五、發明說明（ 免明.背景 該t明。係關於高電壓、高容量可充電電化學電池單元， I:斟早70包括正極、負極、及具有包括電池操作過程中 ’可在各電極處分別進行氧化還原之不同可移動 =加入電解質之分隔材。尤其，本發明關於可充電電 並U〈製備及利用’該電池包括在電池循環過程中 並二，:對陽離子類進行氧化還原反應之多價電極材料， 二多價係在電池電解質'中’但第二種陽離子類主要在電 操：二極處反應。此等同時之氧化還原反應可在電池 =過”’使每一離子之多電子轉移，明顯的增加電池 今I而不損及高電壓之輸出。 十現今市場上小型化'輕重量可充電電池主要爲插入趣之 =舌ί其是…離子電池，其以11電極及電解質成分材 二重里义觀點，可提供明顯之比容量，亦即每單位電池 重量之可由電池儲存且傳輸之能量。叙之高反應性對二提 供包含之可能包括鐘金屬或合金’或插入兹材料之自電、、也 電極意外之低電位產生額外之效益，至於另一優點了爲各 種金屬氧化物、硫化物或氟化物材料均可在高電位下血趣 反應’因而使其可在所得高電壓電池單元中用作正電極。 然而，輕重量及高電壓操作對所得此等可充電電池之比 能量密度有利之影響會因影響電池操作之移動鐘陽離子爲 單價，且因此可視同每一使用之Li+離子僅操作轉移單一 電子之限制，而受到損害。 考量電池容量與電荷移轉離子價之依存性，增加電化學 -4- A7V. Description of the invention (Immunity. Background: This is about high-voltage, high-capacity rechargeable electrochemical cells. I: As early as 70, including positive and negative electrodes, and including battery operation, it can be disposed at each electrode. Do not carry out the difference between redox and removable = separator with electrolyte added. In particular, the present invention relates to rechargeable electricity and U <preparation and utilization '. The battery is included in the battery cycle and the second step: the redox reaction of cationic species Multivalent electrode materials, the second polyvalent system is in the battery electrolyte, but the second type of cations is mainly reacted at the electric operation: the second electrode. These simultaneous redox reactions can be performed at the battery = Multi-electron transfer significantly increases the battery's current output without jeopardizing the high-voltage output. Ten miniaturized 'light-weight' rechargeable batteries on the market today are mainly plug-in batteries, which are ... ion batteries, which use 11 electrodes and The dual meaning of the electrolyte component material can provide a clear specific capacity, that is, the energy that can be stored and transmitted by the battery per unit battery weight. It may include the bell metal or alloy 'or the self-electricity of the inserted material, and also the unexpected low potential of the electrode to generate additional benefits. As another advantage, various metal oxides, sulfides or fluoride materials can be used at high potentials. The bloody reaction 'thus makes it useful as a positive electrode in the resulting high voltage battery cells. However, the light weight and high voltage operation have a beneficial effect on the specific energy density of the resulting rechargeable batteries due to movements that affect battery operation Bell cations are monovalent, and therefore can be considered as a limitation for each Li + ion used to operate and transfer only a single electron, which is harmed. Consider the dependence of battery capacity and charge transfer ion valence to increase electrochemical-4-A7
五、發明說明（2 ) 私池谷量 < 另一方法邏輯上會包含使用多價反應性成分。 孩万法已在美國專利5,601，949號中考量，然而，以多價陽 離子取代單價鋰，以得到較高容量之插入電池單元實際之 成功率並不高。此種電池之失敗明顯的係起因於許多原 因’並非只疋其至少部分爲明顯較大尺寸之可防止影響加 在負極組合物中之多價離子，如本專利説明書中提及之石 墨或碳材料。 對於影響多價離子電池操作之另一因素爲反應材料之純 化層，稱之爲固體/電解質介面（SEI)，且一般爲還原之副 產物’例如電解質陽離子氧化物、氟化物、碳酸鹽等，其 係在第一次循環充電過程中，於負電池電極之表面上形 成。雖然一般L i +離子插入電池之]l i +離子可擴散經過s E j 層’與負極接觸且在還原，多價陽離子無法依此方式擴 散’且明顯受制於負極處之基本氧化還原反應之分離。雖 然可能發生多價陽離子之部分還原，但在固定較高電位之 鈍性層反應產物下發生反應，因此降低電極間之電位差 異’因而降低操作電池電壓。 因此’多價電化學電池成分在增加電池容量之實際利用 而要導入與電池電極間之移動多價陽離子類簡易傳輸不同 之機構。本發明提供此種新穎及有效之機構，以改善利用 多價電池成分之容量。 發明概要 依本發明製造之可充電電化學電池包括正極組件、負極 組件、及離子傳輸及電子隔絕之插入之分隔材組件。插在 -5- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I i_i n -ϋ —ϋ ϋ n I r · i_i n n I Hi ϋ ϋ J 、i n n ϋ n ϋ n 1 I (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 506154 A7 五、發明說明（3 ) %極組件間且包含者爲包括多價陽離子類之電解質，該電 解質較好爲可提供多價陽離子如Y3+，U3+，Mg2+，Ca2+， (請先閱讀背£.之注意事項再填寫本頁) a 或Sr ’容貝之非水性溶液。正極組件包括活性材 料，如過渡金屬氧化物、硫化物、氟化物或氟化碳，其可 在電池操作過程中之插入、合金、吸附等之可逆氧化反應 中參與作用且釋出多價陽離子。負極組件包括活性材料， 其提供電池操作過程中，可以可逆的釋入電解質溶劑中且 參與作用〈第二種、高反應性、負極作用之陽離子類源， 且較好爲驗金屬，如Li+，Na+，K+，Rb+，或Cs+。該負極 活性材料可爲鹼金屬、鹼金屬合金、或可加入鹼金屬;碳 材料’例如焦炭、硬質碳、或石墨。 本發明電池之一具體例包括正極組件v2 〇5、負極組件 LiSi、及吸飽在硼矽酸鹽玻纖分隔材薄膜中之碳酸乙烯酯 (EC)及碳酸二曱酉旨（DMC)之2 : 1混合物中之〇·5 m Y(C 1 〇4)3電解質。電池開始充電過程中，電解質之γ3 +離 子移到正電極處之可逆反應中，同時負極釋出之Li+離子 進入電解質之EC:DMC溶劑中。主要由於物理性的接近相 對高濃度之Y3+離子與較高總電位加入之正 應最主要者爲其各電極。 經濟部智慧財產局員工消費合作社印製 電池充電時，反應依一般方式會傾向可逆，亦即正電極 Υ3+離子之去加入或其他釋出，且二陽離子類在負極處還 原。然而，由於負極之表面會快速形成鈍化產物，因此僅 離子可擴散經過SEI層，到達LiSi負極材料，且在對 SHE理論-3.0 v之電位下還原。除較大之施加電壓外，負 -6- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 B7 五、 發明説明（4 -之鈍化層可防止留在電解質溶液中之Y 3+離子還原，因 此可維持低的負極相對電位，且得到電池之高操作電壓。 製造積層聚合物電解電池電極組件之步驟在實務上已廣 ，的用作本發明電池電極之製備，如美國專利第5,46〇,9〇4 f中所述。依此方式，正極組件可藉由將28份之可加入多 ^陽離子足活性材料（例如各氧化釩及氧化鈷之任一種， 幸乂好爲毛微米材料〈形式)及6份之導電碳分散在包括有機 落液（例如在28份丙酮中，含約15份結合劑聚合物、如聚 (鼠化亞乙晞-共-六氟丙晞））及23份聚合物之一級可塑劑 (例如酞酸二丁酯）之基質組合物中輕易的製備。 訂 將：組合物澆鑄成層狀物，且在切割成電池製造所需尺 寸之則，先於至溫下空氣烘乾成薄膜。再將薄膜樣品積層 至導電電流收集器組件上，隨後積層至另一電極與分隔材 組件上。經積層之組件經常在添加電解質溶液之前，再以 對聚合物惰性之溶劑（如二乙駿）萃取加入之可塑劑。雖然 市二邊池較好以全邵積層之電極分隔材組件製造，但實驗 用實驗1：模型可更輕易的組立，以試驗―㈣仏試驗電 池’該電池基本上與物理壓力型電池單元極相似，如典型 =”鈕扣型”電池。後一類之電池構造可充分的用於本發 圖之簡I料枰 本發明將參考附圖敘述，其中·· 圖1爲本發明之積層電池單元剖面之圖示表示； 圖2爲追蹤先前技藝之單一單價陽離子電池獨特之循環 本紙張尺度適用中國國家標準（CNS ) A4規格（ A7 發明說明（S) (電壓及比電容之圖； ' ·ν,^歡追％—多價陽離子電池獨特之循環電,- 圖4 明-重陽離子電池具體例中之獨、特;盾環V. Description of the Invention (2) Private Pool Grain < Another method logically involves the use of multivalent reactive components. The Haven method has been considered in US Patent No. 5,601,949. However, the replacement rate of monovalent lithium with polyvalent cations to obtain higher capacity for inserting battery cells is not very successful. The failure of this type of battery is apparently due to a number of reasons, 'not only that it is at least partly of a significantly larger size to prevent affecting the multivalent ions added to the negative electrode composition, such as graphite or graphite mentioned in this patent specification Carbon material. Another factor affecting the operation of multivalent ion batteries is the purification layer of the reaction material, called solid / electrolyte interface (SEI), and is generally a by-product of reduction, such as electrolyte cationic oxides, fluorides, carbonates, etc. It is formed on the surface of the negative battery electrode during the first cycle of charging. Although general Li + ions are inserted into the battery, li + ions can diffuse through the s E j layer 'in contact with the negative electrode and being reduced, polyvalent cations cannot diffuse in this way' and are obviously subject to the separation of the basic redox reaction at the negative electrode . Although partial reduction of polyvalent cations may occur, the reaction occurs under the reaction product of a passive layer that fixes a higher potential, thereby reducing the potential difference between the electrodes' and thus the operating battery voltage. Therefore, the 'multivalent electrochemical cell component is actually used to increase the capacity of the battery, and it is necessary to introduce a mechanism different from the simple transmission of the mobile multivalent cations between the battery electrodes. The present invention provides such a novel and effective mechanism to improve the capacity of utilizing multivalent battery components. SUMMARY OF THE INVENTION A rechargeable electrochemical cell manufactured according to the present invention includes a positive electrode assembly, a negative electrode assembly, and an interposed separator assembly for ion transmission and electronic isolation. Inserted in -5- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) I i_i n -ϋ —ϋ ϋ n I r · i_i nn I Hi ϋ ϋ J, inn ϋ n ϋ n 1 I (Please read the notes on the back before filling out this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed on 506154 A7 V. Description of the invention (3)% Electrolytes between and including the multivalent cationic electrolyte, the The electrolyte is preferably a non-aqueous solution that can provide polyvalent cations such as Y3 +, U3 +, Mg2 +, Ca2 +, (please read the precautions on the back of this page before filling in this page) a or Sr 'Rongbei. The positive electrode assembly includes active materials, such as transition metal oxides, sulfides, fluorides, or carbon fluorides, which can participate in the reversible oxidation reaction of insertion, alloying, adsorption, etc. during battery operation and release polyvalent cations. The negative electrode component includes an active material, which can be reversibly released into the electrolyte solvent and participates in the operation during the battery operation. The second type is a cationic source with high reactivity and negative effect, and it is preferably a metal test such as Li +, Na +, K +, Rb +, or Cs +. The negative electrode active material may be an alkali metal, an alkali metal alloy, or an alkali metal may be added; a carbon material 'such as coke, hard carbon, or graphite. A specific example of the battery of the present invention includes the positive electrode assembly v205, the negative electrode assembly LiSi, and the ethylene carbonate (EC) and dicarbonate carbonate (DMC) 2 which are saturated in the borosilicate glass fiber separator film. : 0.5 m Y (C 10) 3 electrolyte in a mixture. During the battery charging process, the γ3 + ions of the electrolyte move to the reversible reaction at the positive electrode, and at the same time, the Li + ions released by the negative electrode enter the EC: DMC solvent of the electrolyte. Mainly due to the physical proximity of relatively high concentrations of Y3 + ions and higher total potential, the most important is the electrodes. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs When charging the battery, the reaction will tend to be reversible in the usual way, that is, the positive electrode Υ3 + is added or released, and the dications are reduced at the negative electrode. However, due to the rapid formation of passivation products on the surface of the anode, only ions can diffuse through the SEI layer, reach the LiSi anode material, and be reduced at a potential of -3.0 v for SHE theory. Except for larger applied voltage, minus -6- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) A7 B7 V. Description of the invention (4-The passivation layer can prevent it from remaining in the electrolyte solution The Y 3+ ions are reduced, so that the relative potential of the negative electrode can be maintained low, and the high operating voltage of the battery can be obtained. The steps of manufacturing the laminated polymer electrolytic battery electrode assembly have been widely used in practice, and are used for the preparation of the battery electrode of the invention As described in U.S. Patent No. 5,46,0904 f. In this way, the positive electrode assembly can be added by adding 28 parts of polycationic active material (such as any of vanadium oxide and cobalt oxide, Fortunately, it is a hair micron material (form) and 6 parts of conductive carbon are dispersed in an organic liquid (for example, in 28 parts of acetone, containing about 15 parts of a binder polymer, such as poly (methylene chloride-co-) Hexafluoropropionamidine)) and 23 parts of polymer first-grade plasticizer (such as dibutyl phthalate) are easily prepared in a matrix composition. Order: The composition is cast into a layer and cut into a battery manufacturing plant If the size is required, it should be dried in air before reaching the temperature. Thin film. The thin film sample is then laminated to the conductive current collector assembly, and then laminated to another electrode and separator assembly. The laminated assembly is often treated with a polymer inert solvent such as diethyl ether before adding an electrolyte solution. (Jun) Plasticizer added by extraction. Although the city's two-sided pool is better made of fully laminated electrode separator components, the experiment for experiment 1: the model can be more easily assembled to test-"test battery" the basic battery It is very similar to the physical pressure type battery cell, such as typical = "button type" battery. The latter type of battery structure can be fully used in the drawings of the present invention. The present invention will be described with reference to the drawings, of which ... Figure 1 This is a schematic representation of the cross-section of a laminated battery cell according to the present invention; Figure 2 is a unique cycle of a single-valent cation battery tracking previous technology. The paper dimensions are applicable to China National Standard (CNS) A4 specifications (A7 Description of Invention (S) (Voltage and ratio Capacitance map; '· ν, ^ 追%-unique cycle electricity of polyvalent cation batteries,-Figure 4-unique and special in the specific example of heavy cation batteries; shield ring
電壓及 圖5爲' f▲本 循環電壓及Voltage and Figure 5.
經濟部智慧財產局員工消費合作社印製 重陽離子電池另一具體例中之獨特 〇 發明説曰^ 如圖1中所f，本發明中'也單元構造U)包括（較好 如上述美國專利第5，偏，9〇4號中户斤述組件之積層組合切 式）正極組件13、負極組件17、含電池電解質之插入分隔 材組件15。結合各正及負極組件之現行收集材組件η、 19可提供電池用之電路連接，如延伸之封端片ΐ2、16。 針對實驗室試驗目的，可在分隔材組件15中裝置中間電 極，如銀線14，以建立各正及負半電極類似參考用之位。 通帛，正包極13包括含可加入或吸收多價電解質陽離子 (例如鹼土族之陽離子）之毫微米尺寸活性材料（如過渡金 屬氧化物，例如％〇5，Μη〇2，或c〇3〇4)分散液之亞乙烯系 共聚物基質。負平衡離子電極1 7包括可以可逆電鍍、合 金、加入或另與其反應之毫微米材料化合物、或簡單之金 屬4之類似共聚物基質分散液，且因此可提供單價陽離子 (如L i、N a或其他鹼金屬）源。分隔材1 5同樣的可爲聚合 物薄膜’如參考説明書中之敘述，或可包括廣用之微孔隙 -8 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） C靖先閱讀背面之注音？事項再填寫本頁) 裝 ----訂--------- 五 Λ發明說明（6 薄膜或簡易之玻纖塾，其任一種均可吸收非水性電解質， =‘5至2 Μ之含多價陽離子化合物之環狀與非環狀碳：酯 :制混5物之溶液。該電解質另可包括小量之對負極有 皿’且可以依放電態製造電池之單價鹼金屬鹽。 a:由選用之Ag電極i 4建立之參考數據提供_般單獨測 疋電極選用之組合物成分之電解質活性之裝置。依此方 式，可確認有效之電極及電解質之結合。例如，該參考 極對於確認電解質電池機構有幫助，其中之多價陽離子 (例如Y，對於鈍化之鹼金屬負極並無法接受，且因此 :電極處無法電鍍或還原，以進行電池充電，除非施加 田超過理論上所需之電壓]衣同樣之方式，決定單一陽離 子3:7也、中〈鈍化負極之可接近表面處之半電池中發生 γ陽離子之高正極還原反應係反應下列列舉之電池呈 之基本上無效之最終電壓水準。 在製造加鈷電池單元中，選用之電池組合物及成分一 標準Swagelok試驗電池裝組立，其中之具有其中吸 電解質之分隔材組件之正及負電極組件係壓在相反之 收集材保護組件間，以達到基本薄膜間之接近。組立後 各忒驗電池與在每克活性材料約7.6 mA之預定循環速 :依猙怨電流（galvanostatic)模式操作之MacPile自動 %乙制/數據紀錄系統排列於電路中，得到試驗電池獨 特徵之電壓/電容輪廓。 、=則面 < 敘述，下列實例將提供熟習本技藝者對本發 (實務有效之成分與組合物結合選擇之導引。 類 在 大 之 訂 般 流 率 循 特 明 -9 本纸張尺度刺 t rnm^(CNS)Aim^Q x 29f^t} _ 506154 第090112106號專利申請案 中文說明書修正頁(91年7月） 中文說明書修正頁(91年7月） 7. ι 〇It is unique in another specific example of printed heavy cation batteries printed by employees ’cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. As stated in Figure 1f, in the present invention, the unit structure is also U) including (preferably the above-mentioned US Patent No. 5. Partial, No. 904, the laminated assembly of the components described in the cut type) the positive electrode assembly 13, the negative electrode assembly 17, the battery separator-containing insert separator assembly 15. Combining the current collection material components η, 19 of each positive and negative component can provide circuit connections for the battery, such as extended end pieces ΐ2,16. For laboratory test purposes, an intermediate electrode, such as a silver wire 14, can be installed in the separator assembly 15 to establish a similar reference position for each positive and negative half electrode. In general, the positive electrode 13 includes nanometer-sized active materials (such as transition metal oxides, such as% 05, Mn02, or c03) containing polyvalent electrolyte cations (eg, alkaline earth cations) that can be added or absorbed. 〇4) The vinylidene copolymer matrix of the dispersion. The negatively balanced ion electrode 17 includes a similar copolymer matrix dispersion that can be reversibly plated, alloyed, nanomaterial materials added or otherwise reacted with it, or simple metal 4, and thus can provide monovalent cations (such as Li, Na Or other alkali metal) sources. The separator 15 can also be a polymer film, as described in the reference manual, or it can include widely used micropores. -8-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm). C Jing first read the phonetic on the back? Please fill in this page for more information) Binding ---- Order --------- Five Λ invention description (6 film or simple glass fiber 塾, any of them can absorb non-aqueous electrolyte, = '5 to 2 A solution of cyclic and non-cyclic carbon, ester, and mixture of polyvalent cation compounds containing M. The electrolyte may further include a small amount of a monovalent alkali metal salt of a negative electrode and a battery that can be manufactured in a discharged state. A: The reference data established by the selected Ag electrode i 4 provides a device that generally measures the electrolyte activity of the composition components selected by the electrode separately. In this way, it is possible to confirm an effective combination of the electrode and the electrolyte. For example, the reference The electrode is helpful for confirming the electrolyte battery mechanism. Among them, polyvalent cations (such as Y, are not acceptable for passivated alkali metal negative electrodes, and therefore: the electrode cannot be plated or reduced to charge the battery, unless the applied field exceeds the theoretical value. The required voltage] is determined in the same way, a single cation 3: 7 is also used, and a high positive reduction reaction of γ cation occurs in a half-cell where the accessible surface of the negative electrode is passivated. Invalid final voltage level. In the manufacture of cobalt-added battery cells, the selected battery composition and composition are standard Swagelok test battery packs, in which the positive and negative electrode assemblies with separator components that absorb electrolyte are pressed in opposite directions. Collecting material protects the components to achieve closeness between the basic films. After assembly, each battery is tested and the predetermined cycle speed is about 7.6 mA per gram of active material: MacPile automatic% B / O operating in galvanostatic mode The data recording system is arranged in the circuit to obtain the voltage / capacitance profile of the unique characteristics of the test battery. The description below, the following examples will provide a guide for those skilled in the art to choose the combination of ingredients and compositions that are effective in practice The flow rate is similar to that in the large order. The paper size is t rnm ^ (CNS) Aim ^ Q x 29f ^ t} _506154 No. 090112106 Patent Application Chinese Specification Correction Page (July 91 ) Chinese manual revision page (July 91) 7. ι 〇
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實例I 鋰插入試驗電池係如先前技藝之單一單價陽離子電池 單元中達到之操作電壓水準及容量之比較例般製備。正極 澆鑄成一層包括28重量份之毫微米尺寸之v2〇5、6份之導 電碳黑（MMM超級P)、15份之聚（亞乙晞氟·共-六氟丙 烯）（Elf Atochem，Kyuar 2801)、及含在28份丙酮中之23份 酞酸二乙酯可塑劑之組合物。該層在22 t下烘乾約〇 · 5小 時’形成自支撐薄膜，且自薄膜切割！平方公分之盤，得 到包括約4至1 〇 t克活性材料之電極組件，亦即。為 了依先前技藝之積層電池構造之方式將電解質導入電池 中，因此以二乙酸自電極盤組件萃取可塑劑。 同樣的自與正極類似之組合物澆鑄層製備Lisi之負極組 件，但以Si取代V2〇5。將一段烘乾萃取之層鋪在一段鋰箔 之上，且自複合材料切割電極組件盤。表面積大於約〇.5 平方米/克之LiSi合金於短時間内自動的於電極盤組件處就 地形成。 在實質上供水之狀態下（-8CTC露點），依Swagelok試驗電 池阻立成具有浸飽1 Μ之含LiClCU之碳酸乙烯酯（EC)及碳 酸二甲酯（DMC)之2 : 1混合物之電解質溶液之硼矽酸鹽 玻纖蟄插入盤之電極組件。該電池再於具有自動試驗控制 器/紀錄器之電路中循環數段時間，此期間放電過程中， 正極處加入之Li電解質陽離子反應及再充電過程中，於負 極處之還原均依一般方式重複《對紀錄之數據作圖，包括 電池之二電極輸出電壓，及顯示約為125 mAh/g之一般比 -10- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐） 506154 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明說明（8 ) 電容，得到圖2中所述之獨特之紀錄。 實例11 包括單一多離子電池單元之第二個比較例係依實例I之 方式，利用實例I之正極組件及包括毫微米尺寸之粉 末狀活性材料製備。電解質爲〇·5 Μ含Y(C1〇4)3之Ec · DMC 2 : 1混合物之溶液。 Y3+陽離子半電池反應在各正及負極處之檢測以半參考 電極1 4之協助，證明在正極處具有明確之加入或吸收，且 在負極處具有明確之還原或合金，因而可確定電 摩:陽離子之活性。然而，不幸的是單一；; 負極材料反應之電壓對於正極反應太高，以至於無法在電 極間建立明顯的電壓差異，該差異爲提供電池單元中最= 操作電壓水準所需之差異。該缺點在圖3中所述之循環電 壓差異上相當的明顯，其顯示實質上需增加之電池容量， 但僅使用少許電壓輸出。 實例111 本發明包含之電池單元，亦即包括至少包含依多價之二 重陽離子之電池一般係依前面實例之方式製備，包括各正 極及負極材料在放電循環段過程中，可加入或吸收多價陽 離子，如釔、鑭或鹼土金屬。或再充電循環鍛過程中，以 較小或活性更高之第二種陽離子（通常爲單價鹼金屬）還 原、電鍍或合金。合併此種電極材料中，電解質提供多價 陽離子’且可立即加入電解質溶液中形成第二種陽離子。 尤其是，該二重陽離子電池之正極組件包括實例I之V2〇 -1 ·:----Γ---* 裝--- (請先閱讀背面之注意事項再填寫本頁) 訂， -11 - 506154 A7 五、發明說明（9 ) ^米㈣’且負極組件包括該實例之LiSi。因此，雖狹 ⑨^活性電極材料可如先前技藝般，用在本發明之電池 構造中，但意外的對所用電解質陽離子會造成極大:差 異。依據本發明，電解質之陽離子係經選擇成爲 子結合之多價陽離子，但期望之陽離子一般爲負極= 心早價％離子成分。本實例中，電解f爲¥(⑽山。之“Μ 溶液。圖4中敘述微量之電池循環電壓，且顯示達到約， mAh/g之明顯的比電容，同時所得操作電壓相 約3至3·5 V.之間。 一本發明之二重陽離子電池之理論操作模式明顯的依下列 -般〈万法，其中在電池放電過程中，正極處會釋出電解 質落液中之多價Y、離子，同時Li +陽離子由負極進入溶 液中，且在電池再充電過程中，γ3+多價陽離子類在進入 電解質溶液中，同時在負極處還原Li+陽離子，且電Μ 合金，以維持對SHE約_3 ν之安定低電壓電池數據。又〆 其-類陽離子之反應主要在—電極處，同時相配合之陽 離子類（反應主要係在另一電極處之操作模式已在各階段 之可逆循環下，以樣品電池電極之一系列能量分散光譜儀 (EDS)分析得聰明。由此等EDS試驗結果，各電極主要 陽離子反應之確定爲正極處之γ/ν比與電池放電極再充電 之程度相符。Example I A lithium insertion test battery was prepared as a comparative example of the operating voltage level and capacity achieved in a single unit cation battery cell of the prior art. The positive electrode was cast into a layer including 28 parts by weight of nanometer-sized v205, 6 parts of conductive carbon black (MMM Super P), and 15 parts of poly (ethylene fluoride · co-hexafluoropropylene) (Elf Atochem, Kyuar 2801), and 23 parts of diethyl phthalate plasticizer in 28 parts of acetone. This layer is dried at 22 t for about 0.5 hours to form a self-supporting film, and it is cut from the film! On a square centimeter disk, an electrode assembly including about 4 to 10 t gram of active material was obtained, that is, an electrode assembly. In order to introduce the electrolyte into the battery according to the structure of the laminated battery of the prior art, diacetic acid was used to extract the plasticizer from the electrode plate assembly. The negative electrode assembly of Lisi was also prepared from a cast layer of a composition similar to the positive electrode, but V205 was replaced with Si. A section of the dried extraction layer was laid on a section of lithium foil, and the electrode assembly disk was cut from the composite material. LiSi alloys with a surface area greater than about 0.5 m2 / g are automatically formed in situ at the electrode pad assembly in a short period of time. In a state of substantially water supply (-8CTC dew point), the battery was erected according to the Swagelok test battery to an electrolyte solution having a 2: 1 mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) containing LiClCU saturated with 1 M The borosilicate glass fiber is inserted into the electrode assembly of the disc. The battery is cycled for a few more times in a circuit with an automatic test controller / recorder. During the discharge, the Li electrolyte cation added at the positive electrode and the recharge process, the reduction at the negative electrode is repeated in the usual way. "Plot the recorded data, including the output voltage of the two electrodes of the battery, and display a general ratio of about 125 mAh / g-10- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 506154 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (8) Capacitor, obtained the unique record described in Figure 2. Example 11 A second comparative example including a single polyion battery cell was prepared in the same manner as in Example I using the positive electrode assembly of Example I and a powdery active material including nanometer size. The electrolyte was a 0.5 M solution of Ec · DMC 2: 1 containing Y (C104) 3. The detection of the Y3 + cationic half-cell reaction at the positive and negative electrodes is assisted by the semi-reference electrode 14 to prove that it has a clear addition or absorption at the positive electrode and a clear reduction or alloy at the negative electrode, so the electric motor can be determined: Cationic activity. However, it is unfortunately single; the voltage at which the negative electrode reacts is too high for the positive electrode to establish a significant voltage difference between the electrodes, which is the difference required to provide the most = operating voltage level in the battery cell. This disadvantage is quite obvious in the difference in the circulating voltages described in FIG. 3, which shows that the battery capacity needs to be substantially increased, but only a small voltage output is used. Example 111 The battery cell included in the present invention, that is, a battery including at least a multivalent dication is generally prepared according to the previous example, including the positive and negative materials, which can be added or absorbed during the discharge cycle. Valence cations, such as yttrium, lanthanum or alkaline earth metals. Or during the recharge cycle forging, the second, lower or more active second cation (usually a monovalent alkali metal) is used to reduce, electroplat, or alloy. In combining such electrode materials, the electrolyte provides polyvalent cations' and can be immediately added to the electrolyte solution to form a second cation. In particular, the positive electrode assembly of the double cation battery includes V2〇-1 of Example I :: ---- Γ --- * Packing --- (Please read the precautions on the back before filling this page) Order,- 11-506154 A7 V. Description of the invention (9) ^ m㈣ 'and the negative electrode assembly includes LiSi of this example. Therefore, although the narrow active electrode material can be used in the battery structure of the present invention as in the prior art, unexpectedly, the electrolyte cation used can cause a great difference: a difference. According to the present invention, the cations of the electrolyte are selected to be multivalent cations that are bound to the ions, but the desired cations are generally the negative electrode = the premature valence% ionic component. In this example, the electrolytic f is ¥ (⑽ 山. The "M solution." A small amount of battery cycle voltage is described in Fig. 4, and it shows a significant specific capacitance of about mAh / g, while the obtained operating voltage is about 3 to 3 · 5 V. The theoretical operating mode of a double cation battery of the present invention is obviously according to the following-general method, in which during the battery discharge process, the polyvalent Y and ions in the electrolyte fallout are released at the positive electrode. At the same time, Li + cations enter the solution from the negative electrode, and during the battery recharging process, γ3 + polyvalent cations enter the electrolyte solution, and at the same time, Li + cations are reduced at the negative electrode, and the alloy is maintained to maintain about _3 for SHE. The stable low-voltage battery data of ν. Also, its-cation-like reaction is mainly at the electrode, and at the same time the matching cations (the reaction is mainly based on the operation mode of the other electrode has been in the reversible cycle of each stage, to A series of energy dispersive spectrometer (EDS) analysis of one of the sample battery electrodes was clever. From the results of EDS tests, the main cation reaction of each electrode was determined as the γ / ν ratio at the positive electrode and the battery discharge electrode was recharged. Inconsistencies degree.
實例I V 本發明二重陽離子電池之另一具體例係以支撑在鎳上之 金屬鋰之負極組件、包括C〇3〇4活性材料之正極組件、及 iII：---* 裝 (請先閱讀背面之注意事項再填寫本頁) 訂·-------—AVI . 經濟部智慧財產局員工消費合作社印製 12- 506154 Λ7 -— ___B7___ 五、發明說明（1〇 ) 0·5 Μ含Y(Cl〇4)3之電解質溶液。該電池所得之結果與實例 111之電池類似。Example IV Another specific example of the double cation battery of the present invention is a negative electrode assembly of metallic lithium supported on nickel, a positive electrode assembly including a C0304 active material, and iII: --- * installation (please read first Note on the back, please fill in this page again) Order · -------— AVI. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 12- 506154 Λ7 ----- ___B7___ 5. Description of the invention (1〇) 0 · 5 Μ Electrolyte solution containing Y (ClO4) 3. The results obtained by this battery were similar to those of Example 111.
實例V 本發明又另一具體例係以支撑在不銹鋼上之金屬鋰之負 極組件、包括如實例ΙΠ中之％〇5活性材料之正極組件、 及〇·33 Μ含Y(CF3S〇3)3之電解質溶液。如圖5中所述電池循 環特性之追蹤確認該二重陽離子構造電池之高電壓安定性 及改吾之容量。類似之電池限於單價構造，亦即使用包括 少谷於杈丙烯酯中之NaCl〇4電解質，且僅提供約9〇 mAh/g 之活性容量。 而了解热習本技藝者在研讀前述之敘述及實例後，將使 本發明之其他具體例及改變會變得顯而易見，且該具體例 及改變同樣的均包含在本發明所列附屬申請專利範圍之範 圍中。 I — ----：----裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Example V Another specific example of the present invention is a negative electrode assembly of metallic lithium supported on stainless steel, a positive electrode assembly including a% 05 active material as in Example III, and 0.33 M containing Y (CF3S〇3) 3 Electrolyte solution. Tracking of the battery cycle characteristics as described in FIG. 5 confirms the high voltage stability and capacity of the dication structure battery. Similar batteries are limited to the monovalent structure, that is, the use of NaClO4 electrolyte, which includes a small amount of propylene in the propylene ester, and only provides an active capacity of about 90 mAh / g. And those skilled in the art who read this article will make other specific examples and changes of the present invention obvious after studying the foregoing descriptions and examples, and the specific examples and changes are also included in the scope of the appended patents listed in the present invention. In the range. I — ----: ---------------- Order --------- (Please read the precautions on the back before filling out this page) Employees of the Intellectual Property Bureau of the Ministry of Economy Consumption The paper size printed by the cooperative applies the Chinese National Standard (CNS) A4 (210 X 297 mm)