TW515124B - Electrode for a lithium battery and a lithium secondary battery - Google Patents

Abstract

The present invention relates to a type of electrode for lithium battery. The electrode on the battery is formed by a thin film of active materials, such as microcrystalline silicon film and amorphous silicon, that can adsorb and release lithium. By means of the joint formed in the thickness direction, the thin film is separated into columnar shape with its bottom closely attached to the battery.

Description

515124 Printed by B7 of the Intellectual Property Bureau Consumer Cooperative Ltd. V. Description of the Invention (1) [Technical Field] The present invention relates to a novel lithium battery and lithium secondary battery (lithium battery) that use the electricity [Background Technology] ] In recent years, research and development of lithium secondary electrodes such as electrode types, their charge and discharge voltage, and charge and discharge cycle life]: So: the characteristics of the battery and other characteristics have a great influence and change. The battery characteristics can be improved by retaining the active material. ’By improving the electrode | s When the six denier is used as a negative electrode active material, it can constitute a battery with two energy densities by weight. However, when charging, the bell metal will squeeze

The precipitation of dendritic crystals causes the problem of internal short circuit. X For the above problems, there is a report using lithium secondary electrodes where aluminum, silicon, tin, etc. are used as electrodes when electrochemical reactions occur during charging (see Solid State Ionics, pages 113 to 115, 57 (1998 》. Especially Shi Xi has a large theoretical capacity, and it is very futuristic as a negative electrode for batteries showing high capacity. “Therefore, there have been research reports on various secondary batteries using this as a negative electrode (refer to Japanese Laid-Open Patent Publication No. Hei. No. 10-255768). However, this alloy negative electrode, which is an electrode active material, becomes fine powder after charging and discharging, and the storage characteristics are deteriorated. Therefore, a sufficient charge-discharge cycle cannot be obtained. [Summary of the Invention] The object of the present invention is to provide a novel lithium battery for a lithium secondary battery which can be used as an electrode of a clock secondary battery and has a high charge / discharge capacity and excellent charge / discharge cycle characteristics. Electrodes, and the paper size of lithium batteries using the electrodes are applicable to China National Standard (CNS) A4 specifications (Q χ 297) (1) 311933 515124 A7 B7 Economy Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau. 5. Description of the invention (2 cells and lithium secondary batteries. The present invention is a lithium battery electrode provided with a thin film made of a storable substance on an electric storage body. The active substance is separated into a columnar shape, and the bottom part of the columnar part is formed into a cut. It is characterized by the animal body being joined together with the active material film of the present invention t by being separated into a slit formed in A. Column-shaped. Therefore, the gap formed in the "-direction" can reduce the stress caused by the charge-discharge cycle during the charge-discharge cycle, and suppress the occurrence of stress such as active material = peeling from the electric body. The tightness between the eight-layered films can be kept in good condition. ^ Bottom storage battery of the knife In the present invention, in the thickness direction of the film, the portion of the film with a thickness of at least 1/2 or more is separated by slitting into A columnar shape is preferred. In addition, when the surface of the film is uneven, and the slit at the end of the unevenness is formed on the film, the columnar ^ Hachimachi columnar trowel is formed on the surface of the film by at least one convex portion. It is also feasible to form a slit. At this time, a slit is formed on the surface of the thin layer so that the columnar portion contains a plurality of convex portions. This slit is formed in the slit of the film, which can be formed during the first charge and discharge. In this case, 'for example, a concave-convex portion is formed on the surface f of the film before charging and discharging', a first and subsequent charge-discharge process forms a slit with the valley portion of the concave-convex portion on the surface of the film as an end. The seam separates the film into a columnar shape.? The unevenness on the surface of the film can be formed corresponding to the unevenness on the surface of the bottom layer of the electricity storage body. The hybrid L_ and the straw are made of the electricity storage body with unevenness on the surface. Home Fresh-: --- Order i 2 311933 MM24 A7 ... Jihui

I system 5. Description of the invention (3) When a thin film is formed on the surface, unevenness can be provided on the surface of the thin film. The surface roughness (Ra) of the electricity storage body is preferably 001 // Π1 or more. Among them, 0.001 to 1 / zm is more preferable, and 005 to 0.05 "111 is the most preferable. The above-mentioned surface roughness ( Ra) is specified in Japanese Industrial Standards (JIS B 〇〇〇〇_1994) 'For example, it can be measured with a surface roughness meter. In the present invention, the surface roughness (Ra) of the electricity storage body is thin for the active material. The thickness of the film In other words, it is preferable to maintain the relationship of Ra ^ t. In addition, it is preferable that the surface roughness (Ra) of the electricity storage body and the average interval (s) of local peaks have a relationship of 1000 to ^ s. Local peaks The average interval has been specified in Japanese Industrial Standard (JIS B0610 · 1994). For example, it can be measured by a surface roughness meter. The shape of the convex and concave portions on the surface of the electricity storage body is not particularly limited, such as a cone. The shape is more suitable. Columnar. The upper part of the P-knife is more suitable to have a circular shape in order to avoid the current during the charge and discharge reaction. In the present invention, the thickness direction formed on the thin film made of the active material The slit can be formed during the first and subsequent charging and discharging, and it can also be formed before charging and discharging. Before charging and discharging, a method of forming a slit on the film can be used to make the film of the electrode occlude lithium and then release it before forming the battery. After the volume of the film has swelled, it can be formed by shrinking. Of course, when using an active material that does not contain a bell at the positive electrode, the shape of the sutra can be stored, and the sigma can also be used. For example, lithography (phοt〇 called nphy) can be separated into a column shape by a slit. The thin film is not a problem. I The active material in the present invention is thin, for example, made of lithium and compounds or formed on this paper. The size of the paper is suitable—CNS A4 specification⑵G x 297 · ^^ 3 311933

-nni (Please read the precautions on the back before filling this page) nn H nnn I equipment • ϋ nn I --- order ----- • line · A7 V. Description of the invention (, formed by the material of the solution. The above material family, IIIB, and IVB are listed with elements on the periodic table, ^, and VB_, as well as the fourth cycle on the teeth, and the fifth cycle. Periodic table compounds and sulphides are selected from at least, oxygen of the transition metal element of the period, and a material selected from the group., Group VIII, Group IVB and; Dream '*, Ci-Gallium, Wrong, Illustrative elements such as carbon, &, and bismuth. Also, the fourth, fifth and fifth cycles on the chronological table of the first phase of tin, antimony, mercury, shavings, and lead. The second week: transition metal elements, specifically, such as sharp, titanium, samarium chromium, manganese, iron, cobalt, nickel, steel, m dynasty, wrong, niobium, molybdenum, hafnium, nail, money, ji, Elements of silver, knitting, lanthanide, nitrogen, hafnium, crane, chain, star, silver, platinum, gold, mercury, etc. Among the above elements, carbon, silicon, germanium, tin, lead, aluminum, indium, zinc, Syria Syria It is advisable to select at least one kind of mercury, especially to make heart and / or germanium #. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Generally speaking, silicon can be roughly divided into non-silicon based on its crystallinity. Crystalline silicon, microcrystalline silicon, polycrystalline silicon, and single crystal silicon. The amorphous silicon in the present invention means amorphous silicon and microcrystalline silicon other than polycrystalline silicon and single crystal silicon. Amorphous When Raman spectroscopy is performed on silicon, it corresponds to the vicinity of 520 cm-1 in the crystalline field, and there is virtually no peak. When Raman spectroscopy is performed on silicon, microcrystalline silicon corresponds to the peak near 52ocnrl in the crystalline field And corresponding to the high front near 480CHT1 in the amorphous field, essentially two peaks will appear. Therefore, microcrystalline silicon is essentially composed of the crystalline field and the amorphous field. Polycrystalline silicon and single crystal silicon Raman paper size is applicable to China National Standard (CNS) A4 (21 × 297 mm) 311933 A7

:) 丄 厶 呻 A7 ______B7 V. Description of the invention (6 electrolytes, immersed in the metal plate ^ and I, the same, through the rotation of the drum and guide M1 to precipitate copper on the surface of the same rotation ' Copper foil obtained by peeling. One or both sides of the electrolytic tincture can be subjected to rough rounding or surface treatment. ^ Electrolytic method can precipitate copper on the surface of dairy copper, and the surface can also be roughened steel or metallurgy. It is also possible to form an intermediate layer on the electricity storage body and form an active material film on the intermediate layer. In this case, the 'intermediate layer preferably contains a component that easily diffuses into the active material film, for example, a copper layer is preferred. A surface-roughened recording box (electrolytic nickel drop, etc.) may use a copper storage layer. Also, copper can be precipitated on the recording by electrolytic method, so that the recording of rough sugar can also be performed. It can be used. ^ In the present invention, the cutting formed on the active material thin film can also be formed along the low-density area by extending in the thickness direction of the active material thin film beforehand. The above low Density field, such as the valley of the uneven part of the electricity storage meter @ It is formed by extending upward. In the middle of this month, it is preferable that the components of the electric storage body can be diffused in the active material film. By diffusing the above-mentioned components of the electric storage body into the film, the adhesion between the electric storage body and the active material can be improved. As a component of the electric storage body, if elements such as copper, which does not alloy with the bell, diffuse, it can suppress the metallization with the bell element ^ in the diffusion field. Therefore, it can also suppress the expansion and contraction of the film caused by the charge and discharge reaction. And it can suppress the stress caused by the active material film from peeling from the electricity storage body. The concentration of the electricity storage body component diffused in the film should be higher near the electricity storage body, and it should be reduced as it approaches the surface of the film. With this paper standard suitable for financial countries iii standard (CNS) A4 $ 格 ⑽χ 297 public issue) 6 311933 ί page I · order miscellaneous 515124 A7 V. Description of the invention (7) Concentration gradient of the components of the electricity storage device The expansion and contraction force of the thin film produced by the discharge reaction can play a stronger role in the vicinity of the electricity storage body, so it is easy to suppress the occurrence of peeling of the active material film near the electricity storage body, which can cause peeling of the active material film. In addition, with the approach of the surface of the thin mold, the decrease in the concentration of the component of the electric storage body is effective for maintaining a high charge and discharge capacity. It is preferable that the diffused electricity storage component component 'forms a solid solution without forming an intermetallic compound with the thin film component in the thin film. The above-mentioned intermetallic compound means that the metals are combined with each other at a specific ratio to form a compound having a specific crystal structure. The thin film component and the storage battery component are formed into a solid solution in the thin film by not becoming an intermetallic compound, so that the adhesion state between the thin film and the storage body is better, and a higher charge and discharge capacity can be obtained. In the present invention, the active material sheet may be covered with a varnish of foreign materials. Examples of the impurities include phosphorus, aluminum, arsenic, antimony, boron, gallium, indium,

Group IIIB of the periodic table of oxygen, nitrogen and other elements! VB, VB, VIB elements. The active material film in the present invention may be formed by laminating a plurality of layers. The composition, concentration of the crystalline 'impurity, and the like in each layer of the stacked layer may be different. Further, it may have an inclined structure in the thickness direction of the film. For example, the composition 'crystallinity, the concentration of impurities, and the like can be changed in the thickness direction to form an inclined structure. The active material film in the present invention is preferably an active material film that occludes the bell by forming an alloy with the bell. The active material film of the present invention can also be stored or added in advance. It can also be added when the active material film is formed. In other words, China (CNS) ^^ i () χ 297 is applied by the size of the paper [7 311933 A7 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs B7 V. Description of the invention (8) = active substance containing a bell Thin film, and added to the active material film: thin = after forming the active material film. The method of storing or adding a bell to the active material, or absorbing or adding lithium to the active material film is exemplified by electrochemical methods. Methods Storage or addition of lithium. / ′ ° Although the thickness of the active material film of the present invention is not particularly limited, a thickness of 2 () _ or less may be adopted as the thickness. In addition, in order to obtain a high charge and discharge capacity, the thickness is preferably 1 // m or more. In the present invention, in order to improve the adhesion between the electricity storage body and the thin film, an intermediate layer may be provided between the electricity storage body and the thin film. The material of the intermediate layer is preferably a substance capable of forming a solid solution between the electricity storage material and the active material material. The L gold is particularly characterized by being capable of forming the lithium battery of the present invention, and including the negative electrode, the positive electrode, and the electrolyte composed of the electrode of the present invention. In the present invention, the term "lithium battery" includes lithium primary batteries and lithium secondary batteries. Therefore, the electrode system of the present invention can be used for lithium primary batteries and lithium secondary batteries. The lithium secondary battery of the present invention is characterized by including a negative electrode, a positive electrode, and a nonaqueous electrolyte composed of the electrode of the present invention. The solvent of the electrolyte used in the lithium secondary battery of the present invention is not particularly limited, such as cyclic carbonates such as ethylene carbonate, propylene carbonate, butene carbonate, and dimethyl carbonate, methyl carbonate, ethyl ester, and diethyl carbonate. Mixed solvents such as chain carbonates. In addition, the cyclic carbonate and ether solvents such as 2-dimethoxyethane, 1,2-diethoxyethane, or r.butyrolactone, tetrahydrothiophene dioxide, and methyl acetate The mixed solvent Y among the chain-like esters, etc., g paper size is applicable to China National Standard (CNS) A4 specification (2_1G X 297 public love) ------------ 8 311933 ---- ------- AWI ^ -------- 1 --------- (Please read the notes on the back before filling this page) 515124 JJ---JJ --- 1 ----. 'Printed A7 by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (9) Solutes of electrolytes, such as LiPF6, LiBF4, LiCF3S03,

LiN (CF3S02) 2, LiN (C2F5S02) 2, LiN (CF3S02) (C4F9S02), LiC (CF3SO2) 3 > LiC (C2F5SO2) 3 ^ LiASF6 > LiC / O4 > Li2B10C / 10 >

Li2B12C / 12 and the like and mixtures thereof. Furthermore, examples of the electrolyte include a sol-like polymer electrolyte obtained by impregnating an electrolyte with a polymer electrolyte such as polyethylene oxide, polyacrylonitrile, and polyvinylidene fluoride, or an organic solid electrolyte such as Lil or Li3N. Wait. The electrolyte of the lithium secondary battery of the present invention is a lithium compound for a solvent that exhibits ionic conductivity, and the solvent for dissolving and maintaining it will not be decomposed by the voltage when the battery is charged, discharged or stored. Can be used without restrictions. The positive electrode active material of the bell secondary battery of the present invention, such as A,

LiNi02, LiMn204, LiMn02, LiCo. 5Ni0 5〇2,

LiNiuCouMn ^ O2 and other lithium-containing transition metal oxides, or manganese dioxide and other lithium-free metal oxides. In addition, other materials capable of electrochemically inserting and removing lithium can be used without any restrictions. The electrode of the present invention can also provide batteries other than lithium such as non-aqueous electrolyte batteries and non-aqueous electrolyte secondary batteries composed of electrode active materials capable of occluding and releasing alkali metals such as sodium or potassium or alkaline earth metals such as magnesium or calcium. Electrode use. Another electrode of the present invention is provided with an electrode material layer composed of a thin film and an electricity storage body in close contact with the electrode material layer. The left side of the film is connected in a mesh shape and extends toward the electricity storage body in the thickness direction. Shape 2 is characterized by its low density area. The above-mentioned electrode for a secondary battery is, for example, in the above-mentioned electrode for a clock battery of the present invention, the Chinese National Standard (CNg) A4 specification is applied along the low-density area toward the thickness M-scale (the χχ 公公 发-also 9 311933 II Μ -------- ^ --------- line (please read the precautions on the back before filling this page) 5. Description of the invention (10) Extending the direction to form a slit The electrode in the aforementioned state. Therefore, it is preferable that the electric storage component is diffused on the thin film, and the positive electrode component does not form an intermetallic compound with the thin film component in the film, but preferably forms a solid solution. It is preferable to form a thin film on a power storage body by a thin samarium formation method. Examples of the samarium film formation method include methods such as a CVD method, an emission reduction method, a vapor deposition method, a flame spraying method, and an electroplating method. It is formed in the low-density field of the film. It is the same as the low-density field described in the above-mentioned bell electrode and the electrode of the present invention. As for the active material thin film and the electricity storage body, the same active material film used in the battery electrode of the present invention and Power storage body. [Simplified illustration Figure 1 is a schematic cross-sectional view of a lithium secondary battery manufactured in an example of the present invention. ▲ Figure 2 is a scanning electron micrograph (2000) showing the state of an electrode of an embodiment of the present invention before charging and discharging Magnification). Μ FIG. 3 is a scanning electron microscope photograph (5000 times magnification) of an electrode of one embodiment of the present invention before charging and discharging. FIG. 4 is an embodiment of the present invention. Scanning electron microscope photograph (500 times magnification) of the electrode after charging and discharging. Fig. 5 is a scanning electron microscope photograph (2500 times magnification) showing the state of the electrode after charging and discharging according to an embodiment of the present invention. Fig. 6 is a scanning electron microscope photograph (1000 times magnification) showing a silicon thin film of an electrode of an embodiment of the present invention as viewed from above. This ϋ standard applies to China (⑽) A4 size ⑵G x 297 male Li) ---------- | _ equipment (please read the precautions on the back before filling this page) ^ · 11111 Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 311933 A7

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 -------- B7__ V. Description of the Invention (12) ~ --- This is a scanning electron microscope photograph showing the state of the electrode of the present invention before charging and discharging (2 〇OOx magnification). Figure 20 is a field-type electron microscope photograph (1000-fold magnification) showing the state of the electrode a7 of the present invention before charging and discharging. The drawing is a scanning electron microscope photograph (2000 times magnification) showing the state of the electrode a8 of the present invention before charging and discharging. Fig. 22 is a scanning electron microscope photograph (10,000 times magnification) showing the state of the electrode of the present invention before charging and discharging. The drawing is a scanning electron microscope photograph (500 times magnification) showing the state of the electrode a7 of the present invention after charging and discharging. The figure is a scanning electron microscope photograph (2500 times magnification) showing the state of the electrode a7 of the present invention after charging and discharging. Fig. 25 is a scanning electron microscope photograph (500 times magnification) showing the state of the electrode a8 of the present invention after charging and discharging. Fig. 26 is a scanning electron microscope photograph (250,000 times magnification) showing the state of the electrode of the present invention after charging and discharging. Fig. 27 is a scanning electron microscope photograph (1000 times magnification) showing the shape of germanium thin film after charging and discharging of the electrode of the present invention, viewed from above. $ 28 is a scanning electron microscope photograph (50,000 times magnification) showing the shape of the thin electrode of germanium after charging and discharging, which is the electrode of the present invention. Figure 29 shows the electrode a7 of the present invention. Scanning electron microscope photograph of the state of the germanium film after charging and discharging viewed from a slightly oblique direction (1000 times the paper size is applicable to China 1¾ 豕 CN (CNS) A4 size⑵G x 29 Factory ----- 12 311933 ----------- * Install -------- Order --------- (Please read the precautions on the back before filling this page) A7

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs). Figure 30 Wei Wei — ^ UL At, the germanium film of electrode a7 of the present invention after charging and discharging

The state of the state is observed by a slightly oblique square A-scanning electron microscope photograph (5000 times magnification). Figure 31 # 矣-′, the state of the germanium film of the electrode a8 of the present invention after charging and discharging is from the top_window β Scanning electron microscope photograph (1000 times magnification • rate). Figure 32 will be 矣-丄 #

At ′, the electrode a8 of the present invention has a shape of a germanium film after charging and discharging. * 3, a sacrifice-type electron microscope photograph (5000 times magnification). Fig. 33 is a scanning electron microscope photograph (1000-times magnification) showing the shape of the germanium film of the electrode a8 of the present invention after charging and discharging. Fig. 34-"I" shows a scanning electron microscope photograph (5000 times magnification) of the germanium film Xin of the electrode a8 of the present invention after charging and discharging, viewed from a slightly oblique direction. ^^ 3 5 Figure Γ ^ ΐ is a scanning electron microscope photograph (1000 times magnification) showing the shape of the germanium film '7 of the electrode a7 of the present invention before charging and discharging. Figure 36 shows the electrode a8 of the present invention being charged and discharged. Scanning electron microscope photograph (1000 times magnification) of the germanium thin film-like shape before discharge viewed from above. Figure 37 is a diagram showing the concentration distribution of the constituent elements of the germanium thin film of the electrode a7 of the present invention in the depth direction. --------------------- ^ --------- ^ (Please read the notes on the back before filling this page) This paper size applies (G x 297 public love) 13 311933 515124 A7 B7 V. Description of the invention (14) The figure shows the concentration distribution diagram of the germanium film of the electrode a8 of the present invention in the deep. It also shows to the figure 39 According to the present invention, the scanning electrode electron microscope photograph (2000 times magnification) is taken from the judgment of the other electrode al 1. Fig. 40 is a scanning electron microscope photograph (1000 times magnification) showing a cross section of the electrode 1 of the present invention, and is also an enemy of the present invention. Fig. 41 is a diagram showing the electrode before charging and discharging of the present invention. Scanning electron microscope photograph (1000 times magnification) of silicon thin film viewed from above. Figure 42 is a scanning electron microscope photograph (100%) of the silicon film of electrode 后 after charging and discharging according to the present invention is viewed from above. 〇 × magnification). Figure 43 shows the transmission electron microscope photograph of copper foil and silicon film near the interface (magnification of 500,000 times). Figure 44 shows the copper foil and silicon film near the interface. Photograph of a transmission electron microscope (magnification of 1 million times). # Figure 45 shows the distribution of copper and nitrogen concentration in the depth direction of the mixed layer on the electrode cl. Figure 46 shows the mixed layer on the electrode c3. Copper and argon concentration distribution map in the depth direction. [Description of element symbols] Property pf 1 1 Positive electrode 2 Negative staff 3 Separator 4 Positive strike consumer 5 Negative electrode 6 Positive electrode battery company 7 Negative electrode battery 8 Margin printed 20 substrate 21 Plasma source This paper size applies Chinese National Standard (CNS) A4 specification (21 × 297 mm 311933 A7) V. Description of invention (15 23 Hydrogen plasma 25 Microwave power 22 Plasma generation chamber 24 Electronics Beam gun 26 Hydrogen [The best embodiment of the present invention] The present invention will be explained in detail in accordance with the following examples. Y Japanese inventions do not bias the scope of the following embodiments, and the present invention is not limited to non-bonded flying moons. "When the change is implemented. … Within the scope of the invention's purpose (manufacturing of the negative electrode) using dry copper foil (thick-sound rabbit / 0., 1 and 18 # melons) as the substrate, and using silane (hH4) as the raw material gas, Jun # uses Lice is the carrier gas, and microcrystalline stone slabs are formed on the printed f by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Steel Economy by CVD. Specifically, a heater is placed on the heater of the reaction chamber as a substrate, and a vacuum exhaust device is used to evacuate the reaction chamber to an IPa or less. Then, the silane (s ^ 4) of the gas raw material and the hydrogen gas of the carrier gas are introduced through the gas raw material introduction hole, and the substrate is heated to 18GC with a heater. The vacuum degree is adjusted by the vacuum exhaust device to the reaction pressure, which is excited by the same cycle power source. High frequency, which is induced by the electrode to induce a glow discharge. The detailed film formation conditions are shown in Table 丨. In addition, the flow unit SCCm in Table j is 0 ° C, and the volume in centimeters (cm / min) at 1 atmosphere (1103 kpa) is an abbreviation of Standard Cubic Centimeters Per Minute. This paper scale is applicable to China National Standard (CNS) A4 specification (210 x 297 mm) 15 311933 515124 A7 B7 V. Description of the invention (16) Table item 1 10 seem carrier gas hydrogen (H2) flow substrate temperature reaction pressure High frequency power 200 seem

180 ° C 40 Pa

555W _ | Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The film thickness of the microcrystalline silicon film deposited under the above conditions has reached about 10 # m. When it was observed with an electron microscope (2 million times), it was confirmed that the amorphous region was arranged around the crystal region composed of the fine crystal material, and it was confirmed that it was amorphous. Next, the obtained sample was punched to a diameter of 17 mm to obtain an electrode al °, which was heat-treated at 400 ° C for 3 hours at the same temperature as the electrode al to obtain an electrode a2. For comparison, 90 parts by weight of monocrystalline silicon powder (grain control 10 # m) on the market, and parts by weight of polytetrafluoroethylene as a binder are mixed, and then a 17 mm diameter die is pressed and formed. The ingot-shaped electrode b 1 0 (manufactured as a positive electrode) was made using Li / O3 and COCO3 as starting materials, and the atomic ratio of the bell and the record was 1: 1. After weighing, they were mixed in a mortar and a 17 mm diameter mold was used. After compression molding, a LiCo0 2 calcined body was obtained by firing at 80 ° C. for 24 hours in the air, and this was ground in a mortar to obtain a powder having an average particle size of ⑽ to 。. The obtained LiCo 02 powder 80 Parts by weight, as the weight parts of acetic acid for conductive materials, and 10 parts by weight of teflon binder, mixed (please read the precautions on the back before filling this page) 515124 A7 V. Description of the invention (After the Π is pressed and formed in a 17mm diameter die to obtain an ingot-shaped positive electrode. (Manufacture of electrolyte) (Please read the precautions on the back before filling this page) Ester and diethyl carbonate in the same volume of mixed solvent, dissolve LiPF0 1 mole / liter and An electrolytic solution was prepared and used in the following batteries. 彳 | (manufacturing of batteries) The above-mentioned electrodes al, a2, and bl were used as negative electrodes, and the above-mentioned positive electrodes and electrolytic solution were used to manufacture flat lithium secondary batteries. The diagram is a schematic cross-sectional view of the lithium secondary battery produced, which is composed of positive electrode 1, negative electrode 2, separator 3, positive electrode 缶 4, negative electrode 缶 5, positive electrode electric storage body 6, negative electrode electric storage body 7, and polypropylene insulating gasket. The positive electrode 1 and the negative electrode 2 are opposed to each other through the separator 3. These are housed in a battery case formed by the positive electrode 缶 4 and the negative electrode 缶 5. The positive electrode is connected to the positive electrode animal body 6 through The positive electrode 缶 4 and the negative electrode 2 are connected to the negative electrode 缶 5 through the negative electrode electricity storage body 7, which is a secondary battery structure that can be charged and discharged. The employee's cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the electrode al as the negative electrode as battery A1 Use electrode ^ as the negative electrode as battery A2, and use electrode bl as the negative electrode as battery B1. (Measurement of charge-discharge cycle life characteristics) At 25t, charge with a current value of 100 / i A to the capacity of the negative electrode. Discharge after 2000mAh / g as this Charge and discharge for one cycle, and measure the capacity retention rate at the 50th cycle for each battery. In addition, if the battery (B1) that cannot be charged to 2000 mAli / g is charged to 4.2 V, perform the cycle test by discharging. The results are shown in Table 2. The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 17 311933 515124 V. Description of the invention (1S) ~ Table 2 'Use the negative active material of each battery by The lice gas concentration measured by SIMS, the ratio of the two peak intensities in the vicinity / 52cm-i near Raman spectrum analysis', and the crystal grain size calculated from the X-ray diffraction spectrum and the equation are given and expressed. In addition, the crystal grain size of the battery (bi) may be almost the same as the particle size of the powder. Therefore, the capacity maintenance rate of the 50th cycle of the watch battery is represented by the particle size of the battery. TTST " Content A1 85% 4% ^ A2 7 8% 0.01% B1 5% 0% peak intensity ratio (480 ^ / 520 cn knot culvert particle size 0.1 0.1 lnm (please read the precautions on the back before filling out this page) T device lnm 1 〇 “m The results shown in Table 2 show the The battery AUA2 has a significantly higher capacity retention rate compared to the Zhao battery (B1). As mentioned above, by using microcrystalline Shixiya film as the negative electrode active material, the charge and discharge cycle characteristics of the clock secondary battery can be significantly improved. Represented. On the crystallized sapphire film, when the storage and material are stored, its swelling is reduced, so it can suppress the micronization of the negative electrode active material, and the deterioration of the characteristics is expected. 1 Experiment 2 Use of electrolytic copper (18) Heart thickness) as the substrate of the electricity storage body. All other tests were carried out in accordance with the above experiment! The battery A1 was also made of a microcrystalline silicon film (about 10 # m thick) in an electrolytic steel box. The battery was then made into a battery A3. Standards apply to China National Standard (CNS) A4 specifications (210 X 297 Public Love 311933 tr --------- Participate-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 515124 A7 B7 V. Description of the invention () ----------- --- ^ --- (Please read the precautions on the back before filling in this page) The surface of the rolled copper foil used in Experiment 1 was made of paper by grinding for one minute, and used. This steel two = No. sand Except for the substrate, all other batteries were prepared in accordance with the above-mentioned battery: a microcrystalline silicon film (about 10 "m thickness) was formed on the substrate, and 5 / white 4.0 sander was used as an electrode", and 12. Research 八 8 and 55. Test 1 The same method was used to obtain electricity. These batteries A3 to A5 and the above-mentioned battery] and battery B1 were prepared according to the same charge and discharge conditions as those in the above-mentioned experiment M. Charge-discharge cycle test 'to obtain the capacity maintenance rate of the 1G cycle. The social results are not shown in Table 3. Also in Table 3, the battery storage of battery A1 and battery Bι: the copper box and the storage bodies of batteries A3 to A5. The surface roughness (Ra) of steel drops and the average interval of local peaks are shown together. The surface roughness (Ra) of steel foil and the average interval of local peaks-丨 Line · • It is measured by using a stylus-type surface shape measuring instrument Dektak ST type (I made by Japan Vacuum Technology Co., Ltd., the measurement distance is set at 2.0mm. The surface roughness and roughness j are calculated after correcting the bent part. The .bending amendment is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Positive values are low-pass value = 20 / zm and high-pass value = 20 am. Surface roughness (R is a value obtained by automatic calculation. The average interval of local peaks § is a value judged from the chart. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 19 311933 515124 5 Description of the invention (20) Table 3 Capacity maintenance rate of battery 10th cycle A1 Surface roughness 0.037 ~ ----_ 0.188 t Electric body (copper foil) Average interval S (// m) A3 97% 99 % 14

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The results shown in Table 3 show +7 I & clothing display. It is not known that the use of copper with a large surface roughness Ra value as the power storage battery A3 to A5 is lower than the surface roughness Ra value. The small copper pig is the battery A1 of the power storage body, and the capacity maintenance rate of the 10th cycle is increased. This is due to the use of copper pigs with a large surface sugar content and a large heart value as the electricity storage body. The closeness between the electricity storage body and the active substance is improved. It is speculated that the activity caused by the expansion and contraction of the active substance can be reduced during storage and release of the bell Influence of structural changes such as matter. Experiment 3 The above experiment! The obtained battery A1 and the above-mentioned cell A3 ′ of the above-mentioned experiment 2 are in accordance with the above-mentioned experiment! Under the same charge-discharge cycle conditions, the charge-discharge cycle test was performed again to obtain the capacity retention rate at the 30th cycle.仃 Not shown in Table 4 〇 The size of the fruit paper is applicable to China National Standard (CNS) A4 (21〇X 297 Public Love 311933 ^ -------- ^ --------- (please first Read the notes on the back and then fill out this page), the description of the invention (Table 4 Battery A1 A3 Capture rate _ 91% 97% Printed by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The results in Table 4 are displayed after the 30th cycle ' Battery magic and A3 have good capacity maintenance rate. In particular, the battery A3 with steel surface with a large surface roughness h value as a livestock electric body shows a better capacity maintenance rate. Therefore, the 'Shishi film of the electrode a3 used for battery A3 The state is as follows: D: submicroscopic observation. First, the electrode a3, which is in the state before the battery and also before the charge and discharge, is observed with a scanning electron microscope. Figures 2 and 3 show the charge and discharge, respectively. The previous electrode was taken with a scanning electron microscope (secondary electron image). The magnification of the second figure is 2000 times, and the magnification of the second figure is 5000 times. The sample is manufactured by embedding the electrode with resin and embedding it. Cut into slices and observe. Figure 2 shows the upper and lower ends. The layer observed at the upper end in Figure 3 is the above-mentioned embedded resin layer. In Figures 2 and 3, the slightly brighter part indicates the copper foil part, and the darker part on the steel foil is formed with a silicon film (about 1 〇 # m thickness). As shown in Figures 2 and 3, "the copper foil surface is uneven," in which the convex part is particularly a cone. Then, the surface of the silicon film provided thereon is also formed in the same manner as the copper foil unevenness. There are irregularities. Therefore, it is speculated that the irregularities on the surface of the silicon film are formed by the irregularities on the surface of the copper box. Secondly, the electric Yang a3 taken out from the battery A3 after the 30th cycle described above is also embedded with a resin for scanning electron microscope observation. In addition, the size of the electrode paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 311933 ^ ----------------- $ (Please read the precautions on the back first Fill out this page again) M5124 ___B7 V. Description of the invention (22 a3 is taken out after discharging, so Figure 4 and 5S are after the state of electricity. Micrograph (2 = Table = scanning electron of electrode Γ) 5 The magnification of the graph is 25 × ^ The magnification of the graph is 5000 ×, and the slit H graph As shown in Fig. 5, the dream film is formed in the thickness direction. • The seam can be seen that the silicon film is separated into columns. In addition, the film is formed in the thickness direction and hardly formed in the plane direction. On the copper box of the electricity storage body. In addition, the columnar part =: part is rounded. It can be seen that there is a slit formed in the valley portion of the uneven portion on the surface of the broken film before charging and discharging. The surface of the Shi Xitao film of the electrode 33 after charging and discharging. Figures 6 and 7 show the type of the electron microscope (secondary electron image) of the Shi Xi film surface viewed from above. The magnification of FIG. 7 is 5000 times. Figures 8 and 9 are scanning electron microscope photographs (secondary electron images) of the silicon film surface viewed from a slightly oblique direction. The magnification of Figure 8 is 1000 times, and the 9th person is 5000 times. Mouth < As shown in Figs. 6 to 9, a slit is formed around the columnar portion of the silicon film, and a hole is provided with the adjacent columnar portion. Therefore, when the charge =, the silicon film occludes lithium, and even if the columnar portion expands to increase its volume, it is estimated that the increased volume can be absorbed by the pores formed around the columnar portion. In addition, during discharge, lithium was contracted by the columnar portion of the silicon film, the volume was reduced again, and pores were formed around the columnar portion. With the columnar structure of the above-mentioned I k kinds of ^, it is possible to ease the charge and discharge, because the paper size of the active material is applicable to the standard (CNS) A4 (21G X 297 mm) " ----——- ^ 22 311933 Order # Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 515124 A7

311933 515124 A7 V. Description of the invention (24) 11 When the bell is released, the volume will shrink. At this time, a tensile stress is generated in the 'Shi Xi film u. The stress is concentrated on the surface ㈣ of the iu_, so the concavity and convexity of the surface should be the same! As shown in Figure ⑷, the thickness is from the valley m as the starting point; the cut 12 is formed, and the cuts 2 formed in this way can prevent the stress-relieving stone film 11 from peeling from the steel drop 10 and shrink the stone film U. . In the m electric cycle separated into columns in accordance with the upper speed, as described above, the pores around the columnar portion are formed by 忐 少 心 ⑴, 々 々, and 由 to reduce the expansion and contraction of the active substance. The sexual substance does not peel off from the electricity storage body, and the charge and discharge cycle is repeated repeatedly. In order to further advance / examine the mechanism of the slit formed by the above Shi Xi film, the electrode a3 with a film thickness of about 10 ... microcrystalline Shi Xi film formed on the electrolytic copper was observed with a transmission electron microscope. Figure „shows a cross-sectional transmission electron microscope photograph of electrode u before charging and discharging (12500 times magnification). Observation samples were obtained by slicing the electrode with resin and sectioning it. i! Photograph of a transmission electron microscope not shown in the figure. In the transmission electron microscope photograph shown in FIG. 11, as shown in FIG. 13, a stone evening film 11 is formed on the surface of the electrolytic steel 10, and in the dental electron microscope photograph, stone evening The thin film ii is indicated by a brighter part than copper. When the ㈣ film u shown in Fig. N is observed, the connection area between the surface lala of the uneven layer llb of the shixi film 11 and the surface 帛 of the ridge 10 of the steel ⑽ 10 has a brighter portion. At time U, the bright part is indicated by A ^ and c by a dotted chain line. In particular, the bright area can be clearly observed with the field command shown in A. This area is the lower silicon area, which is presumed to be part of the low density area. This paper standard ticket standard (CNS) A4 24 311933 ----------- •-installed (Please read the precautions on the back before filling out this page} 11 — — — — — — MW, J 丄 J丄 厶 呻 A7 —_B7 V. Description of the invention (25 In order to observe this low-density field in more detail, under the same conditions as the electrode a3, an electrode a6 with a microcrystalline ㈣ film with a thickness of about 2 # m is formed on the electrolytic copper box. 〇—Figure 12 shows a transmission electron microscope photograph when the electrode a6 is observed by a transmission electron microscope in the same manner as above. In Figure 12, the mounting magnification is 25 times. 帛 14 shows 系 12. A pattern explanatory diagram of the transmission electron microscope photograph shown. From FIG. 12, the electrode "is shown on the electrode" on the surface 11a of the concave-convex valley portion m of the Shixi film 11 and the surface of the copper box ridge. A low-density area can be observed in the area D. When the photos in FIG. 12 are further observed, the fine lines extending in the direction shown by the arrows in FIG. 14 can be cut into the film u. The lines may be accompanied by the silicon film It is formed by the growth. Therefore, the silicon film u can be inferred to the surface 10A of the copper drop 10 It grows in the vertical direction. Therefore, the Shi Xi thin film layer 'and the adjacent copper falling surface which are grown in this direction are piled up, and the layers collide with each other in the area D. As a result, a low mountain may be formed in the area 0 Item i or the contact of such a Shixi film layer continues until the end of film formation. 'It is speculated that low-density areas will continue to be formed until the surface of the silicon film. Μ Figure 15 is a scanning type in which the surface of electrode a3 is viewed from above Electron micrograph (second electron image). The electrode ^ shown in Fig. 15 is the state before charging and discharging. The magnification in Fig. 15 is 1000 times. In Fig. 15, the bright part is the convex part on the surface of Shi Xi film. The dark part around it is the valley on the surface of Shixi film. As shown in Figure 15, the valley on the surface of the diaphragm becomes a mesh and is connected in a mesh. Therefore, the above-mentioned low-density area on the Shixi film can be seen from the surface. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 25 311933 A7 V. Description of the invention (26) It is formed by mesh-like connection. This mesh-like low-density area is shown in Figure 11 and Figure 13 As shown in the figure, it extends toward the power storage body in the thickness direction. Also, the dark part in FIG. 15 is not a cut (gap), and can be viewed in the thickness direction from the scanning electron microscope photographs shown in FIGS. 2 and 3. It can be determined without a slit (gap). Figure 16 is a scanning electron microscope photograph (secondary electron image) of the surface of the electrode "in the state before charging and discharging. The magnification is doubled. From Figure 16 It can be seen that in the electrode 36, the valleys are also mesh-shaped, so it can be seen that the low-density area is also mesh-connected in the plane direction.: The figure shows that the electrode a6 is in the depth direction of the stone evening film. Second: the concentration distribution of Cheng = by _, so that ... sputtering i; two (-(Sl2 +) concentration to carry out. In the figure, the plate axis represents the depth (/ zm) from the surface of the Shixi film 矣 溥 臈, and the vertical axis represents the intensity (count) of each 7L element. The electricity storage body Cheng Bachu H has diffused copper fc, S (CU) 'on the surface of the dream film near the electricity storage body, and it can be seen that the electricity storage volume decreases. In addition, from the field of continuity figures of copper stiffness, θ, (Cu), instead of forming intermetallics of # and copper, a solid solution of Shixi and steel is formed. In consideration of the above problems, by compressing the Shixi film in the thickness direction: caused by the expansion and contraction of the Shixi film, as illustrated in Figure 10, the Shixi film body: mechanism is speculated as follows. In other words, referring to the unevenness of the valleys on the surface of the Shi Xi film, the stress generated by the swelling is concentrated on

Wf scale production, and at the same time, the electricity storage body 311933 from the valley part to the bottom. 515124 V. Description of the invention (27) A low-density area exists in advance. This low-density area is the part with low mechanical strength. It is caused by the formation of cuts (voids) in the rear area. As shown in FIG. 17, the silicon thin film has the diffusion of copper element of the electricity storage component, and the copper concentration is higher near the electricity storage body, and the closer to the surface of the silicon thin film, there is a concentration gradient in which the copper concentration decreases. Therefore, the concentration of copper that does not react with lithium in the vicinity of the electricity storage body becomes higher, and the concentration of silicon that reacts with lithium becomes smaller. Therefore, the electricity storage has less absorption and release of the bell near the body, so the expansion and contraction of the Shi Xi film is relatively small. Therefore, the stress generated by the silicon thin film near the electric storage body becomes smaller, and near the electric storage body, it is difficult to generate a cut (gap) in which the Shi Xi film peels or detaches from the electric storage body. The bottom of the columnar part of the Shi Xi film can be connected with The power storage body is kept in close contact. According to the above, the slit-like thin film is formed by forming a slit, and even during the charge-discharge cycle, it closely adheres to the electricity storage body, and the gap formed around the columnar portion is used to relax With charge-discharge "ring [time expansion and contraction of the film ', excellent charge-discharge cycle characteristics can be obtained. Experiment 4 (manufacturing of electrode a7) The same electrode_3 used for the money electrode a3 was used as the substrate of the electricity storage body, and an amorphous electrode a7 was formed on it by RF irradiation. A non-descriptive quality germanium bond_thickness and thickness of the thin film formation conditions are as follows, mesh # · field. Target · germanium, sputtering gas argon (Ar), flowing. 100sccm, substrate temperature: room temperature, high cycle power is 200W. (Heat) 'Reaction pressure: (MPa, _Spectral analysis results, in 274 < attached version and the standard applies to Chinese national standards 〒 (Please read the precautions on the back before filling out this page)-installed -------- Order · • Line · • I n ϋ n-27 311933 ^ 1M24 V. Description of the invention (M peak was observed recently, but a peak near 300 cm-i was not detected, which shows that the obtained germanium film can be determined to be amorphous Quality germanium film. -----------_ (Please read the precautions on the back before filling this page) (manufacturing of electrode a8) Use the same electrolytic copper foil as the electricity storage body of electrode a7. An electrode a8 is formed by forming an amorphous germanium thin film (thickness about 2 // m) on the vapor deposition method. Specifically, an error thin film is formed on a substrate by using a device having a structure shown in FIG. 18. Figure 8. The ECR Plasma source 21 'is provided with a plasma generating chamber 22, which supplies microwave power 25 and nitrogen (26) to the plasma generating chamber 22. When microwave power (25) is supplied to the plasma generating chamber, it can An argon plasma is generated. This hydrogen plasma 23 is led out from the plasma generation to 22 and is irradiated on the substrate 20. The substrate 2 Below the zero, an electron beam (EB) gun (24) is provided, and an electron beam ′ emitted from the electron beam gun (24) deposits a germanium film on the substrate 20.

I I I Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Before depositing a germanium film on the electrolytic copper network of the substrate, irradiate argon plasma on the substrate for pretreatment. The degree of vacuum in the reaction chamber was adjusted to approximately 0.05 Pa (approximately 5 × 10 · 4 Tom), the hydrogen flow rate was 40 sccm, and the supplied microwave power was 200 W to irradiate the hydrogen plasma on the substrate. When hydrogen plasma is irradiated, a bias voltage of -100V is applied to the substrate. Pretreatment was performed by irradiating hydrogen plasma for 15 minutes. Next, a germanium thin film was deposited on the substrate by an electron beam gun at a deposition rate of 1 nm / second (10 A / second). The substrate temperature is room temperature (without heating). The obtained germanium thin film was analyzed by Raman spectroscopy. As a result, it was confirmed that the germanium thin film was an amorphous germanium thin film. (Manufacturing of electrode b2) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 28 311933 515124 Printed by A7 of the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (¾) Use average grains "10" m2 germanium powder, mixed with 10 parts by weight of germanium powder, 10 parts by weight of acetylene black for conductive material, and 10 parts by weight of polytetrazine ethylene for adhesive. Prepared Chin-like electrode b2. (Manufacturing of the battery) A lithium secondary battery was prepared by using the above-mentioned electrodes 37, 38, and b2 as the negative electrode, and the others in the same manner as shown in Experiment .1. Use electrode a7 as negative electrode as battery A7 ′ Use electrode a8 as negative electrode as battery A8, and use electrode b2 as negative electrode as battery B2. (Evaluation of charge-discharge cycle characteristics). The above-mentioned various batteries were charged to a voltage of 4.2V at a current of G. 1 ma at 2 5 C, and then discharged to a charging voltage of 2 claws. Cycle, and measure the capacity retention rate at the 10th cycle. The measured results are shown in Table 5. Table 5 Capacity maintenance rate of battery 10th cycle A7 96% A8 93% B2 3 9% It is clear from Table 5 that battery A7 and battery A8 whose electrodes are negative electrodes of the present invention with a germanium film formed on the storage body, and using germanium Battery B2, which is made of powder as a negative electrode, shows very good capacity retention. (Observed with an electron microscope) _U9 and Figure 20 are electrodes a7 showing the state before charging and discharging. 'Paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297). —' — ----- 29 311933 --I I --- I --- II -------- Order -------- I (Please read the notes on the back before filling out this page) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative 311933 V. Description of the invention (scanning electron microscope photograph of the section 30 (reflected electron image). The mouth ratio of Figure 19 is 2000x 'and the magnification of Figure 20 is 1,000. The field sample uses a resin-embedded electrode for parallel slicing. In Fig. 19, the layers observed at the upper and lower ends and the layers observed at the upper end in Fig. 20 are the above-mentioned embedded resin layers. In Fig. 19 and Fig. 20, the bright part is a copper foil and a germanium thin film, and the surface thin layer of the clear and redundant part is a germanium thin film, and the lower part is a copper foil. The surface has the same unevenness as that of the steel drop. Therefore, it can be presumed that the unevenness on the surface of the germanium film is affected by the surface of the copper foil. It is formed by the influence of the unevenness. / In Figure 20, a thin, dark portion extending in the direction of the germanium film on the valley at the left end of the steel foil can be observed. Fig. 21 and Fig. 22 are scanning electron microscope photographs (reflected electron images) of the cross section of the electrode 28 before the charge and discharge (reflected electron image). The magnification of the second image is 2000 times, and the magnification of the 22nd image is 100 times. The sample is embedded with resin similarly to the electrode a7 shown in Fig. 19 and Fig. 20. In Figs. 21 and 22, the bright part indicates the copper hafnium part, and the slightly dark part on the copper hafnium forms germanium. The thin film (thickness of about 2 "m). In the electrode, the same unevenness as that of electrode a7 is formed on the surface of the germanium film. Figures 23 and 24 show the battery A7 after the 10th cycle. Scanning electron microscope photograph of the cross-section of the electrode a7 taken out (reflected electron image B2 ^ 25 and Figure 26 show the battery after the 10th cycle As As paper size (eNS) A4 — (2i〇7i77il ----- ---------------- ^ ιρ * ^ —— Order ——— (please first Read the notes on the back and fill in this page again.) W5124 A7 V. Description of the invention (31) Scanning electron micrograph and photomicrograph (reflected electron ~ image) of the cross section of the electrode a8 taken out. Any sample is embedded in resin. The electrode is perforated and used in slices. The magnifications of the 23rd and 25th images are 500 times, and the magnifications of the 24th and 26th prescriptions are 2500 times. The germanium films in FIGS. 23 to 26 The white part observed on the surface is the gold coated on the surface of the germanium film when it is embedded in the resin. In accordance with the above reasons for coating with gold, the reason is to prevent the thin germanium ^ 1 reaction and to make the boundary between resin and germanium thin film clear. As shown in Figs. 23 to 26, it can be seen that the germanium thin film is the same as the silicon thin film, and a slit is formed in the thickness direction of the film by charging and discharging, and the film is separated into a columnar shape by the slit. In addition, it can be seen that the difference between the copper drop and the thin film of the electricity storage body is not very different, so it is not easy to discern the realm. The film is closely attached to the electricity storage body. In the case of the wrong film and the dream film, a slit can be observed in the transverse direction. However, this slit is likely to occur when the germanium film is polished for the purpose of observing the cross section. In addition, the gap between the columnar parts of the germanium film (the gap silicon film is large. The height of the columnar part after charging and discharging is about melons, which is 2 / zm higher than the film thickness before charging and discharging. About 3 times. Therefore, when the lithium film that swells after absorbing lithium due to charging is shrunk due to discharge, the shrinkage in the horizontal direction, that is, the planar direction is the main one. The shrinkage in the thickness direction is small, so it may cause columnar shape. The width of the slit (gap) between the sections is increased. Figures 22 and 28 show the germanium thin film of the electrode a7 after charging and discharging. ΪM: The scale is applicable to the Chinese National Standard (CNS) A4 specification-x 297. (Public love) 31 311933 M5124 A7 L. Description of the invention: Scanning electron microscope photograph (secondary electron image) of the (32) plane viewed from above. The magnification of Figure 27 is 1000 times, and the magnification of Figure 28 is 5 = 〇 ^ '. Figures 29 and 30 show scanning electron microscope photographs (secondary electron images) of the surface of the germanium thin film of the electrode a7 after charging and discharging. The magnification of FIG. 29 is 1000 times, and the magnification of FIG. 30 is $ 100. Figures 31 and 32 show scanning electron microscope photographs (secondary electron images) of the surface of the thin germanium electrode on the electrode after charging and discharging (secondary electron image). The magnification of Figure 31 is 1000 times, and Figure 32 The magnification of the figure is 50 ×. Figures 33 and 34 show the scanning electron microscope photograph (secondary electron image) of the surface of the germanium film on the electrode after charging and discharging from a slightly oblique direction, and the magnification of figure 33. It is 1000 times, and the magnification of FIG. 34 is 50 times. As shown in FIGS. 27 to 34, cuts (voids) are formed around the columnar portions of the germanium film, and there are gaps between the adjacent columnar portions. Therefore, it is possible to reduce the swelling and shrinkage of the active material during charging and discharging like the above-mentioned silicon film. Fig. 35 shows a scanning electron microscope photograph (secondary electron image) of the surface of the germanium thin film of the electrode a7 before charging and discharging as viewed from above. Fig. 36 shows a scanning electron microscope photograph (secondary electron image) of the surface of the germanium film of the electrode a8 of the charge / discharge 4 as viewed from above. The magnifications in Figure 35 and Figure 36 are both 1000 times. As shown in Fig. 35 and Fig. 36, the surface of the germanium thin film is uneven along the unevenness of the electrolytic copper foil of the substrate, and the valley portions of the germanium thin film are connected in a mesh shape. It can be seen that cuts (voids) are formed along the thickness direction of this valley, and columnar parts with germanium film are formed. The paper size is applicable to Chinese National Standard (CNS) A4 specification ⑵G χ 297 public love) η -11933 --------_! 螓 · Installation (please read the precautions on the back before filling this page) nn ι > β · ϋ ϋ ϋ -..... ϋ = 0 # Ministry of Economic Affairs Intellectual Property Printed by the Bureau ’s Consumer Cooperative 515124 _ A7 V. Description of the invention (33) (Depth concentration analysis by SIMS) Figure 37 shows the concentration distribution of the constituent elements in the depth direction of electrode a7 before the assembled battery, that is, before charging and discharging. FIG. 38 shows the concentration distribution of the constituent elements in the depth direction in the electrode a8, which is also before charging and discharging. The concentration distribution of constituent elements can be determined by secondary ion mass analysis (SIMS) using a 0 / sputtering source to measure the concentration of copper (63Cu ·) and germanium (73Ce_) from the surface of the film in the depth direction. . The horizontal axis represents the depth (// m) from the surface of the germanium film, and the vertical axis represents the strength of various constituent elements (count values can be clearly seen from Figure 37 and Figure 38. In the vicinity of the electricity storage body, the germanium film diffuses the electricity storage body The copper (Cu) of the composition is closer to the surface of the germanium film, and the steel (Cu) of the electricity storage component is reduced. According to the above, the copper element of the electricity storage component is diffused in the germanium film, and the steel concentration near the animal body is high. The closer it is to the surface of the wrong film, the less the copper gradient exists. Therefore, in the vicinity of the electricity storage body, the concentration of copper that does not react with lithium becomes higher, and the concentration of germanium that reacts with lithium becomes smaller. Therefore, storage near the electricity storage body Less lithium is released, so the expansion and contraction of the germanium film is relatively small. Therefore, the stress generated on the germanium film near the electricity storage body becomes smaller, and it is not easy for the germanium film to peel off or detach from the electricity storage body near the electricity storage body. The gap (gap) allows the bottom of the columnar portion of the germanium film to closely adhere to the electricity storage body. As described above, the germanium film separated into a columnar shape can firmly adhere to the electricity storage body during the charge and discharge cycle. It can reduce the expansion and contraction of the film during the charge-discharge cycle by the gap formed around the columnar part, so it can obtain excellent charge-discharge cycle characteristics. -------- ^ ----- ---- ^ (Please read the notes on the back before filling out this page) Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Employee Consumer Cooperatives This paper is sized for China National Standard (CNS) A4 (210 x297 public love) 33 311933 515124 A7 V. Description of the invention (34) f Examination 5 (manufacturing of electrode a9) Using electrolytic plutonium (thickness 18 p.m.) as the substrate of the electricity storage body, a thin silicon plutonium was formed on the above electrolytic copper box by RF sputtering method. Under the conditions J: Sputter gas (hydrogen) flow rate: 100 sccm, substrate temperature: room temperature (without heating), reaction pressure (MPa (1.0 × 1〇-3 τ〇ΓΓ), high cycle power: 20 hours The thickness of the silicon film was stacked to about 2 # m. As a result of Raman spectroscopy analysis of the obtained erbium film, a peak was detected near 48 (χ), but a peak was not detected near 52 Genrl. It can be confirmed that the obtained silicon thin film is an amorphous silicon thin film. The electrolytic copper box formed with an amorphous stone film is cut into a size of 2cm X 2cm to make an electrode. The surface roughness Ra of the electrolytic copper plate used and the interval S between the local peaks use a pin-type surface shape tester. Dekut3sT * made by the Technical Co., Ltd.) 'Set the measurement distance to 2 〇 Yan and measure. The roughness Ra of the successful second is 0.188_, the average interval between local peaks 夂 2 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Manufacture of 〇) Using the same electrode used in the above electrode, the thickness of the film was changed to about one, and the others were formed on the electrode with the same conditions as those in Experiment 1 above. The electrode alo was made. ， 人-The results of Raman light analysis on the obtained Shi Xi thin mold, *! The presence of both peaks was detected in the vicinity of both. Therefore, the 311933 34 515124 A7 V. Description of the Invention (35) The Shi Xi film obtained is a microcrystalline shredded film. (Manufacture of comparative electrode b3) Using the rolled steel foil used in the above experiment i as the substrate of the electricity storage body, using the same manufacturing method as the electrode a9, a silicon film (thickness of about 2 // m) was shot by RF method. . Cheng Fei said that the amorphous silicon film obtained was annealed at 65 ° C for 1 hour. The annealed Shi Xi film was analyzed by Raman spectroscopy, and the nearby peak disappeared. It is close to ^ ... melon ^. Therefore, the result of the annealing process confirms that a polycrystalline silicon film is formed. Using the above-mentioned rolled steel foil with the polycrystalline silicon film formed, the electrode b3 was prepared in the same manner as the electrode a9 described above. As a result of rolling copper foil, the surface roughness was measured according to the same method as above, and the average interval s of the mountain peaks was measured. The surface roughness was 037 and the average interval 3 of the local peaks was 14 # m. (Measurement of charge and discharge characteristics) Use The electrode a9, the electrode ai0, and the electrode b3 obtained above were used as working electrodes to prepare a test battery for a counter electrode and a reference electrode metal clock. The electrolyte used was the same electrolyte prepared in the above experiment 1. In addition, a monopolar test The battery is charged by reduction of the working electrode, and oxidized as discharge. The above-mentioned various test batteries are charged at a constant current of 0,5 μA to a reference potential at 25 ° A. After V is reached, discharge is performed until it reaches 2 V. Using the above as one cycle of charge and discharge, the discharge capacity and charge and discharge efficiency of the first and fifth cycles are measured. The results are shown in Table 6. This paper 1 Standards are applicable to Zhongyu ^ Ticket Standard (CNS) A4 specification (21〇τ ^^) 35 31 ^ -------- ^ --------- line (please read the precautions on the back first) (Fill in this page) M5124

Charge and discharge characteristics

Silicon film thickness

Annealing cycle

The results in Table 6 show that the electrode a9, which is a polar active material of the present invention, and the thin film a 1 η ^, which is made of a thin silicon film made by Weishe, and the electrode alO, which is an electrode active material, are compared. The electrode b3 for polycrystalline silicon substrate 1 exhibits a high discharge capacity ratio; and a charge-discharge efficiency. -Brother 5 also exhibited good TMA after mounting. ≪ Examples 1 to 7 and Comparative Examples 1 to 2 > [Manufacture of power storage body] Samples 1 to 4 shown in Table 7 were used as the substrate of the power storage body. Trial; 1 is the same rolled steel using electricity as the electricity storage body. Tests 2 to 4 are those in which the surface of the rolled copper foil is ground with # 1〇00 and "〇〇 # 1000" of corundum sandpaper, and then roughened, and then washed with pure water and dried. This paper standard applies to China National Standard (CNS) A4 size ⑵G x 297

311933 A7 B7, invention description (Table 7 Sample number (please read the precautions on the back before filling this page) __ Roughness Ra (# m) Use the above copper foil as the substrate, according to Table 8 to Table ι〇 Article 1. The film is deposited on the substrate by the RF «device. In Comparative Example 2, after the film is formed, heat treatment (annealing) is performed. In addition, Examples i to 7 and Comparative Example 1 are before the film formation. Pretreatment is applied to the substrate. The above-mentioned front part is further placed into a plasma source to generate ecr argon plasma, which is irradiated to the substrate for 10 minutes at an L skin power of 200W and an argon partial pressure of 0,06Pa. -Determine the crystallinity of the Shixi film by Raman spectroscopy. The results are not shown in Table 8 to Table 10. (Measurement of charge and discharge characteristics) Lu Jiang will be formed in Example 1 $ 7 iu,, to 7 The silicon film on the copper foil of Comparative Examples 1 to 2 was cut into a size of 2 cm x 2 cm, and 兪 L ^ was used in the same manner as in Experiment 5 above to produce a test battery printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The battery for test money is the same as that shown in Experiment 5 above. Charge and discharge tests were performed ^ ^ 1 cycle, 5th cycle, and 20th cycle of the discharge capacity to Table 10 and charge and discharge efficiency. The results are shown in Table 8 this paper scale Peng Zhongguan Jiapi (cns ) A4 size x 297 mm) 37 311933 515124 A7B7 V. Description of invention 0 8) Table 8 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 1 Example 2 Example 3 Example 4 Substrate substrate type sample 2 Sample 3 Sample 4 Sample 3 Surface roughness Ra 0.1 0.18 1 0.18 Substrate thickness IS β m 1S β m IS β m 18 // m Film formation conditions Silicon film thickness 2 β m 2 β m 2 β m 2 β m Thin film formation method Sputtering Sputtering method sputtering method sputtering method argon argon argon argon argon flow lOOsccm lOOsccm lOOsccm lOOsccm target object 99.999% silicon single crystal 99.999% silicon single crystal 99.999% early crystal 99.999% silicon single crystal sputtering environment O. lOPa O.lOPa O.lOPa O.lOPa Sputtering power 200W 200W 200W 200W Substrate temperature 20 ° C 20 ° C 20 ° C 20 ° C Pre-treatment with or without sputtering time 2 hours 2 hours 2 hours 2 hours 孰 Ml Rule Heat treatment without heat treatment heat treatment time — — — — The conclusion is that the Raman spectrum 480CHT1 is determined by the existence of the Raman spectrum 520 ^ 1 ^ 1 No No No No Crystalline Amorphous Amorphous Amorphous Amorphous Amorphous Amorphous 1 Cycle discharge capacity (mAh / g) 3980 3978 3975 3980 Charge and discharge efficiency (%) 100 100 100 100 5th cycle discharge capacity (mAh / g) 3990 3981 3980 3990 Charge and discharge efficiency (%) 100 100 100 100 20th cycle Discharge capacity (mAh / g) 3990 3980 3981 3990 Charge and discharge efficiency (%) 100 100 100 100 ---------- AWI ^ -------- 1 --------- (Please read the precautions on the back before filling this page) This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 38 311933 515124 A7 B7 V. Description of Invention (39) Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by a consumer cooperative Example 5 Example 6 Example 7 Substrate substrate type sample 3 sample 3 sample 3 surface roughness Ra 0.18 0.18 0.18 substrate thickness IS β m 18 β m 18 ju m film formation conditions silicon film thickness 2 β m 2 // m 2 // m film formation Sputtering method sputtering method sputtering method sputtering gas argon argon argon argon argon flow rate 100 sccm lOOsccm lOOsccm object 99.999% cut early crystal 99.999% Shi Xi single crystal 99.999% silicon single crystal sputtering environment O.lOPa l .OPa 10Pa Sputtering power 200W 200W 200W Substrate temperature 50 ° C 20 ° C 20 ° C Pre-treatment with or without sputtering time 2 hours 1.5 hours 2.5 hours Heat treatment conditions Heat treatment No heat treatment time — — — Conclusion Raman spectrum 480cm_1 With or without Raman spectrum 520011 ^ 1 No No Non-crystalline Amorphous Amorphous Amorphous Amorphous No. 1 Cycle discharge capacity (mAh / g) 4060 3585 2500 Charge and discharge efficiency (%) 100 100 100 No. 5 Cyclic discharge capacity (mAh / g) 4060 3592 2505 Charge-discharge efficiency (%) 100 100 100 20th Cyclic discharge capacity (mAh / g) 4060 3590 2505 Charge-discharge efficiency (%) 100 100 100 (CNS) A4 specification (210 X 297 mm) 39 311933 -------------- install --- (please read the precautions on the back before filling this page)-line · 515124 A7B7 Five, hair Description (4〇) Table 10 Comparative Example 1 Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economy Comparative Example 2 Substrate Substrate Type Sample 3 Sample 1 Surface Roughness Ra 0.18 0.037 Substrate Thickness 18 / zm 18 // m Thin Film Formation Conditions Silicon Film thickness 2 β m 2 β m Thin film formation method Sputtering: sputtering sputtering method argon argon argon argon flow rate 100 sccm lOOsccm target 99.999% silicon single crystal 99.999% silicon single crystal sputtering environment 0.1 OPa O. lOPa Sputtering power 200W 200W Substrate temperature 450 ° C 20 ° C Pre-treatment with or without sputtering time 2 hours 2 hours Heat treatment conditions Heat treatment without 650 ° C Heat treatment time — 1 hour The aa property determines the Raman spectrum 480CHT1 No Raman spectrum 520cm -1 polycrystalline with polycrystalline polycrystalline 1st cycle discharge capacity (mAh / g) 1250 1978 charge and discharge efficiency (%) 81 83 5th cycle discharge capacity (mAh / g) 900 731 charge and discharge efficiency (%) 75 75 20th cycle discharge capacity (mAh / g) 700 350 charge and discharge efficiency (%) 69 59 (Please read the precautions on the back before filling this page) ▼ -pack --------- ^ 0, This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 40 311933 Printed by A7, Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs-~~-^ I. Explanation of the invention (41)-From the results in Table 8 to Table 10, it is clear that the amorphous stone film of the present invention is the electrode active material of Examples 1 to 7, compared with the polycrystalline silicon film as In Comparative Examples i to 2 of the electrode active material, a high discharge capacity was obtained, and at the same time, good charge-discharge cycle characteristics were obtained. A test 7 On the surface of electrolytic copper foil (thickness 18 # m, surface roughness Ra = 〇188 // m, average interval S = 6 / zm), an amorphous silicon thin film (thickness of about 3 is formed by RF sputtering method) # m) ， 而 制造 电子 all。 All electrodes were prepared. The film formation conditions are as follows. Object: single crystalline silicon, sputtering gas (argon) flow rate = 100% (111), substrate temperature: room temperature (unheated), reaction pressure: 0.1 Pa, high cycle power · 200w. As a result of Raman spectroscopy analysis of the obtained silicon thin film, a peak near 4 80 cm 1 was seen, but a peak near 520 cm-1 was not seen. Therefore, it is determined that the silicon thin film is an amorphous silicon thin film. Using the obtained electrode all, a battery All prepared according to the same method as shown in Experiment 1 above, and subjected to a charge-discharge cycle test under the same charge-discharge cycle conditions as described in Experiment 丨 above, to obtain the capacity retention rate at the 30th cycle. The results are shown in Table 11. The results of battery A1 and battery A3 are also shown in Table 11. Table 11 Capacity maintenance rate of battery 30th cycle A1 91% A3 97〇 / 〇 ~~~ All 97% From the results shown in Table 11, it can be clearly known that the size of the amorphous paper formed by the sputtering method is applicable to Chinese national standards (CNS) A4 specification (210 X 297 mm) 311933 Μ -------- 1 --------- line (Please read the precautions on the back before filling this page) 515124 A7 —_B7 V. Description of the Invention 〇 Quality Shi Xi thin film is active battery A11. The battery A1 and battery A3 using a microcrystalline silicon film as an active material also exhibited good capacity retention. The state of the silicon thin film of the electrode all was observed by an electron microscope. First, a cross section of the electrode ail in a state before charging and discharging was observed with a scanning electron microscope. Figures 39 and 40 show scanning electron micrographs (secondary electron images) of the cross section of the electrode all before charging and discharging, respectively. The magnification of FIG. 39 is 2000 times, and the magnification of FIG. 40 is 10,000 times. The samples were embedded with resin in the same manner as the samples in Figs. 2 and 3, and then cut into samples. In Fig. 39 and Fig. 40, the lighter part indicates the electrolytic copper foil, and the darker part on the copper foil shows the silicon film (thickness about 3 // m). The surface of the electrolytic copper foil is formed with irregularities as shown in Figs. 40 and 40, and the convex portions have a tapered shape. The surface of the silicon film provided above is also formed with unevenness similar to that of the steel foil, and the convex portion also has a cone-like shape. Therefore, the unevenness on the surface of the silicon thin film is formed by the unevenness on the surface of the copper foil. Figure 41 shows a scanning electron micrograph (secondary electron image) of the silicon thin film surface of the electrode all, with a magnification of 1000 times. As shown in Fig. 41, a large number of convex portions are formed on the surface of the silicon thin film. The protrusions are formed corresponding to the protrusions on the surface of the copper foil as shown in Figs. 39 and 40. Fig. 42 shows the battery A after the 30th cycle of the charge-discharge test. Scanning electron microscope (secondary electron image) of the surface of the Shi Xi film taken out of the electrode all. The magnification of the photograph shown in FIG. 42 is 10 ×. As shown in Figure 42, a slit is formed in the thickness direction of the silicon film (the empty ^ paper size is subject to the Chinese National Standard (CNS) A4 specification (_2W X 297 public love) _ 42 311933 d 丄 J 丄 厶 Η Α7 Β7 V. Explanation of the Invention (43) Gap) 'By using this slit (gap), the Shi Xi film is separated into a columnar shape.图 Figures 6 to 9, the columnar part of the Shi Xi film shown in the figure contains a convex portion on the film surface to form a slit. In contrast, the dream film shown in Figure 42 has the columnar part of the film surface. A plurality of convex portions form a slit. In addition, it can be seen that the width of the slit (gap) is larger than that of the Shixi film shown in FIGS. 6 to 9. ^ Battery A11 and Battery A3-samples have good capacity retention rates. Therefore, as shown in FIG. 42, even when the columnar portion is formed by including a plurality of convex portions on the surface of the film, the expansion and contraction of the active material can be eased by the voids formed around the columnar portion, so the active material will not be removed from the electricity storage. The body is peeled off and the charge-discharge cycle can be repeated. Set up the same thin film formation conditions for making the electrode a1 in Experiment 1, and form a microcrystalline shredded film with a thickness of about 2 "melons on rolled copper and electrolytic copper fl (thickness 18 " m). Second, The obtained sample was punched into a diameter of 17 bands. The electrode formed on the rolled copper box was used as the electrode el, and the electrode formed on the electrolytic copper box was used as the electrode e3. The electrode a2 in Experiment 1 was completed in the same way. The heat treatment of C for 3 hours was used as the electrode C2 and the electrode c4. &Quot; Using the above electrodes cl to c4 as the negative electrode, the rest were the same as shown in the above experiment 1 Methods Lithium secondary batteries were made, which were batteries "4. For the above batteries, the charge-discharge cycle life characteristics were measured in the same manner as in the experiment. In addition, the Shi Xi 'film content of each electrode and the peak intensity ratio in Raman spectroscopy analysis were also measured in the same way as in Experiment i (48 ° cm. This paper is in accordance with the Chinese National Standard (CNS) A4 specification ⑵χχ297). (Public love) 43 311933 515124 A7 B7 V. Description of the invention (44) 752001111) and crystal grain size. The results are shown in Table 12.

(Please read the precautions on the back before filling in this page) From the results shown in Table 12, it is clear that even in the batteries C1 to C4 with a film thickness of about 2 / zm, the microcrystalline silicon film can be obtained Ancient quantity maintains the holding rate. Tani Next, an electrode of microcrystalline silicon thin film on rolled copper foil will be formed. Workers made slices in the thickness direction as samples for microscope observation, and then observed them with a transmission electron microscope. Figures 43 and 44 show transmission electron micrographs near the interface between the copper foil and the silicon film on the electrode 0. The magnification of Figure 43 is 500,000. It is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The 44th figure is a magnification of 1 million times. In each picture, the bottom is the steel box side and the top is the silicon film side.

In Fig. 43 and Fig. 44, the bright part below may be a steel foil part, and the area near the interface between the copper foil and the silicon film gradually darkens toward the upper side. This part (about 30nm to 100nm) is part of a mixed layer in which copper and silicon are particularly mixed in steel foil. In this mixed layer, silicon and copper may be alloyed. Further, as shown in Figs. 43 and 44, a granular portion may be observed near the interface between the mixed layer portion and the steel foil. The granular part can be seen from the steel spreading toward the silicon. 515124 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Affairs Co., Ltd. A7 B7 V. Explanation of the invention (45) The unevenness caused by the scattering is in the interface. Next 'is to measure the concentration distribution of the constituent elements in the depth direction of the mixed layer. Using the SIMS method, O / is the sputtering source, and the concentrations of the copper element (63Cu +) and the hydrogen element (Η) are measured. Fig. 45 shows the concentration distribution of each constituent element in the depth direction of the mixed layer, the horizontal axis represents the depth (/ Zm), and the vertical axis represents the atomic density (a / cm3). As shown in Fig. 45, in the mixed layer, as the depth increases, Deeper, that is, closer to the copper poise and the copper concentration increases. Here, when a layer containing 1% (atomic density of 102 < M @ / Cm3) or more of the storage material is used as the mixed layer in the silicon thin film, it can be seen that the depth ranges from about 1 · 9βπ to about 2 7 / Zm. So far there are mixed layers. -Next, the electrode c3 of a microcrystalline silicon rhenium film having a film thickness of about 2; zm was formed on the electrolytic copper foil, and the concentration of each constituent element in the depth direction of the mixed layer was measured by sms in the same manner as described above. The results are shown in Figure 46. As shown in Figure 46, in the electrode c3, on the surface of the silicon thin film, the atomic density of the copper hafnium is already above 10, / cm3, and the steel has diffused to the surface of the Shixi thin film. Has become a mixed layer. In addition, the battery C3 using the electrode c3 exhibits good charge-discharge cycle characteristics. It can be seen that the entire silicon thin film can also function as an electrode active material as a mixed layer. Figures 45 and 46 clearly show continuous changes in the silicon film. Therefore, in the silicon thin film, the copper compound does not form an intermetallic compound with silicon, but forms a solid solution with silicon. As described above, at the interface between the mi and M films, it was confirmed that the steel was mixed and a mixed layer was formed. With this kind of mixed paper ruler _ home fresh (cns) A4 "^ 311933 ^ -------- ^ --------- (Please read the precautions on the back before filling in this Page) q 丨 year 丨 1} Wow; $ Air? Ui;

V. Description of Invention (%) ___

The existence of the repair layer I can be used as Ρί Λθ > ^ ^ 乂 k-direction silicon film's closeness to steel foil, even when the silicon dioxide film expands and contracts due to the charge of silicon, the silicon film will not self-storage the electricity • Five people were able to get good charge-discharge cycle characteristics. [Possibility of industrial use] By using the electrode for a bell battery of the present invention, a lithium secondary battery having a high charge and discharge capacity and excellent charge and discharge cycle characteristics can be produced. ---------------------------- (Please read the notes on the back before filling out this page) The paper size of the paper is applicable to China National Standard (CNS) A4 (210 X 297 46 311933

Claims (1)

H3 pi No. 89122034 Patent Application Amendment to Patent Scope (October 1991 I.-Electrode for Clock Battery 'is a thin battery made of active material with a release agent installed on the battery, its characteristics are ^ The film is separated into a column shape by a slit formed in the thickness direction, and the bottom of the columnar part is in close contact with the aforementioned t electric body. The thickness direction of the film, at least a thickness of 1/2 or more: in: separated into a columnar shape by the aforementioned slit. &Quot; 3. :: Please use the lithium battery electrode for item i or item 2 of the patent scope, ^ In the formation of the slit, the surface of the film is uneven, and the columnar portion contains at least a thin ridge: a convex portion. ^ 4. If the lithium battery electrode of item 3 in the scope of the patent application, i ， Open, formed in the aforementioned slit, so that the aforementioned columnar section > contains a plurality of convex sections on the thin surface. ~ Printed by the Staff Welfare Committee of the Central Bureau of Standards of the Ministry of Economic Affairs. The electrode for a lithium battery according to item 2, wherein: It is formed during the charge and discharge after the first time. For example, the electrode for a lithium battery in item 5 of the declared patent scope, wherein before the charge and discharge, unevenness is formed on the surface of the film, and for the first time, only charge and discharge are used. The film is slit with the valleys on its surface as the end material, and the slit is used to separate the aforementioned film into a cylindrical paper. Applicable to the standard of paper g f (CNS) A_4 (210 x 297 mm) 311933 • For the electrode for lithium battery in item 6 of the patent application, wherein the unevenness on the surface of the thin film corresponds to the unevenness in the surface of the bottom layer of the electricity storage body. • For the electrode for lithium battery in item 7 of the patent application, wherein the foregoing The convex part of the concave and convex surface of the electric storage body is a cone shape. For example, for the lithium battery electrode of the first or the second item of the patent application scope, the upper part of the middle part of the four pillars has a circular shape. For example, the lithium battery electrode used in item i or item 2 of the patent scope, where the aforementioned slit is formed in advance before charging and discharging. The battery electrode for item 1 or item 2 of the scope of Shenjing patent, Zhongli The 'special membrane system by the classics And elements of compounds IIB, IIIB, IVB and VB in the periodic table of the compounds or solid solutions, as well as oxides and sulfides of transition metal elements in the 4th, 5th and 6th periodic table. At least one of the materials is selected. V. Printed clothing of the Staff Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs 12 · For the lithium battery electrode of item 11 in the patent application scope, in which the aforementioned element is made of carbon, stone Select at least one of tin, copper, shao, steel, diction, editor, bismuth, and mercury. 13. For the lithium battery electrode according to item 11 of the patent application, wherein the aforementioned element is silicon or germanium. 14. If applying for a patent The electrode for a lithium battery in the range of item i or item 2, wherein the thin film is a thin film formed by a CVD method, a sputtering method, an evaporation method, a flame spraying method, or an electroplating method. 2. For the lithium battery electrode of item 1 or item 2 of the patent application scope, this application is ~ 2 311933 515124 H3, where the aforementioned film is an amorphous film. 16. For the lithium battery electrode according to item 1 or item 2 of the patent application scope, wherein the thin film is an amorphous thin film. 17. For the lithium battery electrode of item 1 or item 2 of the scope of patent application, wherein the thin film is an amorphous silicon thin film. 18. For an electrode for a lithium battery according to item 1 or item 2 of the patent application scope, wherein the thin film is a microcrystalline silicon film or an amorphous silicon film. 19. For the lithium battery electrode according to item 1 or item 2 of the patent application scope, wherein the thin film is an amorphous germanium thin film. 20. The lithium battery electrode according to item 1 or item 2 of the scope of patent application, wherein the thin film is a microcrystalline germanium film or an amorphous germanium film. 21. For the lithium battery electrode of item 1 or item 2 of the patent application scope, wherein the thin film is a microcrystalline silicon germanium alloy film or an amorphous silicon germanium alloy film. 22. For an electrode for a lithium battery according to item 1 or item 2 of the patent application scope, wherein the power storage system is selected from at least one of copper, nickel, stainless steel, molybdenum, tungsten, and tantalum. Printed by the Staff Welfare Committee of the Central Bureau of Standards of the Ministry of Economic Affairs. 23. For the lithium battery electrode of the first or second scope of the patent application, the surface roughness Ra of the aforementioned power storage body is 0.01 to 1 / zm. 24. For the lithium battery electrode of item 1 or item 2 of the scope of patent application, wherein the aforementioned electricity storage body is copper foil. 2 5. The electrode for a lithium battery according to item 24 of the patent application, wherein the aforementioned copper foil is an electrolytic copper foil. 2 6. —A kind of electrode for lithium battery, characterized in that it is applicable in the first scope of the patent application and the scale of the application 3 3Π953 ~ H3 H3 Any one of printed items to 25 items printed by the Central Standards Committee of the Ministry of Economic Affairs In an electrode for a lithium battery, a slit is formed in a low-density region extending along a thickness direction in a thin film. 27. The electrode for a clock battery according to item 26 of the patent application, wherein the aforementioned low-level area extends upward from the valleys on the surface of the power storage body. 28. As stated in the scope of the patent], 2, or "or" of the lithium battery electrode ', the component of the power storage body is diffused in the thin film. 29. For an electrode for a lithium battery according to item 28 of the application for a patent, in which the components of the aforementioned electricity storage body which have been diffused in the thin film are not formed into an intermetallic compound with the components of the thin film, and a solid solution is formed. 30. According to the scope of the patent application, the battery power S 'of the bell battery, wherein the thin film is an active material capable of absorbing lithium by forming an alloy with the bell. 31: In the application of the clock battery power item "2, 26 or 27" in the profit range, lithium is stored or added in advance in the aforementioned film. It is characterized by having a negative electrode and a positive electrode constituted by the electrode as described in any one of the item 1 of the scope of the patent application, and 33: the first? Also, it is characterized as being injurious as in any one of the patent application scope item to item 31. Electrode and non-aqueous electrolyte. Negative electrode and positive electrode 34. If the scope of the patent application is 33, the positive electrode system can absorb and release menstrual oxygen. Among them, the foregoing 35. If the scope of the patent application is 33, lithium: active matter is greedy. _,% Pool 'Among them, the aforementioned 311933 H3 positive electrode system includes lithium halide as an active material. 36. An electrode for a secondary battery, comprising an electricity storage body composed of a material layer composed of a thin film and an electrode material layer adhered to the moon, and a thin body formed in a mesh shape in a planar direction and facing the animal. A low-density field in which the electrical body extends in the thickness direction. 7: The electrode for secondary electric ground according to item 36 of the patent application, wherein the component of the aforementioned electricity storage body is diffused in the thin film of month J. 38 = Please use the electrode for secondary battery in item 37 of the patent, and the above-mentioned "thin" component diffused into the above-mentioned thin film will form an intermetallic figure and become a knife, and will not form a solid solution with the aforementioned 39 such as Jiu Kui-9. For example, "the battery electrode in any of the 36th to the Mth patents" wherein the aforementioned thin film is a thin film on the aforementioned electricity storage body. ㈣ & forming method 40. If the scope of the patent application is 帛% ㉟ twice, the aforementioned thin 臈 formation method refers to a CVD method, a sputtering method, among which, a flame spraying method, or an electroplating method. W 〇 Plating method, fire 4! • If the patent application scope item %% to the Ministry of Economic Affairs. The central standard is that the employee welfare committee printed the battery electrode 'Among them, the aforementioned storage system 2-:: 二 * convex, the The valley portion of the unevenness has a concave region on the base. The aforementioned low-density collar is formed. 42. As described in item 41bis of the scope of the patent application, A, the electrode for a convex part of the aforementioned surface of the power storage body, wherein A is as described in the scope of the patent application, 36th to 3rd. Batteries electrodes, 苴 中, 一项 一, 二次, 刖, the surface of the binding m to form a human body corresponding to 297 mm) 3U933 π profit-seeking range item 36 to the battery electrode, the 4, brother The second of any one of 38 items is followed by the expansion and contraction of the aforementioned thin ridges along the lower second, and the cut seam will be formed with a cut seam in the thickness direction, thereby separating the membrane into pillars. • 44 ^ ^ ^% Μ ^ of the scope of the patent application-夂 battery electrode, where 46 such as = expansion and contraction are given by charging and discharging. Jia Ming patent scope of 36 to The third electrode for battery, Item 47, one of the following items: ^ Λ Among them, the thin film is a silicon thin film. • One of the items in the patent application No. 46-4-Λ # —the electrode for human battery, of which, Moon J Mixi Xi thin film is amorphous 48 such as Zhi Xi thin film or microcrystalline silicon thin film. Shen Ya patent range of any of the 36th to 38th of the item-the second 4 of the electrode is also used 'where' the aforementioned film is germanium Thin 臈.: Electrode for secondary battery in the 48th scope of patent application, among which the germanium thin film is not f. Thin film or microcrystalline film. 50. For the secondary battery electrode of any one of the 36th to 38th of the scope of patent application, wherein the aforementioned thin film is a Shixo alloy thin film.胄 50 $ for secondary batteries, where the aforementioned Shi Xi Co alloy thin film is an amorphous rhenium germanium alloy thin film or a microcrystalline silicon germanium alloy thin film. 52. For example, in the 36th to 38th scope of the patent application The electrode for a secondary battery according to any one of the above, wherein the surface roughness R of the power storage body is “0.0 1 to 1 // 111. · ~ ^, The display scale is applicable to γ B g sample standard (CNS) A4 regulations (2i〇χ 297 ^ jy 5 3) such as the second application of any one of the 36th to 38th scope of the patent application ^^ __ 6 311933 515124 H3 battery electrode, in which the aforementioned electricity storage body is copper foil. 54. For example, for the secondary battery electrode in the scope of patent application No. 53, wherein the aforementioned copper foil is electrolytic copper foil. 55. — secondary The battery is characterized by using an electrode according to any one of items 36 to 54 of the scope of application for a patent. 56. A secondary battery such as item 55 of the scope of application for a patent, wherein the aforementioned electrode is a positive electrode of a secondary battery and / 57. For example, the secondary battery according to item 55 of the patent application, wherein the foregoing secondary battery is a non-aqueous electrolyte secondary battery. 58. For example, the secondary battery according to item 57 of the patent application, wherein the aforementioned non-aqueous battery The electrolyte secondary battery is a lithium secondary battery. The paper printed by the Staff Welfare Committee of the Central Bureau of Standards of the Ministry of Economic Affairs is compliant with the Chinese National Standard (CNS) A4 (210 X297 mm) 7 311933