TW512133B - Lithium hydrogentitanates and process for the preparation thereof - Google Patents

Abstract

Lithium hydrogentitanates prepared by acid treatment of lithium titanate and having pH values of 11.2 or below; and those represented by the general formula: Hx, Liy-x, Tix, O4 (wherein y ≥ x > 0, 0.8 ≤ y ≤ 2.7 and 1.3 ≤ z ≤ 2.2). These lithium hydrogentitanates are useful as active materials of positive and negative electrodes for secondary batteries of nonaqueous electrolyte type, and can realize a charging capacity exceeding the theoretical one. The lithium hydrogentitanates take the form of particles which preferably contain voids and preferably have a maximum narticle diameter of 0.1 to 50 μm and a specific surface area of 0.01 to 300 m<SP>2</SP>/g. The lithium hydrogentitanates can be prepared by bringing lithium titanate into contact with an acid such as acetic acid to replace some of the lithium ions by protons.

Description

512133 A7 ____B7 V. Explanation of the Invention (1) Technical Field The present invention relates to those who produce lithium hydrogen titanate by replacing part of lithium with protons, and also related to its manufacturing method. Background Art In recent years, with the advancement of electronic technology and the like, high performance, miniaturization, and portability of various electronic devices have progressed, and storage batteries used as power sources for these electronic devices have also been strongly required to have high performance and miniaturization. As a new storage battery to meet such a demand, a non-aqueous electrolyte storage battery is expected. In particular, the development and practical use of lithium-ion batteries capable of absorbing, storing and releasing lithium is prevailing, and its market is rapidly increasing. As for the positive electrode active material of such an electrode, vanadium pentoxide or manganese oxide, lithium cobaltate, lithium nickelate, spinel-type lithium manganate, and carbon materials such as graphite combined on the negative electrode can be mainly used. It is practically used as a high-voltage, high-energy-density battery. However, batteries using these materials are not suitable for applications where low voltages below 3 V are used. In the future, due to advances in the development of electronic equipment technology and the reduction of IC's usable voltage, it is considered that the machine voltage needs to be further reduced. In this situation, due to the previous technology development, a battery using a spinel-type lithium titanate as a negative electrode has been put into practical use for a clock driven around 1.5 V by combining with a solar generator. The market trend of this market has attracted a lot of attention (new material 1996 · 8 original No · No 03-04 lithium titanate battery). If this paper is standard, the SIS family standard (CNS) Λ4 specification (210X 297 mm) is applicable. Please note the following before reading this page. ^ This page · Γ; ν ·, '·, · ^;-&gt; '!' ^ Γ ': ί-. ^ Π (Ί- 沈 氕 合 ^

512133 V. Description of the invention (2) As for the characteristics of this battery system, it is particularly superior in cycle characteristics, over-discharge, and retention characteristics. If the use of 1 · 5 V-series batteries is expanded in the future, it will be regarded as a charge-discharge capacity. High battery development requirements can be further progressed. In the past, lithium titanate, which is the positive or negative electrode active material of such non-electrolyte storage batteries, has a large impact on battery characteristics due to the characteristics of titanium oxide used in raw materials. Research reports are prevailing. As for the titanium oxide used in raw materials, there are blue kite shape, rutile shape, anatase shape, etc., but until now, • Anatase shape oxidation with superior charge and discharge capacity and good cycle characteristics Titanium is also regarded as a powerful material. As useful lithium compounds for lithium ion battery materials, Li 2 · 6 7 T i 1 33〇4, L i T i 2 0 4 ^ L i 1. 3 3 Li titanate such as Ti 1 66 〇4, Lil.44Til.77 〇4, Li 〇.8 T i 2.2.04. Among these lithium compounds, Li 1. 3 3 T 1 66〇4 has attracted attention due to its large charge and discharge capacity. In order to obtain the above lithium titanate, a method of dry heat-treating a mixture of titanium oxide and a lithium compound at a temperature of 700 to 160 t can be used (for example, refer to Japanese Patent Application Laid-Open No. 6-275263).妖 j \\\ Moreover, the thus obtained defect-type lithium titanate Li 1. 3 3 T i 1 66〇4, for the charge and discharge of one-electron reaction, 而言 theoretical capacity is 175 mA h / g, The material being commercialized is about 130 ~ 150 under the electronic reaction of 0.75 to 1.0. The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297mm). (Please read the back (Please note this page and fill in this page again) p —---- 1—Order --------- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -5- 512133 A7 B7 V. Description of the invention. 3) mAh / g, its current status is far lower than the theoretical capacity (see Electrochemistry V ο 1.62, No9 (1994) p87〇 ~ 875)) 〇 &lt; In recent years, with the laptop, mobile phone, CD portable The popularity of listening, MD Walkmans, etc., combined with the use of batteries that account for these power sources has increased rapidly, and with miniaturization, it has also been strongly required to have a longer life and a longer life. Therefore, the development of materials with large charge and discharge capacity is an urgent task. DISCLOSURE OF THE INVENTION The present inventors and others, in order to obtain a material with excellent charge and discharge capacity, have conducted various reviews and found that lithium hydrogen octylate, which replaces lithium ions of lithium titanate with protons, has a content of PΗ 値, which is the proton substitution amount X. The ratio will increase the charge and discharge capacity. Furthermore, a structure having voids in the particles will further increase the charge and discharge capacity, etc., and complete the present invention. That is, the lithium hydrogen titanate of the present invention is characterized in that ρ Η 値 is less than 1 1.2, and is also represented by the general formula HxL iy ~ xTiz〇4 (but, y ^ x &gt; 0 »〇. 8 ^ y ^ 2. 7. 1 · 3 ^ ζ ^ 2 · 2) are characterized by those who represent them. The lithium hydrogen titanate can be obtained by treating lithium hydrogen titanate with an acid. That is, the method for producing lithium titanate according to the present invention uses the general formula

LiyTiz〇4 (but, 0.8Sy $ 2, 7, 1 · 3Sz $ 2, 2) represents lithium titanate, which is contacted with an acid to replace lithium ions with protons to form the general formula HxL iy — xT iz〇4 (but , Y ^ x &gt; 〇, mound paper scale sincere ΕΚ house standard Xin ((, NS) Λ4 specifications (210X297 male f) ~ 'a--^ 71 read the precautions before filling out this page): Order Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 512133 φ. 3.1¾ V. Description of the Invention (4) 0.8 ^ y ^ 2.7. 1.3 Lithium hydrogen titanate represented by 1.3. The ρ Η 値 of the lithium hydrogen titanate after the above-mentioned acid treatment can be a parameter in adjusting the g-force of the charge and discharge, and the 値 値 is preferably in the range of 7 · 5 to 11 · 2. The above lithium hydrogen titanate can be used as the positive and negative electrode materials of low-voltage lithium ion batteries with a voltage below 3 V, and has a capacity far exceeding the theoretical charge and discharge capacity. Due to the effect of proton replacement treatment, as a material that can far exceed the theoretical charging capacity, the original lithium titanate has a defective spinel structure, and the gap between the defective part is supplied by the lithium source of the counter electrode. The doped state of the lithium ions is in a charged state, and usually does not exceed the theoretical capacity of 1 75 mAh / g of the electronic reaction. However, in the lithium titanate undergoing proton substitution treatment, since protons are used to replace part of the lithium constituting the crystal lattice, lithium and proton exchange can be performed in the crystal lattice of the A position and the B position of the originally restricted gap Create voids where lithium ions can penetrate. Because of this effect, it can be presumed that a material having a charge and discharge capacity far exceeding the theoretical capacity can be produced. The lithium hydrogen titanate of the present invention is characterized in that the lower the firing temperature, the larger the surface area (increased reaction area), and the proton substitution treatment can increase the amount of voids containing lithium ions. Therefore, it is far more than 175mAh / g of the theoretical charge capacity of one of the electronic reactions of lithium titanate, compared with the existing lithium titanate materials. The material itself is novel. Therefore, the present invention has a high industrial price. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) • * *

512133 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs%!-! &Lt; &gt;: λ Α7 Β7 V. Description of the invention (5) The "Best Shaped Bear" adopted in the invention regarding its titanic acid in lithium hydrogen titanate The p Η 値 of lithium after acid treatment, that is, the ρ Η 値 of the obtained lithium hydrogen titanate can be a parameter for adjusting the charge and discharge capacity. Specifically, ρ 锂 of lithium hydrogen octoate, which is obtained by applying an acid treatment, is less than 1 1 · 6, and preferably 1 1 · 2 or less. However, the ρ Η 値 of this lithium hydrogen titanate was measured by the following method. First, 30 g of lithium hydrogen titanate was put into distilled water 5 0 «^ and boiled at a temperature of 100 ° C for 5 minutes. . After cooling, the water having been charged with the lithium hydrogen titanate was passed through a filter paper and filtered, and at a temperature of 20 ° C, the ρ ρ of the obtained filtrate was measured using a ρ Η meter. As for lithium hydrogen titanate, when ρ 测定 measured in this way falls within the above range, it becomes a person who can impart particularly high charge and discharge capabilities to a battery. This reason, as described in the previous paragraph, is that ρ 得 obtained by acid treatment can be a parameter in adjusting the charge and discharge capacity. That is, as the acid treatment concentration is higher, the amount of proton substitution increases, and as a result, P Η 値 becomes on the acid side. ‘: Conversely, when the acid treatment concentration is lower, the ρ Η on the alkaline side is displayed, and the amount of proton substitution becomes smaller. Therefore, in the case where ρ Η 値 is in a certain range, lithium hydrogen titanate can be regarded as a crystal structure with favorable space obtained during charge and discharge, that is, a crystal structure with more space surrounding lithium. The range of P 管制 regulated by the present invention can be presumed to be an index indicating that such a favorable crystalline structure in charge and discharge has been constituted. Therefore, if you take (please read the precautions on the back before filling this page) f

Order --------- Line I This paper size applies to China National Standard (CNS) A4 specifications &lt; 210 X 297 mm) -8- 512133 A 7 B7 V. Description of the invention 6) Use each p As a negative electrode material, lithium hydrogen titanate can obtain superior charge and discharge capabilities. Moreover, the preferred pH range of lithium hydrogen titanate is 5.6 to 1 1 L 2. The above-mentioned P Η 値 is closely related to the proton substitution of lithium titanate. Therefore, the lithium hydrogen titanate of the present invention can be regarded as the proton substituted titanic acid. When viewed from a related viewpoint, the hydrogen titanate of the present invention Lithium is a compound represented by the general formula HxL i y-xT i ζ〇4. When used, it may be a single phase of lithium hydrogen titanate, or a mixture of lithium hydrogen titanate and titanium oxide. In the above general formula, y and ζ 値 are among those having a preferable range of 0.8SyS2.7 and 1.3SzS2 · 2. When the proton substitution amount X is in the range of y ^ x> 0, the point of charge and discharge capacity is appropriate, and the range of 0.9y2x20 · 05y is more preferable, and the range of 0.8.ly is most suitable. All the lithium ions are replaced by protons and have a composition equivalent to y = X, which is also included in the lithium hydrogen titanate of the present invention. If the proton substitution amount X is smaller than the above range, the charge / discharge capacity will not be significantly improved. The lithium hydrogen titanate of the present invention is preferably in the form of particles. In this case, the shape of the particles is not particularly limited, and can be used in various shapes such as particles, plates, and the like. Among them, lithium hydrogen titanate having voids in one leg is more suitable because it can further increase the charge and discharge capacity. The existence of this void can be confirmed by measuring the amount of voids. For example, if the amount of voids is above 0 · 0 0 5m £ / g, it can be determined that there are voids in the particles (read the precautions before reading this page and then fill out this page)

The standard of this paper is K National Standard Peak ((, NS) Λ4 Specification (210X 297 male f) 512133 A7 B7

Ti- * turn.. ^ V. Description of the invention (7) exists. The range of the void amount should preferably be 0 · 〇1 ~ 1 · 5m £ / g, and a more preferable range is 0 · 0 1 ~ 0.7m. By forming the particle shape into a laminated structure, a large amount of voids can be ensured between the layers. Further, the preferred lithium hydrogen titanate of the present invention can be controlled to have a fine particle size. Its longest particle diameter can be appropriately designed, but as the powder's ease of handling, battery characteristics, etc., a range of 0 · 0 5 to 5 0 // m is appropriate, and 0.05 to 10 #m The range is more suitable, and the range of 0.1-1 / zm is most suitable. The specific surface area is preferably in the range of 0.01 to 300 m2 / g, more preferably in the range of 0.1 to 150 m2 / g, and more preferably in the range of 0.5 to 100 m2 / g. Second, the manufacturing method of the present invention is to contact lithium titanate represented by the general formula LiyTiz〇4 (but, 0.8 $ γ ^ 2 · 7, 1, · 3 ^ ζ $ 2 · 2) with an acid, and protons Instead of lithium, hydrogen titanate represented by the general formula HxL i &gt;.-xTiz〇4 (however, y ^ x &gt; 〇, 0.8 ^ y ^ 2.7. 1.3. $ Ζ $ 2 · 2) Lithium is characteristic. Lithium titanate is brought into contact with an acid. For example, lithium titanate is suspended in a solvent such as water, alcohol, 2-ethoxyethanol, methyl ethyl ketone, xylene, toluene, etc., by adding an acid thereto. As the acid, any of inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as acetic acid, formic acid, and the like are not particularly limited. Among these, acetic acid, hydrochloric acid, and nitric acid are preferred. The lithium titanate used in the manufacturing method of the present invention is represented by the general formula L iy _ χ d i i 2 0 4, where y, z becomes 0 · · 7 This paper size applies the Chinese National Standard (CNS) A4 specification ( 210 χ 297 mm) · 10 _ —I, —-— 丨 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

512133 m. Ι3 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of invention (8), one of the most suitable compositions in the range of 1 · 3 S z S 2 · 2, for example: Li2 .67Ti 1.33 〇4, Li T i 2 0 4, Lil.33 Til. 66 〇4, Lil.44 Til. 7104, Li. 8 T i 2. 2.04 and so on. The particle shape is not particularly limited, and it can be formed into various shapes such as a granular shape and a plate shape. The particle shape of the lithium titanate is inherited from the particle shape of the lithium hydrogen titanate. To obtain lithium titanate, for example, (1) a method of heat-treating a mixture of titanium oxide and a lithium compound at a temperature of 5000 to 900 ° C to prepare granular lithium titanate, and (2) making the titanium compound and The first step of reacting an ammonium compound in an aqueous medium to obtain a titanate compound, the second step of reacting the titanate compound and a lithium compound in an aqueous medium to obtain a lithium titanate aqueous compound and heat treating the titanate The third step of lithium water and materials, and a method of preparing plate-shaped lithium titanate. The method (1) above is a preferable method for producing lithium titanate easily and cheaply. The range of the heat treatment temperature is preferably 60 0 to 800 1, and the range of 650 to 750 t: should. The lithium titanate obtained by the above method (2) is a preferred method in which the size or size of the particles can be obtained and lithium hydrogen titanate having voids in the particles is obtained. In the above method (1), titanium oxide means anatase-type titanium oxide, rutile-type titanium oxide, amorphous titanium oxide, metatitanic acid, orthotitanic acid and other titanium oxides or titanium hydroxide, and water-containing oxidation Titanium, hydrated titanium oxide. As the lithium compound, lithium hydroxide, lithium carbonate, lithium nitrate, lithium sulfate, and the like can be used. In order to obtain a mixture of titanium oxide and lithium compounds, there are dry-mixed titanium oxide and lithium compounds, and they are mixed with water, water-alcohol, and other aqueous media. (Please read the precautions on the back before filling this page ) -411 ^ ----- 1_—Order --------- line

This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -11-512133 F] 22 丨 A7 "3 B7___ V. Description of the invention (9) Combining and drying, or 'Using A method of adding a lithium compound to a titanium oxide slurry suspended in an aqueous medium and evaporating and drying it. In the method (2) above, the first step is a step of reacting a titanium compound and an ammonium compound in an aqueous medium to obtain a titanate compound. The titanic acid compound means that ortho titanic acid, part of the protons of the orthotitanic acid are replaced by ammonium ions, etc. As for the titanium compound, an inorganic titanium compound such as titanium sulfate, titanium hafnium sulfate, titanium chloride or the like can be used for oxidation In particular, organic titanium compounds such as organic compounds are preferably titanium chloride which can reduce the amount of impurities in lithium hydrogen titanate. Also, ammonium compounds can be ammonia water, ammonium carbonate, ammonium sulfate, ammonium nitrate, etc. If sodium compounds, When an ammonium compound is replaced by an alkali metal compound such as a potassium compound, the sodium or potassium element remains in the obtained titanium compound, and sintering between particles may be caused during heating and dehydration in the subsequent steps, which is likely to cause sintering. The size or shape of the particles is not uniform, so it is not suitable. As for the aqueous medium, water, water-alcohol, etc. can be used. By mixing the titanium compound and ammonium compound in the aqueous medium, the reaction can be carried out and the original Titanic acid (H4Ti〇4), or a titanate compound represented by fluorene 4-n (N Η 4) η T i 0 4 whose proton is substituted by ammonium ion. Η 4-η (N Η 4) η The amount of ammonium ion substitution of butylene 04 can be arbitrarily changed by adjusting conditions such as the concentration of ammonium ion, the concentration of free hydrogen group, the concentration of hydrogen ion, or the reaction temperature during the reaction. The particles of the obtained titanate compound In order to affect the particle diameter of the lithium titanate obtained in the subsequent steps, the first step is important. To form a fine titanate compound, and then a fine particulate lithium titanate, set the reaction temperature to 0 ~ 50 ° C, preferably 5 ~ 40 ° C, more preferably 10 ~ 30 ° C. (Please read the precautions on the back before filling this page)

I β ^^ ϋιιιιι ^^^ MB · ΙΗϋ βΜ MUM a ··· One: ° 4I ABB ^ ΜΙΙΙ A ··· AM · Ml · MB Intellectual Property Bureau of the Ministry of Economy Employees' Cooperatives Printed garments Paper size Applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) -12 · 512133 A7 __. B7 V. Description of the invention 10) The titanic acid compound thus obtained is filtered, washed with water, pickled or dried as necessary to For the next second step. The first step is a step in which the titanate compound obtained in the first step is reacted with a lithium compound in an aqueous medium to obtain lithium titanate hydrate. As for the lithium compound, lithium hydroxide, lithium carbonate, and lithium nitrate can be used. Water-soluble lithium compounds, such as lithium sulfate. The reaction proceeds by mixing the lithium compound and the titanate compound in an aqueous medium. The reaction temperature is above 50 ° C, preferably 100 ° C or more, more preferably 100 ~ 250 ° C, and most preferably 130 ~ 2 0 ° C. By reacting within this temperature range, lithium titanate hydrate having excellent crystallinity can be obtained. When the reaction is performed at a temperature of 100 ° C or higher, it is preferable to move the lithium compound and the titanate compound into an autoclave, and perform hydrothermal treatment under a saturated vapor pressure or under pressure. By this hydrothermal treatment, a lithium titanate hydrate having a plate-like shape and having voids in the particles can be obtained. The lithium titanate hydrate thus obtained was filtered, and if necessary, washed and dried. If the drying temperature is a temperature below the temperature at which the lithium titanate hydrate emits crystal water, it can be appropriately set to a temperature of 30 to 200 ° C. The third step is the heat treatment of the lithium titanate hydrate obtained in the above second step to obtain the general formula LiyTiz〇4 (however, 0.8S yS2 · 7, 1 · 3Sz22 · 2 Step) shown by lithium titanate. The temperature of the heat treatment may be a temperature above the temperature at which lithium titanate hydrate emits crystal water, and it can be considered that there are different situations such as the composition of lithium titanate hydrate or the amount of crystal water, but it is approximately 2 0 0 Temperatures above ° C. For 13- (Notes for reading back to 1 and then fill out this page) People paper size This state China due to the family standard 彳 ((, NS) Λ4 specifications (210X297 male f) 512133 A7 B7 V. Description of the invention. 11) Lithium titanate with voids can be obtained at a temperature in the range of 2000 ~ 800 ° C. To obtain lithium titanate with more voids, it is preferably at 25 0 ~ 700 ° C, more preferably at 3 5 0 ~ 6 5 0 ° C. In order to obtain dense lithium titanate, heat treatment can be performed at a temperature of more than 8 0 ° C. If the temperature of the heat treatment is set to about 1 3 0 0 t: above, Lithium titanate which will be sintered between particles is obtained. The above lithium hydrogen titanate can be used as an active material for a battery, for example, by using dopable and dedoped lithium materials as counter electrodes and combining them, it can be composed A battery with a large charge and discharge capacity. That is, the lithium hydrogen titanate of the present invention can be used for a positive voltage and a negative electrode active material of a low-voltage battery, which far exceeds the theoretical capacity of the active material itself. The charging and discharging capacity is greatly improved. Hereinafter, specific examples of the present invention will be described based on experimental results. However, the present invention is of course not limited by these examples. &Lt; Review of PΗ &gt; First, the acid-treated lithium titanate will be reviewed from the viewpoint of pH. Example 1 First, L A saturated aqueous solution of i OH was mixed with anatase-shaped TiO 2-(purity 99 · 8%) to make the Li atomic ratio RLi / Ti to 1. 10 and pulverized in a mortar. Second, by covering the gas with oxygen, The powder thus obtained was fired for 8 hours at a temperature of 8 0 ° C to synthesize lithium titanate L i 4 / 3T i 5/3 04. Therefore, the obtained lithium titanate was placed on a wooden paper scale. (Notes for reading due to E family standard (ΓΝ $) Λ4 specification (2 丨 0X2 magic male f) _ 14_ ^ ilw read this page)

d 512133 A7 B7_ 5. Description of the invention. (12) After washing the lithium titanate that has passed through the screen with distilled water on a 7 5 screen, apply acid using a 1.5% by weight acetic acid solution. The treatment is followed by drying the treated lithium titanate at a temperature of 120 ° C. for 8 hours to obtain lithium hydrogen titanate. The p Η 値 of the obtained pot P lithium hydrogen was measured by the following method. 30 g of lithium hydrogen titanate was put into distilled water 504 and boiled at a temperature of 100 ° C for 5 minutes. After cooling, this water containing lithium hydrogen titanate was passed through filter paper and pre-filtered, and the pΗ 値 of the obtained supernatant solution was measured with a pp meter at a temperature of 20 ° C. As a result, p Η 値 was 9 · 2. Example 2 and Example 3 A lithium hydrogen titanate was obtained in the same manner as in Example 1 except that the concentration of the acetic acid solution used in the acid treatment was changed. The pH values of this material were each 8 · 0, 5 · 6. Comparative Example 1 Lithium titanate was synthesized in the same manner as in Example 1 by firing, and this untreated lithium titanate was compared. The pH of this material is 1 2 0. Comparative Example 2 Lithium titanate was synthesized in the same manner as in Example 1 by firing. After the lithium titanate was washed with distilled water, it was obtained in the same manner as in Example 1 except that no acid treatment with an acetic acid solution was applied. Comparative Example Material. The p Η 値 of this material is 11.6 ° The paper size is suitable for Sichuan China K Family Standard Squat ((, NS) M gauge (2 丨 0,297 mm) ^ g-&quot; (Fill in this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 512133 Zu 3 · ’2. ·.: Α7 1—,.. _… B7—_ V. Description of the invention (13) Using the materials obtained above, a coin-type evaluation battery is produced. This coin-type evaluation battery is an external can containing a negative electrode pellet and a current collector, and an external cup containing a counter electrode through a separator, and the outer periphery of the external can and the external cup are laminated. Constructed by locking the washer. Such a coin-type evaluation battery was produced by the following method. First, add 90 parts by weight of the material (L i 4 / 3T i 5 / 3〇4) obtained in each example or comparative example, 5 parts by weight of graphite as a conductive material, and polyvinylidene fluoride pvd as a binder. F 5 parts by weight, after kneading and dispersing in a mortar, n-methylpyrrolidone was added in small amounts to prepare a slurry-like negative electrode mixture. The negative electrode mixture was dried at a temperature of 120 ° C for 2 hours, and then pulverized in a mortar to obtain a powder mixture. This powder mixture was filled into an electrode collector made of stainless steel (SUS 304) in a mesh shape, and compression-molded to an outer diameter of 15 · 5 mm and a thickness of 0 · 2 mm. The powder was vacuum-dried at a temperature of 120 ° C. 2 Hours, making negative pellets. Next, a circular cutter with an outer diameter of 16 · 5mm was used to punch metal lithium with a thickness of 1.0 mm as the counter electrode, and it was pressed into the outer cup. A sealing gasket made of polypropylene was installed in the outer cup. Therefore, a separator made of a microporous polypropylene film with a thickness of 50 / zm stamped to a specified size is placed on the lithium metal that has been pressed onto the external cup. The lmo1e / &lt; ratio dissolves the electrolytic solution in which Li PF6 is dissolved into a solvent in which the volume ratio of propylene carbonate and ethyl methyl carbonate becomes 50:50, and then, the negative electrode ingot prepared in the previous step is placed. Put it on the isolation board, and then cover the outer cans. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm): 16-: (Please read the precautions on the back before filling this page ) ------- Order --------- line

512133 A7 B7 V. Description of the invention. (14) A coin-shaped evaluation battery with an outer diameter of 2 mm and a height of 1.6 mm was produced by locking and sealing the outer peripheral portion. In addition, the outer cans are made of stainless steel (SU6 304) and nickel-plated. The theoretical charge capacity of this battery is 175mAh / g. The battery fabricated as described above was charged at a constant current of 1 mA to 2.5 V at room temperature, and then discharged to 1.0 V. The charging capacity at the time of charging and discharging is shown in Table 1. In addition, as a representative example, the charge-discharge curves of the evaluation batteries using lithium hydrogen titanate of Example 2, Comparative Example 1 and Comparative Example 2 are shown in Fig. 1. (Read the precautions before reading this page), ν &quot; -17- The paper size leftover + family mark (rNS) Λ4 specification (210X297 male f) 512133 A7 B7 V. Description of the invention (15 ) Table 1 Treatment P Η 値 Charging capacity (m Ah / g) Example 1 Distilled water treatment + acetic acid treatment 9. 2 17 1 Example 2 Distilled water treatment + acetic acid treatment 8. 0 2 0 0 Example 3 Distilled water treatment + acetic acid treatment 5.6 2 7 1 Comparative Example 1 No treatment 12.0 16 5 Comparative Example 2 Distilled water treatment only 11.6 16 8 _____I____I I · II (Please read the precautions on the back before filling this page) As can be seen from the figure 1, it is used in titanic acid The battery of Example 2 in which lithium hydrogen titanate was subjected to two washing treatments and acid treatments in lithium was compared with the battery of Comparative Example 1 without any treatment or the battery of Comparative Example 2 only subjected to washing treatment. , Can get longer charge and discharge time. Therefore, as shown in Table 1, the charging capacity of the batteries of Examples 2 to 3 can far exceed the theoretical capacity (175mAh / g). From this fact, it is known that by specifying PΗ 値 of lithium hydrogen titanate, a parameter capable of estimating its charging ability can be obtained. Fig. 2 is a graph showing the relationship between the pH and the charging capacity of lithium titanate (lithium hydrogen titanate). If the pH is 1 2 · 0 or less, it can be seen that the charging capacity will increase rapidly. In addition, it is more desirable to show a pH ranging from 5.6 to 1 1 · 2. &lt; Review related to proton substitution &gt; This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -18- --I .-- Order · ------- • line

Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 512133 A7 B7 89.: s car 5. Description of the invention (16) By treating the acid of lithium titanate with lithium, the pH value will change. Known from previous experiments. &lt; Please read the notes on the back before filling out this page.) In this experiment, the performance of acid-treated protons was reviewed. Example 4 (1) Synthesis of lithium titanate 1-1) Synthesis of titanic acid compound In a glass reaction vessel made of 2 5 &lt; 6. Ammonia water having a concentration of 8 Olmo 1 / &lt; 8 9 8 8 &lt;, Under stirring, while pre-chilling until the temperature of the solution becomes 10 to 20 ° C, disperse the titanium tetrachloride solution at a concentration of 1 · 2 5 m ο 1 over a period of 1 · 5 hours 9 · 0 1 ". The free ammonia concentration at the time of completion of the addition was 0.5mo1 / &lt;, the solid concentration was 50 g / &lt; in terms of T i 〇2, and the pH was 8.3. After aging for 1 hour, 5 m ο 1 concentrated solution of hydrochloric acid aqueous solution 1 · 3 &lt; printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs was added in 1 hour to make the pH 4. Continue to maintain the pH at 4 and age for 1 hour. In order to maintain p Η in the aging, 5 ′ ·-. • m ο 1 aqueous solution of hydrochloric acid 0 · 4 2 &lt; was added. After the aging is completed, it is filtered and washed to obtain a titanate compound. 1-2) Synthesis of Lithium Titanate Hydrate Pure water was added to the titanic acid compound obtained in 1-1), and the mixture was stirred and dispersed with a large mixer to obtain an aqueous dispersion of 17 &lt; The solid concentration is 45 · 38g / &lt; and the pH is -19 in terms of Ti〇2 conversion. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). One time «^-&gt; (6 Ι 合 He Lun ^ India 512133 A7 B7 V. Description of the invention "17) 6 · 7. In a glass reaction container of 25 &lt;, the above-mentioned water dispersion liquid 1 3 · 882 &lt; and pure water 0 · 1 1 8 &lt; were put under ice-cooling while stirring to a solution temperature of 10 to 2 °. C, 2 · Olmo 1 / &lt; lithium hydroxide aqueous solution 4 · 00 &lt; was dispersedly added within one hour, and then matured for 1 hour. The solid concentration after the addition was 3 5 g / in terms of T i 〇2, the Mo / Li ratio was 1.02, and the pH was 11.8. The matured sludge was fed into stainless steel 2 5 &lt; The autoclave was hydrothermally treated at a temperature of 190 ° C for 4 hours with stirring. The sludge after hydrothermal treatment will increase viscosity, and its viscosity at 2 5 ° C is 2 1 4 0 c p. Next, after filtering the hydrothermally treated sludge, it was dried at a temperature of 110 ° C without washing to obtain lithium titanate hydrate (L i 1.33T i 6.666 ○ ^ 2 Ο) 0 1-3) Synthesis of lithium titanate After crushing lithium titanate hydrate obtained in 1-2), put the crushed material in a quartz firing container, and fire it at 5 5 0 ° C under the atmosphere of air. 3 hours, and lithium titanate (sample A) was obtained. (2) Synthesis of lithium hydrogen titanate In a glass-made reaction vessel, feed pure water of 5000 m £ and lithium titanate of sample A of 1000 g, and add 100 g all at once while stirring. Acetic acid aqueous solution 6 72, after reacting at a temperature of 25 ° C for 1 hour, filtering and washing, drying in the atmosphere at a temperature of 110 ° C for 3 hours. 、 Milk eight size 4 (210X297 male f) -20 · (Notes for 1S1 read the back and then fill out this page)

512133 A7 B7 V. Description of the invention. (18) 2 'to obtain lithium hydrogen titanate (sample A1). pH 値 is 1 (Notes before reading this page before you fill in this page) MM m 5 Divide by adding 10% by weight of acetic acid aqueous solution all at once 1 3 3m £ 'Make the reaction at 60 ° C for 1 hour, replace In Example 4, 100% by weight of acetic acid aqueous solution (72) (72) was added all at once, and the reaction was carried out at a temperature of 25 ° C for 1 hour. The rest was treated in the same manner as in Example 4 to obtain lithium hydrogen titanate ( Sample A2). The pH was 9.3.亶 龙 例 6 Divide by adding all 10% by weight acetic acid aqueous solution 2 0 02 'at 60 ° C for 1 hour, instead of adding all the (2) 10% by weight acetic acid aqueous solution 6 at once 72. After reacting at a temperature of 25 ° C for 1 hour, the remainder was treated in the same manner as in Example 4 to obtain lithium hydrogen titanate (sample A3). The pH was 8.0. Example A: Ten times ^. ^-. / ¾¾ ^ ¾¾ ^^ print f divided by adding 20% by weight of acetic acid aqueous solution 167m £ at one time, and reacting at 60 ° C for 1 hour instead of the example Add 4 (7) of 10% by weight of acetic acid aqueous solution (2) all at once, and make the reaction 1 hour at 25 ° C. The rest is treated in the same way as in Example 4 to obtain lithium hydrogen titanate. (Sample A4). The pH was 7.8.

MMMS This paper is standard Chinese state standard ((, NS) Λ4 gauge (210X 297 male f)-21-^ 133 ^ 133 a _χ 合 竹 社 印 3: Comparative Example 3-Example 4 . P Η 値 is 1 1 Α7 ____ ___ i. Description of the invention 19) Divide by adding 40% by weight of acetic acid aqueous solution 67m £ at a time, and react at 60 ° C for 1 hour instead of all of Example 4 at a time. A 10% by weight aqueous solution of acetic acid (67 m) in () was added, and the reaction was carried out at a temperature of 25 ° C. for 1 hour, and the rest was treated in the same manner as in Example 4 to obtain lithium hydrogen titanate (sample A5). PH 値 is 7.6. Duplicate Example 9 Divided by adding 17.6 m of hydrochloric acid aqueous solution at a concentration of 5 m0 in 1 hour, and reacted at 60 ° C for 1 hour, instead of adding 10% by weight of (2) all the time in Example 4 An aqueous acetic acid solution of 67 m £ was allowed to react at a temperature of 25 ° C for 1 hour, and the rest was treated in the same manner as in Example 4 to obtain lithium hydrogen titanate (sample A6). pH 値 is 7 · 4. Example 10 Divided by adding 5mo of a hydrochloric acid aqueous solution of 2002 in a concentration of 1 hour, and reacted at 60 ° C for 1 hour, instead of adding all the (2) 10% by weight acetic acid aqueous solution at once in Example 4 67 m £, except that the reaction was allowed to proceed at a temperature of 25 ° C for 1 hour, and the rest was treated in the same manner as in Example 4 to obtain lithium hydrogen titanate (sample A7). pH 値 is 5 · 6. 1) The obtained lithium titanate of sample A is a comparative test 6 ° (read the precautions on the back before reading this page)

This paper is based on the Chinese standard K (埤) of this state in China (210 χ 297 male f 22- 512133 A7. __B7____ V. Description of the invention .. (20) Example 1 1 (1) Synthesis of lithium titanate Except for firing at 6 2 5 ° C for 3 hours instead of firing at 5 50 ° C for 3 hours, the rest of the process is the same as that in the example to obtain titanium. Lithium acid (sample B). (2) Synthesis of lithium hydrogen titanate In a glass reaction vessel of 1 &lt;, pure water 5 0 02 and lithium titanate 100 g of sample B were fed, and all of them were added at a time while stirring 100%. Aqueous acetic acid solution was 1 3 3m. After reacting at a temperature of 60 ° C for 1 hour, it was filtered and washed, and dried in the air at a temperature of 110 ° C for 3 hours to obtain lithium hydrogen titanate (sample B1). ). pH 値 is 9 · 2. Example 1 Divide by adding all 20% by weight acetic acid aqueous solution 16 at a time, and react at 60 ° C for 1 hour instead of adding all of the 1% by weight (10) acetic acid aqueous solution 1 of Example 1 3 3m £, after reacting at a temperature of 60 ° C for 1 hour, the rest was treated in the same manner as in Example 11 to obtain lithium hydrogen titanate (sample B2). pH 値 is 8 · 2.

Example U Divided by adding an aqueous acetic acid solution at a concentration of 5 mO for 1 7 82 within one hour, and reacted at 60 ° C for 1 hour, instead of adding all the acetic acid of 10% by weight in Example 11 (2) at a time. Aqueous solution 丄 3 3

ί means a note that you should read before and then fill in the book WZ ¥¥ 4, this paper &amp; W f KK g, (CNS) AAim (210 X 297 ^^ · -23- 512133

A7 B7_____ V. Description of the invention (21) J. After reacting at a temperature of 60 ° C for 1 hour, the rest is treated in the same manner as in Example 11 'to obtain lithium hydrogen octylate (sample B 3). pH 値 is 7 · 5. (Please read the precautions on the back before filling in this page.) Comparative Example 4 The lithium titanate of sample B obtained in (1) of Example 11 was used as a comparative sample. p Η 値 is 1 2. Example 1 4 (1) Synthesis of Lithium Titanate A plastic beaker made of 3 &lt; was charged with hydrated titanium oxide (trade name C-II, manufactured by Ishihara Sangyo Co., Ltd.), which was converted to 500 g in the amount of butyl i02. The sludge was added with a lithium hydroxide aqueous solution 1. 8 1 5 &lt; at a concentration of 3.0 m and the mixture was stirred at room temperature for 4 hours. In the atmosphere. 1 50. &lt;: The sludge is dried up by evaporation. The dried filter cake was pulverized, and then fired at a temperature of 700 t in the atmosphere for 3 hours to obtain lithium titanate (sample C).

(2) Synthesis of lithium hydrogen titanate Printed on 1 &lt; glass reaction vessel with pure water 5 0 ^ and test half bucket C of lithium titanate 1 0 0 g Add 1% by weight of acetic acid aqueous solution 1 3 3m at a time while stirring, react at a temperature of 60 ° C for 1 + hours, filter and rinse, and dry in the air at a temperature of 110 ° C 3 小 # to obtain lithium hydrogen titanate (sample C1). pH 値 is 8.9. Example 1 5 This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 24-

512133 In addition to one hour &gt; 3 disperse and add 5 m ο &lt; / &lt; concentration of acetic acid aqueous solution 86 m £, make the reaction at 60 ° C for 1 hour, instead of adding all of Example 14 4 (2 ) Of a 10% by weight aqueous acetic acid solution of 133 m £, except that the reaction was performed at 60 ° C for 1 hour, and the rest was treated in the same manner as in Example 14 to obtain lithium hydrogen titanate (sample C2). pH 値 was 8.3 ° Comparative Example 5 Lithium titanate of sample C obtained in Example 14 (1) was used as a comparative sample. P Η 値 is 1 1 · 5. Comparative Example 6 A lithium titanate was obtained in the same manner as in Example 4 except that firing was performed at a temperature of 8 10 t for 3 hours, and was replaced by firing at a temperature of 5 50 ° C for 3 hours. (Sample D), pH 値 was 3 · 7. Evaluation of characteristics The samples A1 to A7, B1 to B3, Cl, C2, and A to D obtained in Examples 4 to 15 and Comparative Examples 3 to 6 were used to obtain chemical compositions L i and T i by chemical analysis. . The longest particle diameter was read using an electron microscope. The specific surface area and void volume were measured using Bellsorp 2 8 manufactured by Japan Bell Corporation. The amount of substitution of H C protons was determined by the following method by TG-DTA thermal analysis. That is, in the TG-DTA curve, the absorption scale caused by protons becoming water and detachment is applicable to China National Standard (CNS) A4 specifications (210 X 297 public love) -25: (Please read the precautions on the back before filling this page)

--------- Order i n n nt n I

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics Printed by the Employee Cooperative of the Intellectual Property Bureau of the Ministry of Economics 512133

The protons at the B and A positions of the spinel structure are observed separately, so the amount of proton substitution can be calculated from the decrements. • The proton substitution amount calculated by this method corresponds well to the residual amount of Li that was previously obtained by chemical analysis. The lithium titanate samples A1 to A7, B1 to B3, Cl, C2, and A to D obtained in Examples 4 to 15 and Comparative Examples 3 to 6 were used to measure the charge and discharge capacity of the battery. Figure 3 shows the overall structure of the non-aqueous electrolyte battery used in the evaluation. The coin-shaped battery using this embodiment and the comparative example will be described in detail below. First, the active material lithium hydrogen titanate is 90 parts by weight, 5 parts by weight of graphite as a conductive material, 5 parts by weight of polyvinylidene fluoride as a binder, are mixed in a mortar, and NM is added in a small amount. In the dispersion, a mud-like mixture was prepared. The mixture was dried at 120 ° C for 2 hours, and then pulverized in a mortar to obtain a dry powder mixture. This mixture was filled into an electrode current collector 8 of a stainless steel (SUS 304) mesh and compressed to form an outer layer. A diameter of 15 mm and a thickness of 0 · 2 mm were used to make pellets 7. The pellets were dried at 120 ° C for 2 hours under vacuum. In addition, a metal lithium 3 with a thickness of 1.0 mm was punched from a circular cutter with an outer diameter of 16 mm and pressed against the cup 2 as a counter electrode. On this, the separator 6 having a microporous polypropylene film having a thickness of 2 5 / zm which has been punched to a necessary scale is sandwiched by a seal_mouth gasket 5 and a cup 2 which have been inserted in polypropylene, and is used For those who dissolve L i PF6 at a ratio of lmo 1 / &lt;, drip propylene carbonate (PC), vinyl carbonate (EC) into the electrolyte (please read the precautions on the back before filling this page)

This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) • 26- ui-5; ', «Tv- ^ u (_T7; i) 0. ^ print 1 ·· 512133 A7 _ B7 V. Description of the invention i 24), 1,2-dimethoxyethane (DME) in a mixed volume of equal volume. Furthermore, after the pellet 7 is placed, it is covered with a nickel-plated stainless steel ( SUS 304) was formed into a two-layer can 1. The sealing portion was tightly closed and sealed, and then a coin-shaped non-aqueous electrolyte secondary battery having an outer diameter of 20 mm and a height of 1.6 mm was produced. Next, using the coin-shaped battery produced in this way, the battery was charged at a constant current of 1 mA to 2.5 V at room temperature, and then discharged to 1.0 V, and the charge-discharge capacity was measured. The confirmation results of the longest particle diameter, specific surface area, void volume, and charging capacity of the coin-shaped battery using metal lithium on the counter electrode are shown in Tables 2 and 4. Specification (210/297) (Please read the precautions before filling in this page)

512133 A7 B7 V. Description of the invention X 25) [Table 2] 化学 Example chemical composition Longest particle diameter am Specific surface 穣 m2 / ff Gap S ml / g Charge capacity S mA h / g pH 値 Comparative Example 3 A Lil.45Til .6504 0.1 to 0.2 63.0 0.43 163 11.6 実 Example 4 A1 H0.14Ul.24Til.66O4 0 · 1 to 0.2 · 62.2 0.48 175 11.2 実 Example 5 A2 H0.32Lil.08Til.65O4 0.1 to 0.2 · 5 59.3, 0.49 193 9.3 Application Example 6 Λ3 H0.40Li0.96Ttl.6604 0.1 to 0.2 57.2 0.43 204 8.0 Example 7 A4 H0.43Li0.88Ti 1.6704 Oi to 0.2 56.7 0.50 212 7.8 Example 8 A5 H0.54Li0.80Ti 1.6704 0.1 ~ 0.2 52.8 0.56 215 7.6 実 Example 9 A6 Hl.09Li0.16Til.68O4 0.1 ~ 0.2 60.2 0.48 264 7.4 実 Example 1 0 A7 Hl.28Li0.02Ti 1.6704 0.1 ~ 0.2 62.2 0.43 271 5.6 Comparative Example 4 B Lil.43TU. 6504 0.13 to 0.2 26.4 0.13 158 12.3 実 Example 1 1 B1 H0.16Lil.14Til.67O4 0. η to 0.2 29.1 0.20 171 9.2 実 Example 1 2 B2 HO.35LiO.97Tii.6704 0.13 to 0.2 31.4 0.21 200 8.2 例 Example 1 3 B3 H1.05 LiO.lSTi1.6904 0.13 to 0.2 32.5 0.20 221 7.5 Comparative Example 5 C Li i.44Ti 1.6504 0.2 to 0.4 6.1 0.03 145 11.5 実Example 1 4 Cl H0.19Lil.16Til.66O4 0.2 to 0.4 6.6 0.02 151 8.9 実 Example 1 5 Cl H0.53Li0.75TU.6804 0.2 to 0.4 7.9 0.05 204 8.3 Comparative Example 6 D Lil.17Til.8104 0.5 to 1.0 0.9 0.01 83 3.7 ii Please read the precautions on the back before coping with this page) if

Tv Associate Bureau J. Elimination f: The paper size of the joint print is used in accordance with the Chinese National Standard (rNS) Λ4 specification (210X 297 male f) -28- 512133 _: year and month repair A7 B7 V. Description of the invention (26) The detailed conditions of the experimental content in Table 2 described in the comparative examples and the examples, A is a temperature of 5 50 ° C for 3 hours under an atmosphere of atmosphere, B is 6 2 5 ° C for 3 hours, and C is 70 0 ° C. The three-hour calcination was used as a reference, and after the lithium titanate was calcined, it was obtained by changing the amount of proton substitution with water and acid treatment. '' From the results in Table 2, the charging capacity of the electronic reaction of one of the lithium titanates currently being commercialized in the 1.5V series lithium ion battery is equivalent to approximately 15 OmAh / g. Comparative Example 3, which was replaced by protons, also maintained a considerable charging capacity of more than 160 m A h / g. Moreover, in Examples A 1 to A 7 in which the proton substitution of the present invention was performed, the charge and discharge capacities were increased in order of samples A &lt; A1 &lt; A2 &lt; A3 &lt; A4 &lt; A5 &lt; A 6 &lt; A7. Similarly, in Examples B1 to B 3, the charging capacity is increased by the order of samples B &lt; B 1 &lt; B 2 &lt; B 3, and in Examples C ~ C2, the charging capacity is based on that of sample C &lt; C1 &lt; C2. The order is improving. In any case, it can be confirmed that the larger the proton substitution amount is reflected in the charging capacity. Since the influence due to this temperature was observed, Comparative Example 6 revealed the charging capacity of lithium titanate fired at 800 ° C. From Comparative Example 6, the specific surface area is 0.99 m 2 / g, which is 1/6 of Comparative Example 3, and the charging capacity is equivalent to 50% of 8 3 mAh / g. Therefore, it can be confirmed that the influence of the charging capacity due to the above firing temperature is large. Also, as shown in Figure 4, it can be confirmed that the proton substitution amount and charge capacity are in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm). -29-(Please read the precautions on the back first (Fill in this page again) • Fees — — — — — — — — — Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives 512133

The quantity has a proportional relationship, ‘that is, the larger the amount of proton substitution, the greater the charging capacity. The effect of proton substitution on lithium titanate is obvious and visible. In addition, in the order of A (550 ° C) &gt; B (625 ° C) &gt; C (700 ° C), the lower the firing temperature is, the larger the specific surface area is. As the reaction area increases, the charging capacity is also increased. Get bigger. By combining the conditions with an increase in the amount of proton substitution, the efficacy of the present invention can be further improved under low-temperature firing conditions. However, to increase the proton substitution amount, a larger charge capacity can be expected. On the contrary, it is difficult to control the proton substitution amount by water and acid treatment. In the embodiment of the present invention, the larger the proton substitution amount, the It has been confirmed that the greater the dispersion of the charging capacity, as for the proton substitution amount of the present invention, it is preferable to use the general formula HXL iy-xTiz〇4 (however, y2x &gt; 〇, 0 · 8.7, 1 · 3SzS2 · 2 The field of proton substitution represented by) is considered to be a better condition because it can be used as a battery material. Brief Description of Drawings Fig. 1 is a characteristic diagram showing the difference between charge and discharge curves caused by the presence or absence of acid treatment. Fig. 2 is a characteristic diagram showing the PΗ phase relationship in the charging capacity of lithium hydrogen titanate. · Figure 3 is a schematic cross-sectional view showing the structure of a coin-shaped battery for evaluation of characteristics. Figure 4 is a characteristic diagram showing the relationship between the proton substitution rate of the charging capacity. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -30- (Please read the precautions on the back before filling this page ) · 丨 丨 丨 丨 — ， 丨 丨 · 丨 _ 丨 丨 丨 丨 -j Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs

Claims (1)

512133 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 6. Application scope of patents ~ One '... One · One' Uo ,: Patent No. 8. 7113327 Patent application in Chinese. Amendment of patent scope in the Republic of China. Lithium hydrogen titanate is characterized by pre-acid treatment of lithium titanate represented by LiyTi204 (but 0.8 $ yS2.7, i.3SzS2.2), and the pH is 1 1 · 2 or less. ′ 2 · —a kind of lithium hydrogen titanate, which is represented by the general formula HxL iy- xTiz〇4 (but ygx &gt; 〇, 2.7 · 7, 1.3 $$$ 2 · 2). 3. As the lithium hydrogen titanate of item 2 of the patent application, it is in the form of particles and there are voids in the particles. 4 · If the lithium hydrogen titanate of item 3 of the patent application scope, its maximum particle diameter is 0 · 05 ~ 50 / zm. 5. The lithium hydrogen titanate as claimed in item 3 of the if patent, which has a specific surface area of 0.01 to 300 m2 / g.6. A method of manufacturing lithium hydrogen titanate, which is characterized by the general formula LiyTi2O4 (but 0.8SyS2.7, 1.3Sz S 2 · 2) The lithium osmate and the acid shown in the solvent are mixed in the solvent, and the aluminum acetate is contacted with the acid, and the lithium atom is replaced by a proton to form the general formula HxL iy-χΤ iz Lithium hydrogen titanate represented by 〇4 ('y ^ x> 〇, 〇 2 · 7, 1 · 3 $ zS2 · 2). 7 · For the manufacturing method of lithium hydrogen titanate in item 6 of the scope of patent application, the paper size applies to the Chinese National Standard (CNS) A4 specification (210x 297 mm) 丨 丨 -----------: —IT -------- · line &lt; Please read the precautions on the back before filling in this. 1) 512133 Printed clothing A8 C8 D8 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. The scope of the patent application including the above acid For acetic acid. 8. The manufacturing method of lithium hydrogen titanate according to item 6 of the patent application scope, wherein the first step of obtaining an acetic acid compound by reacting a titanium compound with an ammonium compound in an aqueous medium, and making the above titanic acid in an aqueous medium The second step of reacting the compound with a lithium compound to obtain lithium titanate hydrate and the third step of the third step of heat-treating the above lithium titanate hydrate can obtain a general LiyTiz〇4 (but, 0.8SyS2 Lithium titanate represented by 7, 7, 3 $ zS2, 2). 9. The manufacturing method of lithium hydrogen titanate according to item 8 of the application, wherein the second step is a step of hydrothermally treating the titanate compound and the lithium compound in an ice-based medium to obtain lithium titanate hydrate. 10. The method for manufacturing lithium hydrogen titanate according to item 8 of the scope of patent application, wherein the third step is a step of thermally treating lithium titanate hydrate in a temperature range of 2000 to 800 ° C. 1 1. The manufacturing method of lithium hydrogen titanate according to item 6 of the application, wherein a mixture of titanium oxide and a lithium compound is heat-treated at a temperature of 500 to 900 ° C to obtain the general formula LiyTiz〇4 ( However, lithium titanate represented by 0 · 8 · 7, 1 ·· 2). This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) -2- -nn 1 nn -ί i If nn · nn · ϋ n ϋ I ϋS, J8 ϋ — a— I \ 4 /. &lt; Please read the notes on the back before filling this page)