance obtained by heating and melting a mixture in which at least one of the above-mentioned specific oxides is added to O 5 and then rapidly cooling the mixture.
The amorphous material is produced by a conventionally known method. For example, a method of blowing a melt onto a high-speed rotating roll surface or a cooling plate, a method of atomizing the melt with a high-pressure gas and rapidly cooling the same can be effectively used. The same applies essentially to the case where a compound that generates an oxide by heating and melting (for example, a carbonate, a nitrate, a hydrochloride, etc.) is used instead of the above oxide used as a raw material.
本発明では、V2O5に添加する上記酸化物等の割合が１
〜30モル％程度、特に５〜25モル％程度が好適である。
添加量が１モル％未満では、添加物の効果が得られず、
V2O5単独の場合とほぼ同様な電池特性となり、逆に30モ
ル％を越えると、非晶質V2O5の高エネルギー密度が損わ
れるので好ましくない。In the present invention, the ratio of the above oxide and the like added to V 2 O 5 is 1
About 30 mol%, especially about 5 to 25 mol% is suitable.
If the added amount is less than 1 mol%, the effect of the additive cannot be obtained,
The battery characteristics are almost the same as those of V 2 O 5 alone. Conversely, if it exceeds 30 mol%, the high energy density of amorphous V 2 O 5 is undesirably deteriorated.
上記正極活物質を用いて正極を形成するに当っては、
例えば正極活物質粉末にアセチレンブラックやケッチェ
ンブラックE.C.のような導電性粉末を添加し、更にポリ
テトラフルオロエチレンのような結着剤の粉末を加えて
混練、圧延することによってシート状のものとしたり、
これを打抜くことによってペレット状に成形することも
でき、これらをステンレス等の電池ケースに圧着すれば
よい。In forming a positive electrode using the positive electrode active material,
For example, a conductive powder such as acetylene black or Ketjen Black EC is added to the positive electrode active material powder, a binder powder such as polytetrafluoroethylene is further added, and the mixture is kneaded and rolled to form a sheet. Or
It can be formed into a pellet by punching it out, and these may be pressed into a battery case made of stainless steel or the like.
一方、負極活物質は、リチウム金属、リチウム合金、
又はリチウムイオンを電気科学的に電解液中へ生成及び
電解液中から消費せしめる物質であり、この例として
は、ポリアセチレン、ポリパラフェニレン、硫化カーボ
ン、ポリアセン、特開昭62−122066号公報に開示の炭素
質材料（例えば該広報の実施例９に用いられ負極材料と
しての炭素質材料ａ等）、熱分解炭素等を挙げることが
できる。これら負極活物質を用いて負極を形成するに当
っては、プレス成形により所定の形状に形成し、正極の
場合と同様にステンレス等の電池ケースに圧着すればよ
い。この場合、予め電池ケース内壁にニッケル等の導電
体網を熔着せしめる等の工夫をしてもよい。On the other hand, the negative electrode active material is lithium metal, lithium alloy,
Or a substance that electrochemically generates lithium ions in an electrolytic solution and consumes them from the electrolytic solution. Examples thereof include polyacetylene, polyparaphenylene, carbon sulfide, polyacene, and JP-A-62-122066. (For example, carbonaceous material a used as a negative electrode material in Example 9 of the publication) and pyrolytic carbon. In forming a negative electrode using these negative electrode active materials, a negative electrode may be formed into a predetermined shape by press molding, and may be press-bonded to a battery case made of stainless steel or the like as in the case of the positive electrode. In this case, a device such as welding a conductor net made of nickel or the like to the inner wall of the battery case in advance may be used.
更に電解質物質としては、プロピレンカーポネート
（PC）、２−メチルテトラヒドロフラン（2MeTHF）、ジ
オキソラン、テトラヒドロフラン（THF）、1,2−ジメト
キシエタン（DME）、エチレンカーボネート（EC）、γ
−ブチロラクトン、ジメチルスルホキシド、アセトニト
リル、ホルムアミド、ジメチルホルムアミド、ニトロメ
タン等の非プロトン性有機溶媒とLiClO4、LiAlCl4、LiB
F4、LiCl、LiPF4、LiAsF6、CF3SO3Li等のリチウム塩と
の組合せ、又はLi+を伝導体とする有機又は無機の固体
電解質等、一般にリチウムを負極活物質として用いた電
池で使用される既知の電解質物質を用いることができ
る。Further, as the electrolyte substance, propylene carbonate (PC), 2-methyltetrahydrofuran (2MeTHF), dioxolan, tetrahydrofuran (THF), 1,2-dimethoxyethane (DME), ethylene carbonate (EC), γ
- butyrolactone, dimethyl sulfoxide, acetonitrile, formamide, dimethyl formamide, aprotic nitromethane such organic solvent and LiClO 4, LiAlCl 4, LiB
A battery generally using lithium as a negative electrode active material, such as a combination with a lithium salt such as F 4 , LiCl, LiPF 4 , LiAsF 6 , CF 3 SO 3 Li, or an organic or inorganic solid electrolyte using Li + as a conductor The known electrolyte materials used in the above can be used.
また電池を構成する上で、必要に応じてポリプロピレ
ン等よりなる微孔性の薄膜状セパレータを用いてもよ
い。In forming the battery, a microporous thin film separator made of polypropylene or the like may be used as necessary.
発明の効果 本発明によれば、エネルギー密度が高く且つ長期に亙
って優れた充放電特性を示すリチウム二次電池が提供さ
れる。斬かる電池は、コイン型電池等種々の分野に有効
に利用され得る。According to the present invention, a lithium secondary battery having a high energy density and excellent charge / discharge characteristics over a long period of time is provided. The battery can be effectively used in various fields such as a coin-type battery.
実 施 例 以下、本発明を具体的な実施例に基づいて説明する
が、本発明はこれら実施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be described based on specific examples, but the present invention is not limited to these examples.
実施例１ 正極活物質は、次のようにして作成した。V2O5に各種
の酸化物を10モル％となるように添加し、乳鉢で十分に
麻酔・混合した後、白金製のノズル中で加熱・溶融し
た。この溶融物を高速で回転する銅製ローター上に吹き
出し、急冷してリボン状の非晶質物を得た。２種の混合
例では各５モル％とした。Example 1 A positive electrode active material was prepared as follows. Various oxides were added to V 2 O 5 so as to be 10 mol%, sufficiently anesthetized and mixed in a mortar, and then heated and melted in a platinum nozzle. The melt was blown onto a high-speed rotating copper rotor and quenched to obtain a ribbon-shaped amorphous material. In the case of two types of mixing, the content was 5 mol% each.
上記で作成した正極活物質を粉砕機で粉砕した。この
粉砕物、アセチレンブラック及びテトラフルオロエチレ
ンを70:25:5（重量比）の割合で混合し、混練後にロー
ルで厚さ0.5mmのシート状とした。このシートから直径1
6mmの正極合剤ペレットを作製した。The positive electrode active material prepared above was pulverized with a pulverizer. The pulverized product, acetylene black and tetrafluoroethylene were mixed at a ratio of 70: 25: 5 (weight ratio), and after kneading, a sheet having a thickness of 0.5 mm was formed with a roll. Diameter 1 from this sheet
A 6 mm positive electrode mixture pellet was produced.
負極活物質としては、リチウム金属のシートから直径
16mmに打抜いたものを使用した。As the negative electrode active material, the diameter from the sheet of lithium metal
The one punched to 16 mm was used.
リチウム箔をステンレス製封口板に押しつけて貼り付
けてからガスケットを取り付け、リチウム負極の上にに
セパレータ、正極合剤ペレットをこの順に置き、1.5モ
ル／のLiAsF6を２−メチルテトラヒドロフランに溶解
した電解液を適量注入し、正極ケースを被せてかしめる
ことにより直径23mm、厚さ2mmの偏平型リチウム二次電
池を得た。A lithium foil is pressed against a stainless steel sealing plate and attached, and then a gasket is attached. A separator and a positive electrode mixture pellet are placed in this order on a lithium negative electrode, and 1.5 mol / LiAsF 6 is dissolved in 2-methyltetrahydrofuran in an electrolytic manner. An appropriate amount of the solution was injected, and a positive electrode case was covered and swaged to obtain a flat lithium secondary battery having a diameter of 23 mm and a thickness of 2 mm.
これらの作製は、全てアルゴン雰囲気下で行なった。 These fabrications were all performed under an argon atmosphere.
得られたリチウム二次電池の縦断面図を第１図に示
す。FIG. 1 shows a longitudinal sectional view of the obtained lithium secondary battery.
斬くして得られるリチウム二次電池の長期の充放電特
性は、60℃で４ヶ月間保存した後、充放電を繰返し、放
電容量の低下を調べることで評価した。The long-term charge / discharge characteristics of the lithium secondary battery obtained by cutting were evaluated by storing at 60 ° C. for 4 months, repeating charge / discharge, and examining a decrease in discharge capacity.
結果を下記第１表に示す。また第１表には、比較のた
めのV2O5単独の非晶質物質を用いた電池の結果も併せて
示す。尚、充放電は、1mAの定電流で、2Vと3.5Vの間の
電圧規制で行なった。The results are shown in Table 1 below. Table 1 also shows the results of a battery using an amorphous substance of V 2 O 5 alone for comparison. The charge / discharge was performed at a constant current of 1 mA and a voltage regulation between 2 V and 3.5 V.
実施例２ V2O5に添加する酸化物の濃度を変える以外は、実施例
１と同様にしてリチウム二次電池を得、その性能を調べ
た。結果を下記第２表に示す。 Example 2 A lithium secondary battery was obtained in the same manner as in Example 1 except that the concentration of the oxide added to V 2 O 5 was changed, and its performance was examined. The results are shown in Table 2 below.
実施例３ 負極活物質をLi−Al合金とし、電解液の種類を変更す
る以外は、実施例１と同様にしてリチウム二次電池を
得、その性能を調べた。但しLi−Al合金負極の作製は、
通常行なわれているように所定の形状のAl箔とLi箔（Al
箔とLi箔は同じ厚さ）を圧着したものを電池ケース内に
はめこみ、エージングすることによってLi−Al合金負極
とした。結果を下記第３表に示す。 Example 3 A lithium secondary battery was obtained in the same manner as in Example 1 except that the negative electrode active material was a Li-Al alloy and the type of the electrolytic solution was changed, and its performance was examined. However, the production of the Li-Al alloy negative electrode
Al foil and Li foil (Al
The foil and the Li foil having the same thickness were pressed into a battery case, and aged to obtain a Li-Al alloy negative electrode. The results are shown in Table 3 below.
【図面の簡単な説明】 第１図は、本発明の一具体例である偏平型リチウム二次
電池の縦断面図である。 １……封口板、２……ガスケット、 ３……正極ケース、４……リチウム負極、 ５……セパレータ、６……正極合剤ペレットBRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a longitudinal sectional view of a flat type lithium secondary battery as one specific example of the present invention. DESCRIPTION OF SYMBOLS 1 ... Sealing plate, 2 ... Gasket, 3 ... Positive case, 4 ... Lithium negative electrode, 5 ... Separator, 6 ... Positive electrode mixture pellet
Claims (1)
O、CaO、SrO、ZrO2、Nb2O5、Ta2O5、Cr2O3、MnO2、Fe2O
3、Co2O3、NiO、ZnO、CdO、Ag2O、Al2O3、Ga2O3、As
2O3、PbO、Tl2O3、CeO2、Nd2O3、Y2O3及びSc2O3からな
る群より選ばれた酸化物の少なくとも１種又は加熱・溶
融によりこれらの酸化物を生成し得る化合物を１〜30モ
ル％の割合で添加した混合物を加熱溶融後に急冷して得
られる非晶質物質を正極活物質とし、金属リチウム、リ
チウム合金又はリチウムイオンを電気化学的に電解液中
へ生成及び電解液中から消費せしめる物質を負極活物質
とし、前記正極活物質及び負極活物質に対して化学的に
安定であり且つリチウムイオンが前記正極活物質又は負
極活物質と電気化学反応をするための移動を行ない得る
物質を電解質物質としたことを特徴とするリチウム電
池。1. A to V 2 O 5 Na 2 O, K 2 O, Rb 2 O, Cs 2 O, BeO, Mg
O, CaO, SrO, ZrO 2 , Nb 2 O 5, Ta 2 O 5, Cr 2 O 3, MnO 2, Fe 2 O
3 , Co 2 O 3 , NiO, ZnO, CdO, Ag 2 O, Al 2 O 3 , Ga 2 O 3 , As
2 O 3 , PbO, Tl 2 O 3 , CeO 2 , Nd 2 O 3 , Y 2 O 3 and at least one oxide selected from the group consisting of Sc 2 O 3 or these oxides by heating and melting An amorphous material obtained by heating and melting a mixture obtained by adding a compound capable of forming a compound at a ratio of 1 to 30 mol% after heating and melting is used as a positive electrode active material, and lithium metal, a lithium alloy or lithium ions are electrochemically electrolyzed. A substance which is produced in a liquid and consumed from the electrolyte is used as a negative electrode active material, and is chemically stable with respect to the positive electrode active material and the negative electrode active material, and lithium ions are electrochemically mixed with the positive electrode active material or the negative electrode active material. A lithium battery, wherein a substance capable of performing a transfer for performing a reaction is an electrolyte substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63057662A JP2724350B2 (en) | 1988-03-10 | 1988-03-10 | Lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63057662A JP2724350B2 (en) | 1988-03-10 | 1988-03-10 | Lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01231271A JPH01231271A (en) | 1989-09-14 |
| JP2724350B2 true JP2724350B2 (en) | 1998-03-09 |
Family
ID=13062113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63057662A Expired - Fee Related JP2724350B2 (en) | 1988-03-10 | 1988-03-10 | Lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2724350B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0574456A (en) * | 1991-03-07 | 1993-03-26 | Fuji Photo Film Co Ltd | Lithium secondary battery |
| JPH07122275A (en) * | 1993-05-25 | 1995-05-12 | Wilson Greatbatch Ltd | Cathode for electrochemical battery, its manufacture and electrochemical battery |
| JP2003077541A (en) * | 2001-08-31 | 2003-03-14 | Mitsubishi Heavy Ind Ltd | Battery device and its electrode |
| WO2013011568A1 (en) * | 2011-07-19 | 2013-01-24 | 株式会社日立製作所 | Electrode for ion secondary batteries, method for producing electrode for ion secondary batteries, lithium ion secondary battery, and magnesium ion secondary battery |
| CN109461905B (en) * | 2018-09-30 | 2022-01-14 | 肇庆市华师大光电产业研究院 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN111682193A (en) * | 2020-06-12 | 2020-09-18 | 成都理工大学 | Li2O-V2O5-Fe2O3Amorphous state lithium ion battery anode material and preparation method thereof |
| CN114335552B (en) * | 2022-03-15 | 2022-06-24 | 浙江帕瓦新能源股份有限公司 | Positive electrode material, modification process thereof and solid-state battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01128355A (en) * | 1987-11-11 | 1989-05-22 | Nippon Telegr & Teleph Corp <Ntt> | Nonaqueous solvent cell |
-
1988
- 1988-03-10 JP JP63057662A patent/JP2724350B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01231271A (en) | 1989-09-14 |
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| LAPS | Cancellation because of no payment of annual fees |