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TW389001B - Novel lithium batteries - Google Patents

Novel lithium batteries Download PDF

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Publication number
TW389001B
TW389001B TW087109550A TW87109550A TW389001B TW 389001 B TW389001 B TW 389001B TW 087109550 A TW087109550 A TW 087109550A TW 87109550 A TW87109550 A TW 87109550A TW 389001 B TW389001 B TW 389001B
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TW
Taiwan
Prior art keywords
calcium carbonate
lithium battery
patent application
cathode
item
Prior art date
Application number
TW087109550A
Other languages
Chinese (zh)
Inventor
Louis Merckaert
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Solvay
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Publication of TW389001B publication Critical patent/TW389001B/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Separators (AREA)

Abstract

Electrochemical cells known as lithium batteries wherein at least one of the anodes, cathodes and/or separator elements thereof contains PVdF homopolymers and/or copolymers and in which calcium carbonate is also incorporated in said battery and, more particularly, in at least one of the anode, cathode and/or separator element thereof. The incorporation of such calcium carbonate acts to reduce or eliminate free acid available which may contribute to the occurrence and/or intensity of runaway exothermic reactions in said battery. Chlcium carbonates having a mean particle size of at least about 0.10 mu m are preferred

Description

經濟部中夾摞"-局負工消费合作社印奴 A7 B7 五、發明説明q ) 本發明有關於一種電化學的鋰電池，其具有負極、正 極以及介於其間之分隔元件，其中至少電極或分隔器之一 者含有έ成聚合物材料。 鋰電池爲如下類型之電池：具有至少一個電化電池， 其中，在放電循環時鋰離子由陽極移動至陰極（以及，若 爲充電式鋰電池，在充電循環時鋰離子由陰極移動至陽極 )。這類電池可爲單一或多個排列方式，各個包括負電極 (陽極）、正電極（陰極）與介於陰極與陽極間之分隔元 件。 有許多不同類型之鋰電池。第一代之鋰電池的陽極爲 鋰金屬，陽極包括可於放電時將鋰離子內插（intercalating )至結構中之化合物。此類鋰電池的例子見於U. Von Sacken 等人，Solid State Ionics, 69(1994)284-290。 在第二代之鋰電池中，建議將陽極中之鋰金屬換成能 夠將鋰內插之各種形式的碳，如，石墨，石油焦炭，所以 其電極能夠可逆地將鋰離子內插至其結構中。此類鋰電池 的例子見於 U. Von Sacken 等人，Solid State Ionics，69 ( 1994) 284-290 。 鋰電池另可具有各種不同結構之分隔元件（或「膜」 )以及下述結構，此結構中含有電解質而在電池的放電循 環（或是充電電池之充電•循環）中令鋰離子經過該電解質 而在電極間移動。此電解質可呈下列形式：液體（例如， 鋰鹽，如L i PF6，L i BF4或L i C 1 〇4，於有機 溶劑（如，環烯碳酸酯，二乙氧基乙烷或二甲基甲醯胺） 本纸張尺度適用中國國家揉準（CNS >A4規格（2丨0X297公釐） ---------- r _ (請先閲讀背面之注意事項再填寫本頁)In the Ministry of Economic Affairs " -Industrial Cooperative Consumer Cooperative Innu A7 B7 V. Description of the Invention q) The present invention relates to an electrochemical lithium battery having a negative electrode, a positive electrode, and a separator element therebetween, wherein at least the electrode Or one of the dividers contains a polymer material. Lithium batteries are types of batteries that have at least one electrochemical cell in which lithium ions move from the anode to the cathode during a discharge cycle (and, in the case of a rechargeable lithium battery, lithium ions move from the cathode to the anode during a charge cycle). These batteries can be arranged in a single or multiple ways, each including a negative electrode (anode), a positive electrode (cathode), and a separator between the cathode and anode. There are many different types of lithium batteries. The anode of the first-generation lithium battery was lithium metal, and the anode included a compound capable of intercalating lithium ions into the structure during discharge. Examples of such lithium batteries are found in U. Von Sacken et al., Solid State Ionics, 69 (1994) 284-290. In the second generation of lithium batteries, it is recommended to replace the lithium metal in the anode with various forms of carbon capable of intercalating lithium, such as graphite and petroleum coke, so its electrodes can reversibly interpolate lithium ions into its structure in. Examples of such lithium batteries are found in U. Von Sacken et al., Solid State Ionics, 69 (1994) 284-290. Lithium batteries can also have separator elements (or "films") of various structures and the following structure. This structure contains an electrolyte to allow lithium ions to pass through the electrolyte during the battery's discharge cycle (or the charge / cycle of a rechargeable battery). And move between the electrodes. This electrolyte can be in the form of a liquid (for example, a lithium salt, such as Li PF6, Li BF4, or Li C 1 〇4, in an organic solvent (for example, cycloolefin carbonate, diethoxyethane, or dimethyl ether). Methylmethoxamine) This paper size applies to the Chinese national standard (CNS > A4 size (2 丨 0X297 mm) ---------- r _ (Please read the precautions on the back before filling in this page)

,1T -4- 經濟部中央標準局負工消费合作社印^ A7 B7 五、發明説明i ) 中所成溶液，凝膠（例如’ PVdF與碳酸酯，如，碳酸 乙二酯，丙二酯與二甲酯）或是固體（例如，聚偏二氟乙 烯（P + d F )與碳酸酯，如.’碳酸乙二酯，丙二酯與二 甲酯，以及特別設計之高離子導性的玻璃狀物質）。 此類鋰電池的例子見於US 5587253與 5 5 8 0 6 8 2。 其他被提出之鋰電池爲其陰極亦包括能夠內插鋰離子 之物質，所以，陰極與陽極均包括內插物質。 亦發現，爲了多種目的，在鋰電池的電極及/或分隔 元件之結構與疊層中使用聚合材料（例如，作爲結合劑） 。此聚合材料的例子爲聚偏二氟乙烯（P V d F )均聚物 與共聚物樹脂，如，聚（偏二氟乙烯-氯三氟乙烯），聚 (偏二氟乙嫌一四氟乙稀），聚（偏二氟乙嫌一六氟丙嫌 )(PVdF:HFP)與聚（偏二氟乙烯—三氟乙烯） 。特佳者爲含8%HFP之PVdF:HFP共聚物，市 售者有SOLEF®20810;與含約8%至20% CTFE之SOLEF ®3XXXX系列聚（偏二氟乙烯 —氯三氟乙烯）（PVdF:CTFE)共聚物，二者均 爲S 0 L V A Y ( Belgium )之產品。使用此類聚合材料之 鋰電池的例子見於U S 5 5 7 1 6 3 4。 鋰電池在使用時會有一個顯著的問題，即內部短路與 過充電，而引起不可收拾的放熱反應。這些短路或過充電 可能是電池本身的設計所引起（例如，鋰樹枝狀結晶形成 的結果）或是外部因素的結果，例如，不當使用或意外。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁), 1T -4- Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Consumer Cooperatives ^ A7 B7 V. Description of the invention i) Solution, gel (for example, 'PVdF and carbonates, such as ethylene carbonate, propylene glycol and Dimethyl esters) or solids (for example, polyvinylidene fluoride (P + d F) and carbonates, such as. 'Ethylene carbonate, propylene esters and dimethyl esters, and specially designed high ion conductivity Glassy substance). Examples of such lithium batteries are found in US 5587253 and 5 5 0 6 8 2. Other proposed lithium batteries include cathodes that include substances capable of intercalating lithium ions. Therefore, both cathodes and anodes include intercalating substances. It has also been found that for a variety of purposes, polymer materials (for example, as binders) are used in the structure and stacking of electrodes and / or separators of lithium batteries. Examples of this polymeric material are polyvinylidene fluoride (PV d F) homopolymers and copolymer resins, such as poly (vinylidene fluoride-chlorotrifluoroethylene), poly (vinylidene fluoride-tetrafluoroethylene) Diluted), poly (vinylidene fluoride, hexafluoropropylene) (PVdF: HFP) and poly (vinylidene fluoride-trifluoroethylene). Particularly preferred are PVdF: HFP copolymers containing 8% HFP. Commercially available are SOLEF®20810; and SOLEF®3XXXX series poly (vinylidene fluoride-chlorotrifluoroethylene) containing about 8% to 20% CTFE ( PVdF: CTFE) copolymer, both of which are products of S 0 LVAY (Belgium). Examples of lithium batteries using such polymeric materials are found in US 5 5 7 1 6 3 4. Lithium batteries have a significant problem when they are used, that is, internal short circuits and overcharges, which cause an exorbitant exothermic reaction. These short circuits or overcharges may be caused by the design of the battery itself (for example, the formation of lithium dendrites) or external factors, such as improper use or accident. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

-5- 經濟部中央標隼局貝工消费合作社印衮 A7 ______B7__ 五、發明説明& ) 不可收拾的放熱反應之真正起因並不淸楚，而且特別危險 ’因爲其有時可能造成，例如，嚴重爆炸。 消#及/或控制此等不可收拾之反應的對策主要是改 變/置換所用電解質（參考，例如，U S 4 8 3 0 9 3 9 與EP申請案號0766329案）。 雖然PV d F不被認爲是造成短路及/或過充電的因 素，但認爲不可收拾的放熱反應會使得P V d F均聚物及 /或共聚物去氫.氟化，因而釋出酸，如H F及/或H C < ，其已知會自催化Ρ V d F均聚物及/或共聚物之降解。 我們相信這會使得上述現象更加嚴重。 所以有人建議將所用P V d F均聚物及/或共聚物換 成其他聚合物，如，聚環氧乙烷（PEO)，聚丙嫌腈（ PAN)與聚四氟乙烯（PTFE)。不幸地，這些其他 聚合物並未得出有利的性質，例如，在寬廣溫度範圍中之 離子導電性以及形成凝膠（這些是P V d F均聚物及/或 共聚物所擁有的優點）。 因此仍有需要解決不可收拾放熱反應之其他方法，並 可將P V d F均聚物及/或共聚物倂入鋰電池之電極及/ 或分隔元件至少一者之中，使不可收拾的放熱反應消除或 是強度降低。 本發明主要目的在於提出鋰電池之陽極、陰極及/或 分隔元件，其中倂有P V d F均聚物及/或共聚物，所以 消除了或降低不可收拾放熱反應之程度。 .本發明另一主要目的在於提出一種鋰電池，其中 本紙張尺度適用中國國家梂準（（:NS ) Λ4現格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁)-5- Seal of the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 ______B7__ 5. Explanation of the invention &) The real cause of the exorbitant exothermic reaction is not clear, and it is particularly dangerous because it may sometimes cause, for example, Serious explosion. The countermeasures to eliminate these and / or control these uncontrollable reactions are mainly to change / replace the electrolyte used (see, for example, US 4 8 3 0 9 3 9 and EP application number 0766329). Although PV d F is not considered to be a cause of short circuit and / or overcharge, it is believed that the exothermic exothermic reaction will cause the PV d F homopolymer and / or copolymer to dehydrogenate. Fluorination, and thus releases acid , Such as HF and / or HC <, are known to autocatalyze the degradation of the P V d F homopolymer and / or copolymer. We believe this will make the above phenomenon even worse. Therefore, it has been suggested to replace the P V d F homopolymers and / or copolymers with other polymers, such as polyethylene oxide (PEO), polyacrylonitrile (PAN), and polytetrafluoroethylene (PTFE). Unfortunately, these other polymers do not lead to advantageous properties, such as ionic conductivity over a wide temperature range and gel formation (these are the advantages possessed by P V d F homopolymers and / or copolymers). Therefore, there is still a need for other methods to solve the exothermic exothermic reaction, and the PV d F homopolymer and / or copolymer can be incorporated into at least one of the electrodes and / or separators of the lithium battery to eliminate the exothermic exothermic reaction. Or the intensity decreases. The main purpose of the present invention is to propose an anode, a cathode and / or a separator of a lithium battery, in which a P V d F homopolymer and / or a copolymer are incorporated, so that the degree of unrecoverable exothermic reaction is eliminated or reduced. . Another main purpose of the present invention is to propose a lithium battery, in which the paper size is applicable to the Chinese national standard ((: NS) Λ4 current grid (210X 297 mm) (Please read the precautions on the back before filling this page)

經濟部中央標準局負.工消费合作社印製 A7 B7 五、發明説明ς ) P V d F均聚物及/或共聚物被併人電極及/'或分隔元件 之至少一者中，因而消除或降低不可收拾放熱反應之程度 〇 本發明另一目的在於確認P V d F均聚物及/或共聚 物在鋰電池之短路/過充電引起之不可收拾放熱反應中所 扮演的角色，進而消除及/或減輕該因素。 本發明另一目的在於提出消除及/或降低不可收拾放 熱反應之危險度的方法，前述反應會發生於特定類型之鋰 電池中，即，其陽極、陰極及/或分隔元件中至少一者倂 有P V d F均聚物及/或共聚物。 .依本發明之教導，揭示一種鋰電池，其陽極、陰極及 /或分隔元件至少一者含有聚偏二氟乙嫌（P V d F )均 聚物及/或共聚物，且其陽極、陰極及/或分隔元件至少_ 一者含有碳酸鈣（CaC〇3)。此設計中，碳酸鈣（ C a C 0 3 )可作爲酸淸除劑（例如，淸除H F及/或 H C 〇 ，因而降低或消除可用的自由酸（HF及/或 HC<)〔其會助長不可收拾放熱反應發生及/或使之增 強〕。 ， 在較佳具體例中，碳酸鈣被倂入至少該鋰電池之陽極 中。 另一較佳具體例中碳係呈石墨形式。 另一較佳具體例中，該碳酸鈣之平均粒徑至少爲約 0 . 1 0 // m。 ’另一較佳具體例中，碳酸鈣之平均粒徑至少爲約 本紙張尺度適用中國國家標嗥（CNS ) Λ4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本買) 訂 經濟部中央標準局員工消费合作社印褽 A7 _ B7 _ 五、發明説明（5 ) 0 . 1 8 A m 〇 另一較佳具體例中，碳酸鈣之平均粒徑至少爲約 0 · 2 β τα a 另一較佳具體例中，碳酸鈣之平均粒徑至少爲約 0 . 3 6 y m。 本發明另一方面揭示用於鋰電池之陽極，其中含有聚 偏二氟乙烯（PV d F )均聚物及/或共聚物，且該陽極 中另含有碳酸鈣（CaC〇3)。依此設計，碳酸鈣（ C a C〇3)可作爲酸淸除劑（例如淸除HF及/或HC < )，因而降低或消除可用的自由酸（HF及/或HC<) 〔其會助長不可收拾放熱反應發生及/或使之增強〕。 另一較佳具體例中，碳係呈石墨形式。 另一較佳具體例中，碳酸鈣（C a C〇3)爲市售商標 爲SOCAL ®之碳酸鈣。 另一較佳具體例中，碳酸鈣之平均粒徑至少爲約 0 . 1 0 // m。 另一較佳具體例中，碳酸鈣之平均粒徑至少爲約 0 . 1 8 // m。 另一較佳具體例中，碳酸鈣之平均粒徑至少爲約 0 . 2 # m。 < 另一較佳具體例中，碳酸鈣之平均粒徑至少爲約 0 . 3 6 # m。 依本發明教導，本發明另一方面揭示用於鋰電池之陰 極，其中含有聚偏二氟乙烯（PV d F )均聚物及/或共 本紙張尺度適用中國國家揉率（CNS ) Λ4規格（210X 297公釐） ---------------訂------武 -~ (請先閲讀背面之注意事項再填寫本頁) -8- 經濟部中央標隼局員工消費合作社印製 A7 B7 7、發明説明（6 ) 聚物，且該陽極中另含有碳酸鈣（C a C〇3)。依此設計 ，碳酸鈣（C a C 0 3 )可作爲酸淸除劑（例如淸除H F及 /或H b ，因而降低或消除可用的自由酸（HF及/ 或HC<)〔其會助長不可收拾放熱反應發生及/或使之 增強〕。 另一較佳具體例中，碳酸鈣（Ca C〇3)爲市售商標 爲SOCAL ®之碳酸鈣。 另一較佳具體例中，碳酸鈣之平均粒徑至少爲約 〇 . 1 〇 m。 另一較佳具體例中，碳酸鈣之平均粒徑至少爲約 〇 . 1 8 # m。 另一較佳具體例中，碳酸鈣之平均粒徑至少爲約 0 . 2 〆 m。 另一較佳具體例中，碳酸鈣之平均粒徑至少爲約 〇 . 3 6 〆 m。 較好此陰極亦含有碳。 另一較佳具體例中，碳係呈石墨形式。 本發明另一方面揭示消除及/或降低不可收拾放熱反 應之危險程度的方法，該危險會發生在下述類型之鋰電池 中：該電池之陰極、陽極及/或分隔元件$中至少一者倂有 P V d F均聚物及/或共聚物。此方法的特徵在於將碳酸 鈣倂入鋰電池之陰極、陽極及/或分隔元件中至少一者之 中〇 此方法另一較佳具體例在於碳酸鈣爲SOCAL⑧。 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)The Central Standards Bureau of the Ministry of Economic Affairs bears the responsibility. A7 B7 printed by the Industrial and Consumer Cooperatives. 5. Description of the invention) PV d F homopolymer and / or copolymer is incorporated into at least one of the electrode and / 'or the separator, thus eliminating or Reducing the degree of unrecoverable exothermic reactions. Another object of the present invention is to confirm the role of PV d F homopolymers and / or copolymers in unrecoverable exothermic reactions caused by short-circuit / overcharge of lithium batteries, thereby eliminating and / or Mitigate this factor. Another object of the present invention is to propose a method for eliminating and / or reducing the danger of an unpackable exothermic reaction, which may occur in a specific type of lithium battery, that is, at least one of its anode, cathode, and / or separator element. There are PV d F homopolymers and / or copolymers. According to the teachings of the present invention, a lithium battery is disclosed, in which at least one of the anode, cathode and / or separator element contains polyvinylidene difluoride (PV d F) homopolymer and / or copolymer, and its anode, cathode And / or at least one of the separation elements contains calcium carbonate (CaC03). In this design, calcium carbonate (C a C 0 3) can be used as an acid scavenger (for example, to remove HF and / or HC 〇, thereby reducing or eliminating available free acids (HF and / or HC <) [its It promotes the occurrence of exothermic reactions and / or enhances them.] In the preferred embodiment, calcium carbonate is incorporated into at least the anode of the lithium battery. In another preferred embodiment, the carbon is in the form of graphite. In a preferred embodiment, the average particle size of the calcium carbonate is at least about 0.10 // m. 'In another preferred embodiment, the average particle size of the calcium carbonate is at least about 1 CNS) Λ4 specification (210X 297 mm) (please read the precautions on the back before filling in this purchase) Order the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 _ B7 _ V. Description of the invention (5) 0. 1 8 A m 〇 In another preferred embodiment, the average particle size of calcium carbonate is at least about 0.2 β τα a. In another preferred embodiment, the average particle size of calcium carbonate is at least about 0.36 ym. Another aspect discloses anodes for lithium batteries, which contain polyvinylidene fluoride (PV d F) homopolymer and / or copolymer, and the anode additionally contains calcium carbonate (CaC03). Based on this design, calcium carbonate (CaC03) can be used as an acid scavenger (for example, HF and And / or HC <), thereby reducing or eliminating available free acids (HF and / or HC <) [which promotes and / or enhances the occurrence of uncontrollable exothermic reactions]. In another preferred embodiment, the carbon system It is in the form of graphite. In another preferred embodiment, calcium carbonate (CaCO3) is a commercially available calcium carbonate under the trademark SOCAL®. In another preferred embodiment, the average particle diameter of calcium carbonate is at least about 0. 1 0 // m. In another preferred embodiment, the average particle diameter of calcium carbonate is at least about 0.1 8 // m. In another preferred embodiment, the average particle diameter of calcium carbonate is at least about 0. 2 # m. ≪ In another preferred embodiment, the average particle diameter of calcium carbonate is at least about 0.3 6 # m. According to the teaching of the present invention, another aspect of the present invention discloses a cathode for a lithium battery, which contains Polyvinylidene fluoride (PV d F) homopolymer and / or co-paper size applicable to China National Kneading Rate (CNS) Λ4 specification (210X 297 mm) -------------- - ------ Wu- ~ (Please read the notes on the back before filling out this page) -8- Printed by the Consumers Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 7, Invention Description (6) Polymer, and the The anode additionally contains calcium carbonate (C a C03). Based on this design, calcium carbonate (C a C 0 3) can be used as an acid scavenger (eg, to remove HF and / or H b), thereby reducing or eliminating the available Free acid (HF and / or HC <) [which promotes and / or enhances the occurrence of unpackable exothermic reactions]. In another preferred embodiment, calcium carbonate (Ca C03) is a calcium carbonate commercially available under the trademark SOCAL®. In another preferred embodiment, the average particle size of the calcium carbonate is at least about 0.10 m. In another preferred embodiment, the average particle diameter of the calcium carbonate is at least about 0.18 #m. In another preferred embodiment, the average particle size of the calcium carbonate is at least about 0.2 μm. In another preferred embodiment, the average particle diameter of the calcium carbonate is at least about 0.36 μm. Preferably this cathode also contains carbon. In another preferred embodiment, the carbon system is in the form of graphite. Another aspect of the present invention discloses a method for eliminating and / or reducing the degree of danger of an unpackable exothermic reaction, which may occur in the following types of lithium batteries: at least one of a cathode, an anode and / or a separator element of the battery 电池There are PV d F homopolymers and / or copolymers. This method is characterized in that calcium carbonate is incorporated into at least one of the cathode, anode, and / or separator of a lithium battery. Another preferred embodiment of this method is that calcium carbonate is SOCAL (R). This paper size applies to Chinese National Standard (CNS) Λ4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

-9 - 經濟部中央標準局貞工消費合作社印-11 A7 B7____ 五、發明説明（7 ) 此方法另一較佳具體例爲碳酸鈣之平均粒徑至少爲約 0 . 1 0 〆 m。 在i發明中，吾人相信鋰電池在不當使用或意外時產 生的不可收拾放熱反應可能與酸（如H F及/或HC < ) 自催化Ρ V d F均聚物及/或共聚物之去氫氟化有關。、有 鑑於此，使用碳酸鈣（CaC〇3)〔併入電池之陽極及/ 或陰極及/或分隔元件〕，其作爲酸淸除劑，可以降低或 消除可用的自由酸（如HF與HC<)，該自由酸可使不 可收拾之放熱反應發生或是使其增強。此外，於陽極及/ 或陰極及/或分隔元件中加入C a C〇3並不會影響鋰電池 之電化性質。 本發明另有關吾人另外之意外發現：平均粒徑爲至少 約0 . ΙΟμιη的CaC〇3(較好爲至少約Q . 18vm )，相較於少於約0.10#m者，具有顯著較強之「酸 淸除劑」功效，更特別地，「H F淸除劑」功效。 此一發現相當出人意料之外，因爲通常會認爲 C a C 0 3之酸（如H F及/或H C < )淸除力直接與總表 面積（可用來與酸接觸而淸除之）成正比，亦却，與酸起 化學反應而化學鍵結之程度成正比。所以，一般會認爲平 均粒徑較小的C a C 〇3，因爲總表面積p大，較有效地作 爲「酸淸除劑」（相較於同用量但平均粒徑較大的 CaC〇3而言）。所以，發現到平均粒徑至少約0.18 之C a C〇3具有特別高之酸淸除效率更是特別出人意 料且値得注意。 本紙張尺度適用中國國家標準（CMS ) A4規格（210X297公釐） ---------Ά------1T------d. (請先閲讀背面之注意事項再填寫本頁) -10- 經濟部中央標率局貝工消费合作社印裝 A7 B7 五、發明説明（8 ) 文中所用「平均粒徑」指依Carman與Malherbe公式算 出之尺寸（Appl. Chem.，I，March 1951，105-108 )，而起 失係用^Blaine的方法進行滲透測量而得出（American Society for Testing and Materials ( ASTM ) norm C 204-81) o 可用於本發明鋰電池與陽極中之C a C 〇3包括，但不 限於，商標爲SOCAL ® (購自SOLVAY)與 Hydrocarb 95T (天然碳酸銘）者。 可用之SOCAL ®的較佳類型包括，但不限於， SOCAL®E2，SOCAL®Np、-9-Printed by Zhengong Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs -11 A7 B7____ 5. Explanation of the invention (7) Another preferred specific example of this method is that the average particle size of calcium carbonate is at least about 0.10 〆 m. In the invention of i, I believe that the unpackable exothermic reaction generated by lithium batteries when used improperly or accidentally may react with acids (such as HF and / or HC <) to auto-catalyze the removal of homopolymer and / or copolymer of PV D Related to hydrofluorination. In view of this, the use of calcium carbonate (CaC03) [anode and / or cathode and / or separator element incorporated into the battery] as an acid scavenger can reduce or eliminate available free acids (such as HF and HC <), The free acid can cause an uncontrollable exothermic reaction to occur or enhance it. In addition, adding Ca C03 to the anode and / or cathode and / or separator does not affect the electrochemical properties of the lithium battery. The present invention is also related to another unexpected discovery of us: CaC03 (preferably at least about Q. 18vm) having an average particle size of at least about 0.1 μm, which is significantly stronger than that of less than about 0.10 # m. "Acid Remover" effect, more specifically, "HF Remover" effect. This finding is quite unexpected, because it is generally thought that the acidic force of Ca C 0 3 (such as HF and / or HC <) is directly proportional to the total surface area (which can be used to contact and remove the acid). However, it is directly proportional to the degree of chemical bond between acid and chemical reaction. Therefore, it is generally considered that C a C 〇3 with a smaller average particle diameter is more effective as an "acid scavenger" because of the large total surface area p (compared with CaC 0 with the same amount but a larger average particle diameter). In terms of). Therefore, it was found that C a C03 having an average particle size of at least about 0.18 having a particularly high acid removal efficiency was particularly unexpected and noticeable. This paper size applies Chinese National Standard (CMS) A4 specification (210X297 mm) --------- Ά ------ 1T ------ d. (Please read the notes on the back first (Fill in this page again) -10- Printed on A7 B7 by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (8) The "average particle size" used in the text refers to the size calculated according to Carman and Malherbe formula (Appl. , I, March 1951, 105-108), and the start-loss system is obtained by ^ Blaine's method for penetration measurement (American Society for Testing and Materials (ASTM) norm C 204-81) o It can be used in the lithium battery of the present invention and The C a C 03 in the anode includes, but is not limited to, those whose trademarks are SOCAL ® (available from SOLVAY) and Hydrocarb 95T (natural carbonate). The preferred types of SOCAL® available include, but are not limited to, SOCAL®E2, SOCAL®Np,

SOC AL®90A、SOCAL®92E， SOCAL®N2，SOCAL®N2R 與 SOCAL ®9 1 CV。特佳者爲 SOCAL ®9 1 CV o 本發明鋰電池中所用，特別是陰極、陽極及/或分隔 元件所用，C a C〇3的量需足以提供各種效能，但也不能 多到影響元件（如電極及/或分隔元件）中活性物質（如 ，碳或石墨）的含量。 所以，依本發明教導，本發明鋰電池與陽極中之 C a C〇3用量可以低至佔電極（即，陽<極）塗層總重之約 0 . 5 % ( w/w )，更好是至少約1% (w/w) ，最 好是至少約5 % (w/w) ，更佳的是至少約7% (w/ w)，而更佳的是至少約8%(w/w)，亦更好的是至 少約10%(w/w)。 本紙張尺度通用中國國家標哗（CNS ) Λ4規格（210Χ 297公釐） (請先閲讀背面之注意事項再填寫本頁) 、?τ -11 - 輕濟部中夬榡準局貝工消費合作社印製 A7 、一 ____ 五、發明説明（9 ) 較好，其用量不超過電極（即，陽極）塗層總重之.約 2 0 % (w/w)，更好是不超過ll%(w/w) ’最 好是不运過1 0% (W'/w.)·。 本發明鋰電池的陰極亦可具有含鋰化過渡金屬氧化物 ，碳，聚偏二氟乙烯（PVdF)均聚物及/或共聚物樹 脂與CaC〇3之塗層。 本發明陰極塗層中可用的锂化過渡金屬氧化物包括 L ixCo〇2，L ixMn2〇4，L ixN i 〇2， L i χ V 2 〇 5與混合氧化物，如， L ixNiaC〇bMn<：〇2，其中 a+b + c = l。可用 於本發明陰極塗層之聚偏二氟乙烯（PVdF)均聚物及 /或共聚物樹脂包括聚（偏二氟乙烯一六氟丙烯）（ PVdF : HFP)共聚物，其含 8% (w/w) HFP ’市售商標爲SOLEF®20810;與含約8%(w /w)至20%(w/w)CTFE之 SOLEF ®3XXX系列聚（偏二氟乙烯一氯三氟乙烯 )(PVdF:CTFE)共聚物，二者均爲 S 0 L V A Y ( Belgium )之產品。本發明陰極中可用之特 佳 P V d F 爲市售 S 0 L V A Y ( Bolgium )之 SOLEF ®1 〇〇8 的 PVdF 均聚物I» 可依本發明將C a C 〇3倂入之陰極的例子係如E P申 請號049 2 586與J P申請號6 3/1 2 1 262與 04/095363 以及 EP 申請號 0205856。 本發明鋰電池中最佳適用之陰極係如下述者：包括位 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210Χ297公釐） ---------',d------ΐτ------Μ • (請先閱讀背面之注意事項再填寫本頁) -12- 經濟部中央標準局員工消费合作社印裝 A7 B7 五、發明説明（彳〇 ) 於銘箱上之含6.0 — 9 4% (w/w)鋰化過渡金屬氧化 物，約3 - 1 0% (w/w)碳（石墨及及/或碳黑）’ 約3_i 〇% (w/w) PVdF均聚物及/或共聚物與 約〇 . 5 — 2 0% (w/w) CaC〇3的塗層’如上文所 說明者。 本發明鋰電池之陰極可視所需地含有其他·元件與成份 ，如添加劑、安定劑等。本發明鋰電池之陰極可具有含碳 (特別是石墨）’聚偏二氟乙烯（p v d F )均聚物及/ 或共聚物樹脂與CaC〇3之塗層。 本發明陽極塗層中較佳之碳爲石墨，可用於本發明陽 極塗層中之聚偏二氟乙烯（PV d F )均聚物及/或共聚 物樹脂包括P V d F均聚物與共聚物。此PV d F共聚物 的例子有：聚（偏二氟乙烯一六氟丙烯）（PVdF: HFP)共聚物，其含8%(w/w) HFP，市售商標 爲 SOLEF®20810 ;與含約 8% (w/w)至 2 0% (w/w) CTFE 之 SOLEF ®3XXX 系列 聚（偏二氟乙烯一氯三氟乙烯）（PVdF:CTFE) 共聚物，二者均爲SOLVAY ( Belgium )之產品。本發 明陽極中可用之特佳PVdF爲市售SOLVAY ( Bolgium )之 SOLEF ®1008 的 PfclF 均聚物。 可依本發明將C a C〇3倂入之陽極的例子係如EP申 請號0492586與JP申請號63/121262與 04/095363 以及 EP 申請號 0205856。 本發明鋰電池中最佳適用之陽極係如下述者：包括位 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210><297公嫠） (請先閲請背面之注意事項再填寫本K ) 4------1T------d--------------^--- •13- 經滴部中夾標準局負工消费合作社印製 A7 B7 五、發明説明（u ) 於銅箔上之含6 0 — 9 9% (w/w)碳（石墨及及/或 碳黑），約1 — 20%(w/w)PVdF均聚物及/或 共聚物备約〇 . 5 — 2 0% (w/w) CaC〇3的塗層’ 如上文所說明者。 若需要，本發明鋰電池之陽極塗層可含有其他元件與 成份，例如，添加劑、安定劑、硬化劑等。此其他元件與 成份的例子爲丁二酸鉍、氫氧化鋁、氫氧化鈣與氫氧化錄 〇 此添加劑的用量可低至佔塗層中p v d F均聚物/共 聚物含量之0%(w/w)，高至約5%(w/w)，即 ，電極塗層總量之0 . 05至1% (w/w)。 本發明鋰電池之電解質可爲任何適宜之固體、凝膠或 液體者，例子有P V d F均聚物及/或共聚物與碳酸酯， 例如，伸乙基、伸丙基與二甲基碳酸酯，以及具有高離子 導電性之特殊設計之玻璃狀物質。本發明鋰電池可用之凝 膠電解質的例子有P V d F均聚物及/或共聚物與碳酸酯 ，如，伸乙基、伸丙基、二甲基與二乙基碳酸酯。可用於 本發明鋰電池之液體電解質的例子有L i PF6， LiBF4，LiCl〇4，且其混有伸乙基、伸丙基、二 甲基與二乙基碳酸酯。 < 本發明鋰電池電極（陰極與陽極）之比面積容量可爲 0 .5mA h / cm2 (電極塗層厚0. 0 2 5mm在乾燥 與壓延後算出）至10mAh/cm2 (電極塗層厚〇 . 5 mm在乾燥與壓延後算出）。較佳比面積容量爲約 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） ----------- -· (請先閲讀背面之注意事項再填寫本頁)SOC AL®90A, SOCAL®92E, SOCAL®N2, SOCAL®N2R and SOCAL®9 1 CV. Particularly preferred is SOCAL ® 9 1 CV o used in the lithium battery of the present invention, especially for the cathode, anode and / or separator element, the amount of C a C03 should be sufficient to provide various performances, but not too much to affect the element ( Such as the electrode and / or separator element) active material (such as carbon or graphite) content. Therefore, according to the teachings of the present invention, the amount of C a C03 in the lithium battery and the anode of the present invention can be as low as about 0.5% (w / w) of the total weight of the electrode (ie, anode < electrode) coating, More preferably at least about 1% (w / w), most preferably at least about 5% (w / w), more preferably at least about 7% (w / w), and even more preferably at least about 8% ( w / w), and more preferably at least about 10% (w / w). This paper is in accordance with China National Standard (CNS) Λ4 specification (210 × 297 mm) (please read the precautions on the back before filling this page),? Τ -11-China Industrial Standards Bureau, Ministry of Light Industry Print A7, one ____ five, the description of the invention (9) is better, the amount does not exceed the total weight of the electrode (ie, anode) coating. About 20% (w / w), more preferably not more than ll% (w / w) 'It is best not to pass 10% (W' / w.) ·. The cathode of the lithium battery of the present invention may also have a coating containing a lithiated transition metal oxide, carbon, polyvinylidene fluoride (PVdF) homopolymer and / or copolymer resin and CaCO3. The lithiated transition metal oxides usable in the cathode coating of the present invention include LixCoO2, LixMn2O4, LixNiO2, LixV2O5 and mixed oxides such as LixNiaC0bMn < : 02, where a + b + c = 1. Polyvinylidene fluoride (PVdF) homopolymer and / or copolymer resins that can be used in the cathode coating of the present invention include poly (vinylidene fluoride-hexafluoropropylene) (PVdF: HFP) copolymer, which contains 8% ( w / w) HFP 'is sold under the trade name SOLEF® 20810; with SOLEF® 3XXX series poly (vinylidene fluoride-chlorotrifluoroethylene) containing about 8% (w / w) to 20% (w / w) CTFE (PVdF: CTFE) copolymer, both of which are products of S 0 LVAY (Belgium). A particularly good PV d F that can be used in the cathode of the present invention is a commercially available PVdF homopolymer I of SOLEF ® 008 of S 0 LVAY (Bolgium). An example of a cathode in which C a C 0 3 can be incorporated according to the present invention. Examples are EP application number 049 2 586 and JP application numbers 6 3/1 2 1 262 and 04/095363 and EP application number 0205856. The most suitable cathodes in the lithium battery of the present invention are as follows: Including the paper size, the Chinese National Standard (CNS) Λ4 specification (210 × 297 mm) --------- ', d ---- --ΐτ ------ Μ • (Please read the notes on the back before filling out this page) -12- Printed on A7 B7 by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (彳 〇) in the name box Contains 6.0 — 9 4% (w / w) lithiated transition metal oxide, about 3-10% (w / w) carbon (graphite and / or carbon black) 'about 3_i 〇% (w / w ) Coatings of PVdF homopolymers and / or copolymers with about 0.5-20% (w / w) CaCO3 'as described above. The cathode of the lithium battery of the present invention may optionally contain other components and components, such as additives, stabilizers, and the like. The cathode of the lithium battery of the present invention may have a coating containing carbon (especially graphite) 'polyvinylidene fluoride (pv d F) homopolymer and / or copolymer resin and CaCO3. The preferred carbon in the anode coating of the present invention is graphite, and the polyvinylidene fluoride (PV d F) homopolymer and / or copolymer resins that can be used in the anode coating of the present invention include PV d F homopolymers and copolymers. . Examples of this PV d F copolymer are: poly (vinylidene fluoride-hexafluoropropylene) (PVdF: HFP) copolymer, which contains 8% (w / w) HFP, sold under the trademark SOLEF®20810; and containing About 8% (w / w) to 20% (w / w) CTFE SOLEF ® 3XXX series poly (vinylidene fluoride-chlorotrifluoroethylene) (PVdF: CTFE) copolymer, both of which are SOLVAY (Belgium ) Products. A particularly good PVdF usable in the anode of the present invention is a commercially available SOLEF® 1008 PfclF homopolymer of SOLVAY (Bolgium). Examples of anodes into which CaCo3 can be incorporated according to the present invention are EP application numbers 0492586 and JP application numbers 63/121262 and 04/095363 and EP application number 0205856. The most suitable anodes for the lithium battery of the present invention are as follows: Including the paper size applicable to the Chinese National Standard (CNS) Λ4 specification (210 > < 297 gong) (Please read the precautions on the back before filling in this K) 4 ------ 1T ------ d -------------- ^ --- • 13- System A7 B7 V. Description of the invention (u) 60% to 9% (w / w) carbon (graphite and / or carbon black) on copper foil, about 1 to 20% (w / w) PVdF Polymers and / or copolymers are prepared with a coating of about 0.5-20% (w / w) CaCO3 'as described above. If necessary, the anode coating of the lithium battery of the present invention may contain other components and ingredients such as additives, stabilizers, hardeners, and the like. Examples of these other components and ingredients are bismuth succinate, aluminum hydroxide, calcium hydroxide and hydroxide. The amount of this additive can be as low as 0% (w / v of the homopolymer / copolymer content of pvd F in the coating). / w), up to about 5% (w / w), that is, 0.05 to 1% (w / w) of the total electrode coating. The electrolyte of the lithium battery of the present invention may be any suitable solid, gel or liquid, examples are PV d F homopolymers and / or copolymers and carbonates, for example, ethylene, propyl and dimethyl carbonate , And specially designed glassy substance with high ion conductivity. Examples of gel electrolytes which can be used in the lithium battery of the present invention are P V d F homopolymers and / or copolymers and carbonates such as ethylene, propyl, dimethyl and diethyl carbonate. Examples of the liquid electrolyte that can be used in the lithium battery of the present invention are Li PF6, LiBF4, LiCl04, and they are mixed with ethylene, propyl, dimethyl, and diethyl carbonate. < The specific area capacity of the lithium battery electrode (cathode and anode) of the present invention can be 0.5 mA h / cm2 (the electrode coating thickness is 0. 0 2 5mm calculated after drying and rolling) to 10mAh / cm2 (the electrode coating thickness 0.5 mm is calculated after drying and calendering). The better specific area capacity is about. This paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 mm) ------------· (Please read the precautions on the back before filling this page)

*1T -14- 經濟部中央標率局員工消費合作社印聚 A7 B7 五、發明説明（12 ) 3mAh/cm2 (電極塗層厚〇 . 1 5mm在乾燥與壓延 後算出）至6mAh/cm2 (電極塗層厚〇 . 3mm在乾 燥與壓後算出）。 本發明鋰離子電池可如熟習此技藝人士公知之習用方 式加以建構。例如，將薄的活性材料塗覆在平坦之更薄的 金屬箔及/或網上。使用聚合物結合劑將碳或石墨陽極塗 在銅箔及/或網上，並將鋰過渡金屬氧化物陰極塗在鋁上 。然後將這些電極堆叠在一起或捲成圓形或橢圓形之果凍 捲（jelly roll )(使用微孔聚合物分隔元件）。該堆叠或 捲繞之果凍捲電極接著被放入金屬容器中，加入電解質， 賦予其形成循環（formation cycle )。剛製成時電池爲放電 狀態，所有的鋰離子均在陰極。 本文揭示之鋰電池適用於多種目的，包括，但不限於 ，電動車之電池。 上文已說明本發明鋰電池、陽極、陰極與分隔元件， 以及彼之製法，下述實例則僅用於例示而非，也不應，用 來作爲限制。 實例1 負極（陽極）之結構 "........... i 製成14個如下述之負極（陽極）： 將98 . 8gN_甲基一2 —吡咯啶酮（NMP)各 置入不銹鋼燒杯中並維持在氬氣流中。於各NMP試樣中 加入4 . 3 9 g表1所示特定C a C〇3，並溫和攪枠。 本紙張尺度適用中國國家標準（CNS ) A4说格（210X297公釐） (請先閱讀背面之注f項再填寫本頁) 訂 -15- 五、發明説明（ 13 經濟部中央標率局負工消費合作社印掣 表 試 樣 Ca,C〇3 之 -類 平均粒 徑（滲 透法）（ β m ) 標準規則 BET表 面積 (m2/g) 自由 流動 密度 (g/1 ) 塗 覆 量 (g/k g) 晶形 1 SOCAL 91CV 0.36 0.30-0.45 7 275 -- 1 2 SOCAL N2R 0.35 0.32-0.38 6 310 -- 1 3 SOCAL N2 0.3 0.2-0.5 6 250 -- 1 4 SOCAL 92E 0.29 0.18-0.34 7 170 -- 1 5 SOCAL 90A 0.24 0.16-0.30 11 143 2 6 SOCAL Np 0.20 0.1-0.3 9 210 -- 3 7 SOCAL E2 0.18 0.1-0.3 10 300 一 3 8 SOCAL 31 0.07 0.055-0.1 20 210 -- 3 - 9 SOCAL 311 0.07 0.05-0.09 19 290 19 3 10 SOCAL 312N 0.07 0.05-0.09 19 286 28 3 11 SOCAL 313 0.07 0.05-0.09 19 (310) 38 3 12 SOCAL 322 0.05 0.04-0.07 26 282 28 3 13 SOCAL U3 0.02 0.015-0.025 70 170 - 3 14 Hydrocarb 95T 天然 0.85 0.2-2 ±2 土 400 -- 天然 形 晶 澧 面 角體 三方 偏斜 角體角 三方三 石斜石 解石解 方文方 本紙張尺度適用中國國家標率（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 -16- A7 B7 五、發明説明（14 ) 然後令各試樣經超音波（Braun Labsonic 2000B，高段）處理2 分鐘而形成分散液，將其置於真空（ImmHg )中1小 時。然無再次以超音波（BraunLabsonic 2000B，高段）處 理2分鐘》 各試樣於1000RPM攪拌中各添加7.65g PVdF，攪拌至完全溶解（溶液變澄淸，約花1 〇 — 2 0分鐘）。 緩慢地將43 · 3g石墨狀碳各加入攪拌（1〇〇〇 RPM)中的試樣，令攪拌速率提高至4000RPM歷 時1分鐘，並將攪拌盤升高降低數次以確保混合物之均勻 性。 然後依序將裝有各試樣（漿狀）之不銹鋼燒杯置於真 空中去氣，但注意勿使產物濺出。試樣於最大真空度（5 _ 1 OmmHg )下歷1 〇分鐘而完成去氣。 取14張銅箔（200x60mm)同時浸入CFC 一 1 1 3浴中3 0分鐘而去除油脂，然後與紙間隔他們後 置入氣密罐中。 經濟部中央標準局負工消费合作社印裝 (讀先閲讀背面之注意事項再填寫本頁) 各箔片標示後稱重（精稱至約0 . lmg範圍）。然 後置於剛性有孔金屬板上而攤平（下方施以真空）。 1 4張箔片各以一個槳狀試樣塗覆上$約3 0 0 之 厚度，然後各置於不銹鋼架（已包覆有聚四氟乙烯）後放 入15 0°C烘箱中3 0分鐘。 乾燥後令各電極冷卻至室溫。接著測量塗覆層之厚度 與電極重量。 本紙張尺度適用中國國家搮率（CNS ) A4規格（210X297公釐） -17- 經濟部中央標準局貝工消费合作社印裝 A7 ______B7 五、發明説明（15 ) 然後令電極一個一個地通過BRABENDER實驗用壓延機 。壓延機滾輥之間距調成使第一次通過之厚度降低比爲 1 0% ;。若需要再次壓延，直主厚度不再變化（指厚度約 爲所得濕漿狀物之5 5 % ) » 如此製成1 4個含不同類型C a C〇3之電極》 實例2 正極（陰極）之結構 如下述製備正極（陰極）： 稱取6 7 . 5g已用分子篩乾燥之N —甲基一2 —吡 咯啶酮（NMP)，置入不銹鋼燒杯中，然後於溫和攪拌 中將2 . 5g碳酸鈣（如S〇CAL®91CV)加入 Ν Μ P 中。 所得混合物經超音波（Braun Labsonic 2000Β，高段）處理 2.分鐘而形成分散液，將其置於真空（1 mmHg )中1 小時。然後再次以超音波（Braun Labsonic 2000B，高段） 處理2分鐘。 各試樣於1 0 0 0RPM攪拌中各添加4 . 9 5g PVdF，攪拌主完全溶解（溶液變澄淸，約花5 — 10 分鐘）。 依序將3 · 3g碳黑，3，3g石墨加入攪拌（ 1000RPM)中的試樣。接著加入70.95g LiNi〇2 (先於150°C真空烘箱中乾燥），令攪拌速 率提高至4000RP Μ歷時1分鐘，並將攪拌盤升高降 本紙張尺度適用中國國家標.华（CNS ) Λ4規格（210X297公釐） ---------ί------ΐτ------Μ < (請先聞讀背面之注意事項再填寫本頁} -18- 經濟部中央標準局貝工消费合作社印繁 A7 B7 五、發明説明（16 ) 低數次以確保混合物之均勻性。 然後燒杯及內容物置於真空中使試樣（漿狀）去氣， 但注意&使產物濺出。漿狀試樣於最大真空度（5-1〇 mmHg)下歷10分鐘而完成去氣。 取將鋁箔（200x 6 0mm)浸入CFC— 1 1 3 浴中30分鐘而去除油脂，精稱至約〇.lmg範菌）。 然後置於剛性多孔有孔金屬板上而攤平（下方施以真空） 。此箔片以手術刀塗覆上約3 0 0 之厚度之漿狀試樣 ，然後置於不銹鋼架（已包覆有聚四氟乙烯）後放入 1 50 °C烘箱中30分鐘。 乾燥後令此陰極冷卻至室溫。接著測量塗覆層之厚度 與陰極重量。 然後令此陰極通過BRABENDER實驗用壓延機。壓延機 滾輥之間距調成使第一次通過之厚度降低比爲1 0%。若 需要再次壓延，直主厚度不再變化（指塗層厚度約爲施加 在鋁箔上濕漿狀物之55%)。 如此製成含不同類型C a C 〇3之陰極。 實施例3 測量各種C a C 〇3作爲酸淸除劑之效率 - 、 使用實例1所得電極，移除其中之金靥支撐物，將各 電極之剩餘部份稱重後放入各皿（boat )中，皿中含有欲 置入酸（HF)中的材料。然後將各皿置入與容器同材質 之管中，接著各管分別放入管狀烘箱，於5 0 0°C恆溫下 本紙張尺度適用中國國家標準（C:NS ) Λ4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 ---- -V M· -19- A7 B7 五、發明説明（17 ) 加熱3 0分鐘’其間令已預熱之氮氣流通過各管子而帶出 因熱釋出而未被CaC〇3捕獲之酸（HF)。被氣流帶出 之酸（iiF)用已知體積之乙酸/乙酸鈉緩衝溶液（p Η 約爲5至6)來吸收。 緩衝溶液吸收的酸（HF )直接用電位法測定，即， 用F—離子特異電極（指示電極）與參考電極測量。連續記 錄指示電極與參考電極的電位差，然後.與預先作好的參考 曲線相比。如此相比，便可得知任一時間點之氟含量，即 ，酸（H F )的量。 如下計算「淸除的酸」與「酸淸除效率」： —在沒有加C a C〇3的參考實驗中，測得有3 1 . 9 g酸（HF) / kg塗層的釋出。 —含有CaC〇3 (7 9 . 2g/kg塗層）之試樣中 ，可由PV dF去氫氟化之酸（HF)的最大量計算爲 2 9 . 4g/kg塗層（因爲C a C〇3之「稀釋」效應） 〇 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) —理論上可被7 9 . 2gC a C〇3中和之酸（HF) 的最大量爲3 1 . 7 g。 —上述實驗中，由氮氣沖提出的酸（H、F )量爲xg 酸（H F ) / k g塗層，貝(1 淸除的酸=29 . 4-x g/kg塗層* 1T -14-Industrial Consumer Cooperative Cooperative A7 B7 of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (12) 3mAh / cm2 (electrode coating thickness 0.15mm is calculated after drying and rolling) to 6mAh / cm2 (electrode The coating thickness is 0.3 mm (calculated after drying and pressing). The lithium ion battery of the present invention can be constructed in a manner known to those skilled in the art. For example, a thin active material is coated on a flat, thinner metal foil and / or web. A polymer binder is used to coat the carbon or graphite anode on copper foil and / or wire, and the lithium transition metal oxide cathode on aluminum. These electrodes are then stacked together or rolled into a round or oval jelly roll (using a microporous polymer separation element). The stacked or rolled jelly roll electrode is then placed in a metal container, and an electrolyte is added to give it a formation cycle. The battery is discharged when it is just made, and all lithium ions are at the cathode. The lithium batteries disclosed herein are suitable for a variety of purposes, including, but not limited to, batteries for electric vehicles. The lithium battery, anode, cathode, and separator of the present invention, and their manufacturing methods have been described above. The following examples are for illustration only and should not be used as limitations. Example 1 Structure of the negative electrode (anode) " .......... i was made into 14 negative electrodes (anode) as follows: 98.8 g of N_methyl-1 2-pyrrolidone (NMP) Each was placed in a stainless steel beaker and maintained under a stream of argon. To each NMP sample, 4.39 g of the specific Ca C03 shown in Table 1 was added and gently stirred. This paper size applies the Chinese National Standard (CNS) A4 scale (210X297 mm) (please read the note f on the back before filling this page) Revision -15- 5. Description of the invention (13 Central Standards Bureau of the Ministry of Economic Affairs Consumption Cooperative Printing Co., Ltd. Samples Ca, C〇3-Class average particle size (permeation method) (β m) Standard rules BET surface area (m2 / g) Free flow density (g / 1) Coating amount (g / kg ) Crystal 1 SOCAL 91CV 0.36 0.30-0.45 7 275-1 2 SOCAL N2R 0.35 0.32-0.38 6 310-1 3 SOCAL N2 0.3 0.2-0.5 6 250-1 4 SOCAL 92E 0.29 0.18-0.34 7 170-1 5 SOCAL 90A 0.24 0.16-0.30 11 143 2 6 SOCAL Np 0.20 0.1-0.3 9 210-3 7 SOCAL E2 0.18 0.1-0.3 10 300-3 8 SOCAL 31 0.07 0.055-0.1 20 210-3-9 SOCAL 311 0.07 0.05-0.09 19 290 19 3 10 SOCAL 312N 0.07 0.05-0.09 19 286 28 3 11 SOCAL 313 0.07 0.05-0.09 19 (310) 38 3 12 SOCAL 322 0.05 0.04-0.07 26 282 28 3 13 SOCAL U3 0.02 0.015-0.025 70 170-3 14 Hydrocarb 95T Natural 0.85 0.2-2 ± 2 Soil 400-Natural-shaped crystal facet Hexahedron Hexagonal Hexahedron Hexagon Oblique calcite solution. The paper size is applicable to China National Standards (CNS) A4 specifications (210X 297 mm) (Please read the precautions on the back before filling this page) Order-16- A7 B7 V. Description of the invention (14 ) Then each sample was treated with ultrasound (Braun Labsonic 2000B, high section) for 2 minutes to form a dispersion, and it was placed in a vacuum (ImmHg) for 1 hour. However, there was no ultrasound (BraunLabsonic 2000B, high section) again. Treatment for 2 minutes "Each sample was added with 7.65g of PVdF in 1000RPM stirring, and stirred until completely dissolved (the solution became clear, it took about 10-20 minutes). Slowly add 43.3 g of graphitic carbon to each sample in the stirring (1000 RPM), increase the stirring rate to 4000 RPM for 1 minute, and raise and lower the stirring plate several times to ensure the homogeneity of the mixture. Then sequentially place the stainless steel beakers containing the samples (slurry) in the air to degas, but be careful not to spill the product. The sample was degassed for 10 minutes at the maximum vacuum (5 -1 OmmHg). 14 sheets of copper foil (200x60mm) were simultaneously immersed in a CFC 1 1 3 bath for 30 minutes to remove grease, then separated from the paper and placed in an airtight tank. Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives (read the precautions on the back before filling out this page). Each foil is labeled and weighed (fine weighing to about 0.1 mg range). It is then laid flat on a rigid perforated metal plate (vacuum is applied below). Each of the four foils is coated with a paddle sample to a thickness of about $ 300, then placed in a stainless steel rack (coated with polytetrafluoroethylene) and placed in a 15 ° C oven. minute. After drying, allow each electrode to cool to room temperature. Then, the thickness of the coating layer and the electrode weight were measured. This paper size applies to China's National Standard (CNS) A4 specification (210X297 mm) -17- Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 ______B7 V. Description of the invention (15) Then let the electrodes pass the BRABENDER test With a calender. The distance between the rollers of the calender is adjusted so that the thickness reduction ratio of the first pass is 10%; If it needs to be rolled again, the straight main thickness will not change any more (referring to a thickness of about 55% of the obtained wet slurry) »In this way, 14 electrodes with different types of C a C03 are made. Example 2 Positive electrode (cathode) The structure is as follows to prepare a positive electrode (cathode): Weigh 67.5 g of N-methyl-2-pyrrolidone (NMP) that has been dried with a molecular sieve, place it in a stainless steel beaker, and then 2.5 g with gentle stirring Calcium carbonate (such as SOCAL® 91CV) is added to NMP. The resulting mixture was treated with ultrasound (Braun Labsonic 2000B, high section) for 2 minutes to form a dispersion, which was placed in a vacuum (1 mmHg) for 1 hour. Then it was treated with ultrasound (Braun Labsonic 2000B, high section) again for 2 minutes. Add 9.5 g of PVdF to each sample in 100RPM agitation, and the main part of the agitation is completely dissolved (the solution becomes clear, it takes about 5-10 minutes). 3 · 3g of carbon black and 3,3g of graphite were sequentially added to the sample under stirring (1000RPM). Then add 70.95g LiNi〇2 (drying in a 150 ° C vacuum oven) to increase the stirring rate to 4000RPM for 1 minute, and raise and lower the stirring plate. The paper size is in accordance with Chinese national standard. China (CNS) Λ4 specification (210X297 mm) --------- ί ------ ΐτ ------ Μ < (Please read the notes on the back before filling out this page} -18- Ministry of Economy Central Standards Bureau Shellfish Consumer Cooperatives Printing Fan A7 B7 V. Description of the invention (16) Low several times to ensure the homogeneity of the mixture. Then place the beaker and contents in a vacuum to degas the sample (slurry), but note & The product was splashed. The slurry sample was degassed for 10 minutes under the maximum vacuum (5-10 mmHg). Take the aluminum foil (200 x 60 mm) and immerse it in the CFC-1 1 3 bath for 30 minutes to remove grease. , Finely weighed to about 0.1mg Fan bacteria). It is then laid flat on a rigid porous perforated metal plate (vacuum is applied below). This foil was coated with a paste sample with a thickness of about 300 with a scalpel, then placed in a stainless steel rack (coated with Teflon) and placed in an oven at 50 ° C for 30 minutes. After drying, the cathode was allowed to cool to room temperature. Then, the thickness of the coating layer and the weight of the cathode were measured. This cathode was then passed through a BRABENDER test calender. The distance between the rollers of the calender is adjusted so that the thickness reduction ratio of the first pass is 10%. If rolling is required again, the main thickness will not change any more (referring to the coating thickness of about 55% of the wet slurry applied to the aluminum foil). In this way, cathodes containing different types of C a C 03 were made. Example 3 Measurement of the efficiency of various CaC03 as acid scavengers-Using the electrode obtained in Example 1, removing the gold scaffold support, weighing the remaining parts of each electrode and placing them in boats ), The dish contains the material to be placed in the acid (HF). Then put each dish into a tube of the same material as the container, then put each tube into a tube oven separately. At a constant temperature of 500 ° C, this paper applies the Chinese national standard (C: NS) Λ4 specification (210X297 mm). (Please read the precautions on the back before filling this page) Order ---- -VM · -19- A7 B7 V. Description of the invention (17) Heating for 30 minutes' during which the pre-heated nitrogen flow is passed through the tubes and Take out the acid (HF) which is not captured by CaCO3 due to thermal release. The acid (iiF) carried by the gas stream is absorbed with a known volume of acetic acid / sodium acetate buffer solution (p Η approximately 5 to 6). The acid (HF) absorbed by the buffer solution is directly measured by a potentiometric method, that is, measured using an F-ion specific electrode (indicating electrode) and a reference electrode. The potential difference between the indicator electrode and the reference electrode is recorded continuously, and then compared with the reference curve prepared in advance. In this way, we can know the fluorine content at any time point, that is, the amount of acid (H F). The "eliminated acid" and "acid elimination efficiency" are calculated as follows:-In a reference experiment without Ca C03, the release of 31.9 g of acid (HF) / kg coating was measured. —In samples containing CaC03 (79.2 g / kg coating), the maximum amount of PV dF dehydrofluorinated acid (HF) can be calculated as 29.4 g / kg coating (because of C a C 〇3 "Dilution" effect) 〇 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) — theoretically the acid that can be neutralized by 79.2gC a C〇3 ( The maximum amount of HF) is 31.7 g. —In the above experiment, the amount of acid (H, F) extracted from the nitrogen gas is xg acid (H F) / k g coating, shellfish (1 acid removed = 29. 4-x g / kg coating

0Q 4 — JC 酸淸除效率=—rpr- ·100〇/〇 本紙張尺度適用中國國家揉率（CNS)Λ4規格（210x297公釐） -20- A7 B7 五、發明説明（18 ) 〔應注意到，因爲使用略微過量之c a C〇3 (相較於參考 實驗中_出的HF)，所以本案定義之酸淸除率的最大可 能値爲92.7% (在x = 0時）。 ---------------ΪΤ------鏞.' >- (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標挲局兵工消費合作社印製 本紙浪尺度適用中國國家揉準（CNS ) Λ4規格（210X297公釐） -21 - S89001 五、發明説明（ A7 B7 經濟部中央標率局貝工消費合作社印聚 19 試樣 試樣之CaC〇3 __B_- 平均粒徑（ 滲透法）（ β m ) Ά---- 淸除的酸（g /kg電極塗 層） 酸淸除效率 (%) 1 SOCAL91CV 0.36 21.0 66 2 SOCAL N2R 0.35 21.2 67 3 SOCAL N2 0.3 19.9 63 4 SOCAL 92E 0.29 21.2 67 5 SOCAL 90A 0.24 _ 20.8 66 6 SOCAL Np 0.20 19.7 62 7 SOCAL E2 0.18 _ 18.7 59 8 SOCAL 31 0.07 15.4 49 - 9 SOCAL 311 0.07 14.6 46 10 SOCAL 312N 0.07 13.6 43 11 SOCAL 313 0.07 14.0 44 12 SOCAL 322 0.05 13.6 43 13 SOCAL U3 0.02 _ 9.0 28 14 Hydrocarb 95T 天然 0.85 17.7 L—---- 56 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） -22- 389001 b； 五、發明説明（20 ) 顯然，在不背離本發明基本精神下可有許多改良。所 以，在本發明所附申請專利範圍內，熟習此技藝人士可進 行未被k體例示之本發明。 —-------------,玎------绩 ·钃 (請先聞讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印裝 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210Χ297公釐） -23-0Q 4 — JC Acid removal efficiency = —rpr- · 100〇 / 〇 This paper size is applicable to China National Kneading Rate (CNS) Λ4 specification (210x297 mm) -20- A7 B7 V. Description of the invention (18) Therefore, because a slightly excessive amount of ca C03 is used (compared to the HF in the reference experiment), the maximum possible acid removal rate defined in this case is 92.7% (when x = 0). --------------- ΪΤ ------ 镛. '≫-(Please read the notes on the back before filling out this page) Military Standards Bureau, Ministry of Economic Affairs, Military Consumption The scale of the paper printed by the cooperative is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297 mm) -21-S89001 V. Description of the invention (A7 B7) CaC〇3 __B_- average particle size (permeation method) (βm) Ά ---- eliminated acid (g / kg electrode coating) acid removal efficiency (%) 1 SOCAL91CV 0.36 21.0 66 2 SOCAL N2R 0.35 21.2 67 3 SOCAL N2 0.3 19.9 63 4 SOCAL 92E 0.29 21.2 67 5 SOCAL 90A 0.24 _ 20.8 66 6 SOCAL Np 0.20 19.7 62 7 SOCAL E2 0.18 _ 18.7 59 8 SOCAL 31 0.07 15.4 49-9 SOCAL 311 0.07 14.6 46 10 SOCAL 312N 0.07 13.6 43 11 SOCAL 313 0.07 14.0 44 12 SOCAL 322 0.05 13.6 43 13 SOCAL U3 0.02 _ 9.0 28 14 Hydrocarb 95T Natural 0.85 17.7 L —---- 56 (Please read the precautions on the back before filling this page) The paper dimensions Applicable to China National Standard (CNS) Λ4 specification (210X297 mm) -22- 389001 b; (20) Obviously, there can be many improvements without departing from the basic spirit of the present invention. Therefore, within the scope of the patent application attached to the present invention, those skilled in the art can carry out the present invention which is not exemplified by the k-type. ------ ---------, 玎 ------ Ji · 钃 (Please read the notes on the back before filling out this page) Central Standards Bureau, Ministry of Economic Affairs National Standard (CNS) Λ4 Specification (210 × 297 mm) -23-

Claims (1)

經濟部中央標準局工消費合作社印装 A8 389001_i_ ττ、申請專利範圍 1·—種如下類型之鋰電池，其陽極、陰極及/或分. 隔元件至少一者含有聚偏二氟乙烯均聚物及/或共聚物， 此電池的特徵爲該陽極、陰極及/或分隔元件至少一者另 包含碳酸鈣，其中該碳酸鈣作爲酸淸除劑而減少或淸除可 用的自由酸C._其會使電池中不可收拾放熱反應發生及/或 增強）。 2 .如申請專利範圍第1項之鋰電池，其中碳酸鈣係 包含於Μ極與陰極中至少一者。 ,3.如申請專利範圍第1項之鋰電池，其中碳酸鈣係 包含於陽極與分隔元件中至少一者。 4.如申請專利範圍第1項之鋰電池，其中碳酸鈣係 包含於陰極與隔元件中至少一者。 5 .如申請專利範圍第1項之鋰電池，其中碳酸鈣係… 包含於陽極、陰極與分隔元件中至少一者。 6.如申請專利範圍第1項之鋰電池，其中之碳酸鈣 爲 S 0 C A L ®。 7 如申請專利範圍第1項之鋰電池，其中之碳酸鈣 的平均粒徑至少約0 . 10 /zm。 8 .如申請專利範圍第1項之鋰電池，其中之碳酸鈣 的平均粒¥至少約0 . 18#m。 9 .如申請專利範圍第1項之鋰電池，其中之碳酸鈣 的平均粒徑至少約0 · 20jam。 1 0 .如申請專利範圍第1項之鋰電池，其中之碳酸 鈣的平均粒徑至少約〇.36/zm。 (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 本紙張尺度適用中國國家標準（CNS ) Λ4洗格（210X 297公釐) -24- A8 389001 ll D8 六、申請專利範圍 鈣的平均粒徑至少蔚0 . 1 0 // m。 (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標隼局負工消費合作社印裝 本紙張尺度適用中國國家標準（CNS ) Λ4規格（2丨0 X 297公釐） -26-A8 389001_i_ ττ printed by the Industrial Standards and Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, patent application scope 1 · —A lithium battery of the following types, the anode, the cathode and / or the branch. At least one of the separators contains polyvinylidene fluoride homopolymer And / or copolymer, the battery is characterized in that at least one of the anode, cathode and / or separator element further comprises calcium carbonate, wherein the calcium carbonate acts as an acid scavenger to reduce or eliminate available free acid C._ 其Will cause unrecoverable exothermic reactions in the battery and / or enhance). 2. The lithium battery according to item 1 of the patent application scope, wherein the calcium carbonate is contained in at least one of the M electrode and the cathode. 3. The lithium battery according to item 1 of the scope of patent application, wherein calcium carbonate is contained in at least one of the anode and the separator. 4. The lithium battery according to item 1 of the patent application scope, wherein calcium carbonate is contained in at least one of the cathode and the separator. 5. The lithium battery according to item 1 of the patent application scope, wherein calcium carbonate is included in at least one of the anode, the cathode and the separator. 6. The lithium battery of item 1 in the patent application scope, in which the calcium carbonate is S 0 C A L ®. 7 The lithium battery according to item 1 of the patent application scope, wherein the average particle diameter of the calcium carbonate is at least about 0.10 / zm. 8. The lithium battery according to item 1 of the patent application scope, wherein the average particle of calcium carbonate is at least about 0.18 # m. 9. The lithium battery according to item 1 of the patent application scope, wherein the average particle diameter of the calcium carbonate is at least about 0 · 20 jam. 10. The lithium battery according to item 1 of the patent application scope, wherein the average particle size of the calcium carbonate is at least about 0.36 / zm. (Please read the precautions on the back before filling out this page) The size of the bound and bound paper is applicable to the Chinese National Standard (CNS) Λ4 Washing (210X 297 mm) -24- A8 389001 ll D8 The particle size is at least 0. 1 0 // m. (Please read the notes on the back before filling out this page) Order Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Printed by the Consumers' Cooperative, This paper size applies to the Chinese National Standard (CNS) Λ4 specification (2 丨 0 X 297 mm) -26-
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