TWI358148B - Lithium metal oxide materials and methods of synth - Google Patents

Description

1358148 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a lithium metal oxide composition, and an electrochemical device using the composition, particularly a composition of magnesium oxide, which is suitable as a clock The composition of the electrochemical device. [Prior Art] Rechargeable lithium and lithium ions can be used for various purposes such as cell phone phones, laptop computers, digital cameras and video cameras, and mixed electric vehicles, etc. due to their high energy density. Commercially available chain ions and batteries typically comprise a graphite anode and a LiQ) tantalum cathode material. However, LiCo〇2 cathode materials are expensive and typically have a low capacity of about 150 mAh/g.

An alternative to LiCo〇2 cathode materials, including LiNi〇2 cathode materials, is relatively inexpensive. A typical LiNiO 2 cathode material comprises a composition having the formula LiNi〇8C〇〇2〇2 or LiNio.sCoo^AIq.osO2. These materials are more expensive than cobalt-free L|Nj〇2 cathode materials because cobalt is more expensive than nickel. In addition, the LiNiCo02 f cathode material is generally less complex, more complex, and has a higher n-cycle efficiency than the LCo〇2 cathode material because the LiNi〇2 cathode has a lower structural stability and a higher surface resistivity.

Li (Ni, Co) 〇 2 cathode materials have also been disclosed. For example, the method of preparing a cathode material shown by Lecerf et al. in U.S. 4,980,080 LiyNi, y〇2^ Li, xCox02 secondary battery. Xie et al., U.S. Patent No. 5,750,288, which is based on a LixMyOz material, wherein M is a non-transition metal selected from the group consisting of sulphur, gallium, tin, and rhodium. The LixNiyCozMn〇2 material is disclosed in U.S. Patent No. 5,783,333. The material of the formula LixNiyCozMn〇24 υχΜη2 ιΜ1Λυ^ is disclosed in U.S. Patent Nos. 6, 947 and 6,379,842, the bismuth is a metal selected from the group consisting of sho, titanium, crane, collateral, turn, town, group, stone. Xi, and its combination, ❿M1 series chrome, Chin, He, Lu, Ming, 5 1358148 鉄, tin, zinc, wrong, one of Shi Xi, or a combination thereof. Kumta et al., U.S. Patent No. 6,007,654, discloses a cathode material having the formula Lii+xMi as a group 2(4) and LiNi^MyNxOp, wherein M is a transition metal selected from the group consisting of titanium, vanadium, chromium, manganese, lanthanum, cobalt, and aluminum. And N is an element of the nth group, and is selected to contain magnesium, about, recognize, bismuth, and zinc. A positive electrode material based on Li-Ni-Co-Mn-〇2 is disclosed in U.S. Patent No. 6,040,090 to Sunagawa et al.

An active cathode material having the formula LiLNVc-A^CocAUMgMO2 is disclosed in U.S. Patent No. 6,274,272. A lithium metal oxide material containing a complex dopant of the formula LiNikCOyMJVi'bO2, wherein the M system is selected from the group consisting of a metal containing Qin, a dream, and combinations thereof, is disclosed in U.S. Patent No. 6,277,521. It is selected from the group consisting of magnesium, calcium, strontium, barium, and combinations thereof. A LiCo02 coated LiNiO 2 or Li (Ni, Co) 02 material is disclosed in U.S. Patent No. 6,71,649. None of them revealed a Li-Mg-Ni-02 cathode material. ,

A cathode material having a formula of Liy_xlNilx2Mx〇2, wherein M is selected from the group consisting of metals containing lanthanum, lanthanum, manganese and magnesium, Χ = χ1+Χ2, 〇<lt;>>;χ1^〇2,〇<χ2乞0.5,〇<xg〇.5, and 〇.9gygi.3. ^ Most manufacturers also manufacture cathodes commercially, using materials of the general formula LiNic〇M〇2. TODA (formerly Fuji Chemical Co., Ltd.) manufactures products CA5, CA1505N and NCA. Ηοηέ-Ο-FMC and Nichia (both Japanese companies) also provide riding cathodes. Typical disadvantages of these products are low safety performance and poor productivity. SUMMARY OF THE INVENTION According to one or more specific examples, the present invention relates to UxMgyNi〇2 materials, when utilized in an electrochemical application or system, characterized in that it is a system or a system that is safer and less expensive to use. High capacity, long cycle life, and high yield, especially high power. In a number of specific examples, 8 6 features 4, lower cost, improved chemical stability

LiCoO iJ/Check South can provide more capacity, especially for example cathode materials compared to 1^〇〇2 and/or LiNi〇2. One or more specific examples' The present invention provides a composition of the formula LixMgyNi〇2, 〇.9<x<1.3, 0.01<y<〇1*〇9i<x^<i3. The present invention provides a core layer of the formula

ϋ: ν·9<Χ<1·3'〇·〇1<π〇.1 and 〇.9<X+y<L2), and LlaC〇b〇2g core layer coating (where 〇7<;&< 13 and 〇 9 < b < 1.2) composition. According to - or the above specific examples, the present invention provides an electrochemical cell comprising a composition having the formula LixMgyNi〇2, wherein 〇9<χ<1 3, 〇〇1 <y<0.1 and 〇.9<x +y< 1 3. According to - or the above specific examples, the present invention provides an electrochemical cell comprising a Jadeite whose particle comprises a core layer of the formula LixMgyNi02 (where 0.9<x<.' 0.01<y<y<0.1 and 〇.9i<x +y<1 3), and the coating on the core layer. The coating has the formula LiaCob02' where 〇 7 < a < 1 3 and 〇 9 < b <

The composition is prepared by providing a mixture of a compound of cerium, magnesium and lysine, and the mixture is heated in an oxidizing atmosphere for a period of time sufficient

LixMgyNi〇2 composition, wherein 〇9<χ<1 3, 〇〇1 <y<0.1 and 0.91<x+y<i.3 〇 According to one or more specific examples, the present invention provides coated granules The method comprises the steps of: providing a compound conjugate of nickel and nickel, sintering the first mixture in an oxidizing atmosphere at a first temperature for a first period sufficient to crystallize the first mixture into a heterogeneous 'having a formula LixMgyNiC) Wherein 〇9<χ < 1.3 '0.01 <y<〇.l and 〇% <x+y<丨3; and coating the core particles with a second mixture of compounds comprising lithium and cobalt, coated The core particles are sintered at the second temperature for a second period of time sufficient to crystallize the layer having < LiaC〇b〇2, wherein 0.7 <a <1.3 and 〇.9<b<1.2. 7 1358148, while Ni mainly in the surname S and Bu% away 1 mainly in crystallography 3a Others in the invention rely on = and and: = <-. ΐ:::Γ白' The drawings are simplified and not drawn to scale _ Φ as shown in the drawing. For the sake of clarity, each of the figures is shown in the same number. The present invention is not necessarily illustrated, and each component does not necessarily have various details and configuration details, including ί 乂 二 二The change 'is intended to cover the items listed later? and i et al.: shape=提=池本2 ΪΪί subcell, and the method of manufacture and use, for example, the electrochemical device of the present invention using the present invention is characterized in particular by the amount of cost. Having a child's temperament and providing a high degree of capacity during long-term operational life, according to a number of specific examples, the composition of the present invention typically exhibits utilization of uc〇〇2 and UNi〇" in an electrochemical device including but not limited to primary and secondary batteries. ; Improved capacity, circulation and safety. The material of the present invention can provide, and is suitable for, because of the typical production and / or utilization costs, compared to UC 〇〇 /,

LiNi02 or LiNi〇8C〇〇2〇2 is low in material. The present invention provides a composition of a metal oxide of a bell and a solid; a layer of a metal associated with a crystal lattice in the crystal lattice of R3m. At the end of the day, I learned that 'invented several: f is the place' and b is called 3b. According to this: the genus is associated at 3b. When, for example, the material of the present invention is used, it is the second type of gold; in, or in several cases. In the process of "two-embedding and silk, providing the step of crystallographic centering, t-structure", the composition of the invention is used in the process of de-mtercalation, at least partially crystallizing the crystal or In the above preferred embodiment, the composition may include a crystallized crystal and a t fine crystallographically and % _, shouting at the junction or the above specific example 'provided by the present invention—the remainder, the general formula of which is I^ MgyNiO〗 'where 〇.9<x<1.3 and 〇〇1<y<〇J, and 〇91<^曰^:^^1·1 *a〇2<y<0·05 is preferred. Composition , "Lithium I. Born, lithium and magnesium are associated with 3a, and nickel is associated with the north. According to yet another specific example, the present invention provides a granular material, including an inner layer, an applied layer or a plurality of layers of metal oxide. Coating.

LiaCob〇2^b^ , ^ 〇曰9<b<1.2: In some cases T, the coating is characterized by subtraction from the recording in the core layer, and its Co/Ni molar ratio is about 〇.〇1 to about! 4 range. In this specific example, 0.9 < a < 1.3, L8 < b < 2.2, and c〇 / Ni molar ratio in the range of about 〇.〇2 to about G.8. The layer or layers are characterized by a concentration gradient with a distance (for example, the lining of the silk gauge Φ). The concentration gradient of the recording relative to the surface distance of the disc, ranging from about 1% to about g g of the outer surface of the particle. The invention also provides a technique for synthesizing the species, having the first species = lion, and in some cases 1" , with the second metal, ί first "I according to other specific examples of the step-by-step" (4) provided by the synthesis _ weight station (four) weight% of the Gu 1 accounted for the pellet in the technology, can reduce the second metal and 3a Any tendency of _ can be provided during the clock-embedding/de-intercalation cycle, providing a clock-mixed student set =, ί hair: _ can provide the amount, low cost, and high voltage, and improve the cycle life = one or more In a specific example, the present invention may utilize a precursor compound such as a metal oxide of a clock, preferably a crystal lattice stabilizer metal compound. According to other specific examples, the present invention may provide or promote a method; = forming an ionic substance from a precursor compound, preferably becoming a special site. The treatment conditions of the present invention promote the formation of a metal oxidation read and a predetermined crystallographically specific site. For example, the present invention provides a donor. Compound, which can preferentially become crystallized One or more metal donor compounds associated with a death may preferentially become one or more metal donor compounds associated with 3b on the day of the mouth. Therefore, according to one or more specific examples, the present invention may utilize lithium. The compound is given, the magnesium gold donor compound, and the nickel metal compound (10); the treatment conditions promote the formation of ionic substances, are mixed, and the crystal forms a mixed metal oxide, and the first metal in the pot can be preferentially crystallized. 3a is associated, and the second metal can be preferentially associated with the replenishment. According to yet another specific example, the present technology can provide a lithium magnesium oxide composition freely or above, a precursor compound can be utilized, including, for example, a dilithium donor, a magnesium donor, and a nickel donor. In some cases, the oxidant or compound may be used. Thus, the precursor compound mixture may be listed as a lithium source, an oxidant, a first metal donor, and a second. a metal donor, - [lithium source, oxidant, first metal donor and second metal donor, in about the same processing conditions, for example in the same treatment The degree of one or more phase changes or phase transitions, the predetermined atomic valence of the precursor of the selected precursor compound' until (or in some cases through the t phase change. _ ' utilized processing conditions Any valence change may be inhibited or at least not promoted. Therefore, in accordance with one or more preferred embodiments of the present invention, the individual precursor compound or individual donor component will encounter processing conditions that promote or maintain chemical stability until the reaction is completed. The desired phase. The lithium donor or lithium source comprises lithium hydroxide, lithium carbonate, or a mixture thereof. The oxidizing agent may include lithium nitrate or nickel nitrate, or a mixture thereof. In some cases, the clock source may include or contain a can acid clock And a hydroxide clock. The first metal is given to include magnesium hydroxide, carbonic acid, oxidized town, or a mixture thereof. The second, the donor may include nickel hydroxide, sulfur self-recovery, nickel tartaric acid, oxidation record Its mixture. The 〃 π precursor compound may have any form which is convenient to be mixed in the precursor mixture. For example, the precursor mixture may include a powder mixture of each precursor compound, or a slurry of each precursor compound. Further, the precursor compound may be a hydroxide of the master batch including lithium, the first metal donor, and/or the second metal donor. The oxidant can be added to the masterbatch as needed to facilitate handling and storage prior to use. According to one or more specific examples, the precursor compound needs to have a structure which preferably promotes efficient use of the lithium metal oxide material of the present invention. Thus, the synthetic techniques of the present invention provide morphologically desirable lithium metal oxide materials. The precursor compound can have various shapes and can be converted into a material which can be coated or coated to form a composition of the electrochemical device which can be spherical. It is also possible to visualize the expectations of the end user with two or more. In order to match or suit the lithium magnesium oxide material, two shapes are provided to provide, for example, a pole. Thus, according to - or in the case of, for example, a negative body in a rechargeable electrochemical device, such as a mixture having a spherical oxyhydrin, is included herein. However, the hydrogen density of the present invention, the nickel (4) may include a high density (for example, the high-dispersion particle size method is, the paste is pre-defined or pre-selected.) Any particle size may be used. Use to produce the invention

Li is about to smuggle sangha, can be in about 2 ratios, the system 'can choose the precursor compound material Moer m ^ LixMgyNK) 2 Deyu, where 〇.1 ◊, strong ΖϋΙΓ0.1, and 0.9<x+y&lt ;1.3. In some cases, =, =t makes 〇.9<x<U and 〇〇2<y<〇〇5. In other cases, X can be approximately Ι-y. In still another specific embodiment of the present invention, LixMgyNi〇2 or ^ ton of material may have any of the following formulas::Li] πύα, by age_brain 2, ii.〇5Mg〇.02Ni〇2 . ^ Li1.05Mg〇 .〇3〇Ni02 >

Lii.osMgo^NA and LiU5Mg0.05NiO2. Thus, a precursor compound can be used in this molar ratio to provide the composition. The precursor compounds are typically pre-mixed to allow for homogeneous mixing. In still another embodiment, the material of the present invention can be crystallized by, for example, heating to facilitate the cost of the composition of the invention. The synthesis process involves mixing the precursor compounds into a substantially homogeneous mixture. The synthesis process may further comprise dividing the precursor mixture into one or more heating stages or step 1358148 to heat, for example, by two or more heat soaks in accordance with a predetermined heating pattern. The synthesis process typically promotes oxidation of the corresponding donor component, or formation of a disk oxygenate; mixing of the components, typically a meridian mixture; a bell metal oxide composition; wherein the first metal of the composition (eg, magnesium) Associated with, and a second metal (such as nickel) is associated with 3b. For example, in a lithium magnesium nickel oxide composition, the mixture can be heated to a first heating temperature and preferentially forms Ni3+ over Ni2+. According to a specific embodiment of the invention m, the first heating step or step involves heating the newly formed precursor mixture such that the formation of the oxide and/or the donor compound does not change the valence, or at least the change of the minimum, The precursor mixture is heated to a temperature of about 45 Torr in the first heating step. The first hot dip temperature can range from about 35 Torr to about 7 Torr. The heating step includes utilizing about 70 (the second hot dip temperature of TC is crystallized by hot dip. The second heat can be about 6.). Hold for about 6 hours. According to other _, the first - J π no heating stage: "s s ^ things have been knotted; Si process = temperature s hold for about 1 hour" but can be maintained for up to about 6 hours. The heat and soaking can be exposed to an oxidizing atmosphere (such as air or pure oxygen), which is high enough to promote oxides - per minute = about =: quality: combined heating The rate control is as follows; because = the number of processed f, the required relative composition, and exposure to oxygen 13 such as flute a second heating stage including increasing the temperature, sufficient to facilitate crystallization, the genus tends to associate with 33 ' The two metals tend to be in contact with each other. For example, the oxide mixture can be heated at a rate of about thief per minute, preferably about 5 ° C for the mother, or even about 2. for every minute. From the _ stream, naturally cooled to room temperature, can be carried out by the gamma. Example _ accommodating the furnace or oven The furnace can be filled with air and/or oxygen. The sintered crystalline material can be ground in any suitable grinding device. For example, a grinder equipped with a horse and a honing machine (York State: _Brillkmaun or Model ship produced and sold by Brinkmann Instruments (9) Grinding machine) 'The crystal composition is ground to have the required particle size. Other suitable grinding methods or systems include, for example, ball milling, jet milling, wet milling, hammer grinding and needle grinding. The particle size may vary, depending on the particular formulation or _. Therefore, according to one or more specific examples of the present invention, LixMgyNi〇2 is ground for about 5 minutes to form granules until an average particle size of about 2 to about 2 Å is achieved. m, and preferably from about 10 to tzm. According to one or more preferred embodiments of the present invention, the composition of the granules, χΜ1〇2, which is typically granulated, further includes a coating to further improve the first cycle efficiency. , sacred and/or safety 'even when the composition is used as a cathode material in an electrochemical device' can reduce the generation of gas. According to yet another embodiment of the invention, the =MgyNi02 particles further comprise one or more coatings, Electrode paste, can be reduced Any tendency to gel. For example, after the particles are coated, it is easy to gel in a mixture including NMP, PVDF, LixMgyNi 2 and conductive carbon (better than uncoated). In a specific example, the coating may comprise a composition of the formula LiCG〇2. The coated LixMgyNi〇2 particles may be combined with a clock solution or mixture such as, but not limited to, LiN〇3, LiOH, LiAc, Li2S〇4, Li2C. 〇3, mixed with the solution containing the name. According to the invention - or the above specific examples, the bribe may include LiN〇3, and the cobalt ruthenium may include Co(N〇3)2.6 〇. Li/c〇 The molar ratio can vary, but is typically in the range of from about 0.6 to about Μ. The Li/c〇 molar ratio is preferably from 0.95 to about 1.05, so the molar ratio of the c〇 content in the coating to the (10) content in the core layer ranges from about 〇.〇4 to about 〇.4. And better with about 〇5 〇·15. u — If there is water in a typical upper scorpion, it should be allowed to use appropriate techniques to make it = hair. For example, the mixture can be heated on a hot plate while stirring to dry in a drying oven. The precursor coating material can be heated and sintered in air using any suitable means, such as a chamber furnace, to facilitate oxidation and/or crystallization of the coating on the core layer, such as by coating at any suitable rate (such as about every minute). 5. Increasing the temperature of the precursor coated LixMgyNi〇2 and maintaining or soaking at about 45 (the temperature of rc is synthesized over about 1 hour. The second soaking temperature can be used to provide the temperature at a rate of about rc per minute, And maintained at about 7 saki for about 2 hours to promote the coating. The sintering treatment can provide a coated material with a concentration gradient structure, or near the outer surface, at or near the core layer. The region is ^=may other technology, providing a coated core material having the composition of the present invention. The rideable straight-water compound is sufficient. For example, twisting, heating at a rate of (four) degrees about U (rc for drying. Drying) Warm again and maintain the necessary length 'continued for 1 hour or more. The milk-forming or the first coating-heating rate* can be changed, in the range of == about thief per minute. The first-hot dip temperature can be = f ° This first hot dip temperature can be maintained until sufficient or required Change from about rc per minute to about every minute of the wrist. From room to room temperature. The core layer is lowered. The coated particles allow for cooling. Any halogenation can be utilized during the drying/heating/soaking process. Box or furnace 'to provide a suitable oxidizing atmosphere. ® 〇3 Sintered coating material is subjected to further processing to obtain particles with a particle size of about 8 to about. For example, the sintered coating material is more polished. In-machine, grinding for about 5 minutes. The functions and advantages of the composition and the advantages of the present invention are illustrated by the following embodiment 2, but the invention is not shown. The following test procedures were carried out in the examples. 4SJ. · Rate capability test and formation of a first continuation tree rate using coin batteries for material life testing, using clock metal as the counter electrode. Positive electrode of coin battery, Made of composite yin made according to Example 2. The electrolyte is EC/DEC (1:1) - LiPF6, 1 Μ (available from ΕΜIndustrial Co., Ltd., New York), and the separator is made of glass fiber (Fisher) Scientific Public > Division available). Battery Full charge and discharge 'rate for C/20 for first cycle efficiency measurement' This is the ratio of discharge capacity to charge capacity. Then, the battery cycles at approximately C//, 'C/2, 1C, 2C, 3C, and 5C From about 2.7 volts to about 4.2 volts. The 1C rate is defined as a discharge of about 15 mAh/g for 1 hour. Procedure 2: Life cycle test uses a coin cell for material life test. The positive electrode of the coin cell is made up of a composite cathode. Made of negative electrode made of composite anode, including intermediate such as carbon particulate graphite (MCMB 2528, 90% by weight), PVDF binder (7% by weight), and carbon black (3% by weight). Electrolyte is EC/DEC ( 1:1 ) _ LiPF6,1 Μ (available from EM Industries, Hawthorne, NY), and the partitions are made of fiberglass (available from Fisher Scientific). The battery is initially fully charged and discharged, and is cycled three times at approximately C/5 rate for deep circulation. The deep cycle consists of charging to approximately 4.2V (full charge) and discharging to approximately 2.7V (fully discharged). The battery is fully charged to approximately 4.2V (100% state of charge (SOC)) and the battery is then discharged at a current rate of approximately 1C to approximately 20% of full capacity to approximately 80% SOC. Battery recirculation discharges about 1% (to about 70% SOC)' and charges 10% (to about go% SOC) at about ic rate current, typically referred to as shallow cycle. After every 200 shallow cycles, a deep cycle is performed. This test represents the estimated useful life of the battery. Procedure 3: Area Specific Impedance (ASI) Measurement The ASI (in Ω«η2) for various starting SOC conditions is determined by the pulse discharge of the coin battery. ASI is calculated according to the following formula: ASI = A · (Δν / Ι) where Α is the electrode area, and I is the discharge current pulse at a rate of about 6C. The voltage change (Δν) is a voltage change at the time of discharge pulse. For example, when the SOC = 90%, the initial voltage is measured. The battery was discharged at a rate of 6 C and the final voltage was measured after 18 seconds. ASI is related to potential power, and for lithium-ion batteries, the power capacity is compared between materials and recipes. This is especially important for high pulse power applications. Example 1 - Synthesis Group $ A composition of LiwMgo.oMNiO2 was prepared and evaluated. The composition was prepared by dry blending of the following ingredients: - about 242.91 grams of Li(OH)2 (anhydrous fine powder, available from Sigma-Aldrich, Inc., St. Louis, Missouri, USA). - Approximately 14.79 grams of Mg(OH)2 (fine powder, available from Alfa Aesar, Waldorf, MA). Approximately 34.97 grams of LiN〇3 (crystals available from Alfa Aesar, Waldorf Assay, MA). In a 1 liter 瓮, about 940.31 grams of Ni(OH)2 (#543 high density spherical powder, available from OM Group, Cleveland, Ohio, USA), 1358148 mixed material was added. The compound was shaken and mixed in a crucible. The homogenous powder (precursor compound) was placed in an alumina crucible and sintered. It is heated to a temperature of about 5 ° C / minute to about 450 T: and maintained at about 450 ° C for about 4 hours for sintering. The temperature was then increased to about 7 cc at about 2 〇 c / minute for about 4 hours. Allow the sample to naturally cool to room temperature. The cooled sample was ground for about 5 minutes to break any coagulum. The powder material was screened through a 27-inch sieve to remove larger particles to ensure a desired 10/ζηη particle size. Figure 1 is a photograph of a scanning electron micrograph showing the morphology of a spherical core material. X-ray diffraction pattern (XRD) analysis showed that the resulting composition had phase purity and no impurities were observed. Figure 2 is a copy of the XRD pattern of the resulting composition. The xrd data shows that the resulting powder is substantially free of impurities.

Ui^MgacmNiO, ΜElectrical battery fabrication and lightning energy evaluation will be about 90% by weight of active cathode material powder prepared as described in Example 1, about 6% by weight carbon black (AB 1%, Texas Texas | 〇〇 (11 sold by Chevron Phillips Chemical Co., Ltd.), and approximately 4% by weight of K1120 binder, containing 12% PVDF (available from Kureha Chemical Co., Japan) in NMP 〇5Mg〇.〇25Ni〇2 cathode. Add nmp (N-fluorenyltetrahydropyrrolidone) to make the desired viscosity and promote mixing. The bath is in 250 ml 有 with about 50 steel balls. It was mixed by a paint shaker for about 30 minutes. The mixed slurry was coated on an aluminum foil with a micro-coating gap of about 15 Å/m, about 20/zm thick. The coating vl was dried at about 130 C for about 30 minutes. The foil is passed through a pressurized stone tooth roller, and the pressure is set to about 1 〇〇 (4) with a diameter of about 30 ,, and the dry coating 羯 is densified. The compacted dry _ _ into about 2 em 2 wafer is used as an electrode. The weight of the active material is typically about 2 〇. The wafer electrode is vacuumed and 阙 8GI is dried for about 16 hours to assemble the battery. 8 18 1358148 Group Coin battery (Hosen type #2025), using the wafer electrode as the pole. The coin battery includes a glass fiber separator containing EC/DEC (1:1) seven swollen electrolyte (available from EM Industrial Co., Hawthorne, NY) ), and Zhong 6 gold pole. All groups of cranes are in the hydrogen-filled glove box for water and oxygen content less than about 2ppm., hard battery use cycle machine / test machine (Oklahoma, USA) Fresh Ma_ is fed with f), according to Shang Wei Cheng Bu 2, capacity, efficiency, rate ability, power and circulation. The electrochemical performance of LiiG5Mg_Ni 〇 (ie 0% coating) data is listed in the table below. 3 Lil05M^Ni〇2

The gluten of the material is typically about 19 〇 mAh/g. X ϋ · Lii.osMgo.cmNiO, Thunder &

LiMgyNi02 core layer with LiCo02 coating content Mohr% first cycle efficiency % C/5 mAh/g 0% 87 203 5% 92 202 10% 89 197 15% 90 191 Specific ratio specific capacity

--- ή buried ms 胆 13⁄4 • 独 独 令 测 测 测 测 测 测 测 测 测 测 测 测 测 测 测 测 测 测A flag electrode which was densified into a shape of about 60 x 50 mm2 was prepared as described in Example 2. The active material weight on the electrode is typically about 300 mg. Like the cathode, the anode method is to apply MCMB: PVDF (93: 7) to copper red, and cut into (8) χ 5 〇 2 flag electrode. Also used to densify at 175 psii. The flag electrode was dried and dried at about 80 ° C for about 16 hours.

19 1358148 Assemble a two-electrode pouch battery. The battery consists of a dry anode and a cathode, separated by a glass-fiber separator of approximately 65 x 55 mm2. Approximately 16 ml of EC/DEC (1:1)-LiPF6, 1 Μ electrolyte was immersed in the electrode and separator and the assembly was compressed between two 70 x 60 mm2 glass plates. The entire assembly was placed in an aluminum laminate bag, approximately gOx^mm2, sealed under vacuum. ~ - All assembly operations were carried out in an argon-filled glove box with a water and oxygen content of less than about 2 ppm. The μ bag-shaped battery is charged and discharged at a current rate of about c/io, between about 4 lv and about 2.7 V, and then charged at a current rate of about C/5 to a capacity of about 18 〇 about 200 mAh/g. The battery passing through the composite cathode was disassembled in a glove box filled with argon. The composite cathode powder was removed from the aluminum current collector. The composite electrode powder, and the EC/DEC (1:1) - LiPF6, 1 Μ electrolyte, powder / electrolyte weight ratio of 1: 1, was loaded into a sealed compacted Dsc pot. DSC measurements were taken at a continuous scan rate of about 51 / min up to about 450 °C. The safety data shown in Figure 13 shows the DSC curve of 5% LiC〇02 coating material compared to UNi〇8C〇〇i5AW〇2 (CA1505N battery produced and sold by Japan TODA). The DSC curve has a sign of the chemical reaction coefficient in the deuterium reaction. tMMA: Royalized Electron Ray, "Approximately 244.42 g of Li(OH)2 (anhydrous fine powder) and about 35.18 g (crystal) were dry-blended to form a Li^NiC^ composition. The mixed material was added to about 946.15 g of Ni(OH)2 (OM Group #543 high density spherical powder) in a 1 liter 瓮. The precursor powder mixture is mixed by vibration. The precursor powder was placed in an alumina crucible and sintered. Sintering is heated to about 450 at a rate of about 5 ° C / minute. (: 'And proceed at about 450 ° C for about 4 hours. The temperature is raised to about 7 ° C at about 2 ° C / min and held for about 4 hours. 8 20 1358148 Gu Xu οσ naturally cooled to room temperature Cold grinding for about 5 minutes to break any agglomerates. The powder material was screened by the No. 270 division to remove large particles to ensure the required 10/zm particle size. XRD analysis showed that the material was pure, no obvious impurities. This powder was carried out in accordance with the procedure described in Example 2, and the results are listed in Table 2 (ie, coating). Magic: ^1Ηί〇2 battery Thunder hM can

LiNi02 core layer with specific ratio of specific capacity LiCo02 coating content J ear% first cycle efficiency C/5 mAh/g 1C mAh/g 2C mAh/g 3C mAh/g 5C mAh/g _ 〇% 89 211 192 184 178 154 5% 88 214 203 197 190 166 _ 10% 90 209 196 192 184 168 _ 15% 89 197 185 179 172 151 The data shows the effectiveness of the specific capacitance of the LiMgyNi02 electrochemical cell of the invention (see table) 1) 'Compared with the performance of typical lithium nickel oxide materials, listed the highest.

:Compared with LiCoO, the quality of the electric cell, using the LiCo〇2 (the c_5 grade produced and sold by Sakamoto Tokyo Sakamoto Chemical Industry Co., Ltd. as the active material to prepare a comparative composite cathode in the electrochemical cell. As described above, the preparation of the example is similar. The coin battery is for evaluation. The electrochemical data of this material are listed in Table 3. Table 3: LiCoO, electrochemical performance sample of the battery---_ specific ratio specific capacity first cycle efficiency C/5 mAh/g 1C mAh /g 2C mAh/g 3C mAh/g 5C mAh/g _LiCo〇2 —97 157 143 127 108 71 8 21 1358148 Ο m , 〇·〇2· 0.025. g^3, .QJ4 and 0.05) The sundries can make λλι Λ seven kinds of Lll〇5MgyNl〇2 compositions, where y is evaluated from 0.005, 〇.01, j it0·04 to 〇.05*, etc. The synthesis of these compositions was substantially similar to the procedure described in Example 1 'only the level change of Mg(〇H)2' to obtain various dopant contents.

. All samples (except y = 5% of the samples) showed a pure mouth 'no significant impurities' by XRD analysis. For the latter composition, the Lii 〇5Mg_5Ni〇2 impurity was detected to indicate the presence of mixed nickel oxide. All samples were tested electrochemically in a coin cell made in a procedure similar to that described in Example 2.

Id : LlMgvNiQ2 is different in different Mg impurity levels

LiMgyNi〇2 Specific ratio of Mg doping level tolerance First cycle efficiency % C/20 mAh/g C/5 mAh/g 1C mAh/g 2C mAh/g 3C mAh/g 5C mAh/g 0 89 227 211 192 184 178 154 0.005 90 226 210 191 183 176 166 0.01 90 223 207 191 184 178 169 0.02 89 218 204 189 183 178 169 0.025 87 214 203 192 185 180 172 0.03 87 210 199 187 181 176 167 Table 4 data representation The electrochemical performance of the LiMgyNi02 battery of the present invention, such as the specific capacitance of the 1C rate, is better than that of the LiNi 2 battery and is superior to that of the LiCo 2 battery. 1358148

f Off 7: granules coated with LiCoC^I In this example, the lithium magnesium oxynitride composition prepared substantially as described in Example ’ was coated with a lithium cobalt oxide layer. For the synthetic coating, approximately 105.55 grams of LiN〇3 (crystalline powder, available from Alfa Aesar, Inc., Huadeshan, MA, USA), and approximately 445.50 grams of Co(N03)2 · 6H20 (crystalline agglomerate 'Eight Aesar also Available for sale), play about 200-300 ml of secret water a. About 1000 g of Lii.〇5Mga〇25Ni02 powder, substantially as described in Example 添加, was added thereto. Excess water was removed by evaporation on a hot plate until the mixture became a thick slurry. The slurry was poured into an alumina crucible and sintered in the following heating form; at about 2 °C. The rate of /min is heated to about 11 ° C, heated to about 45 以 at a rate of 5 ° C / min at about U (rc for about ) hours, at about 45 (Γ (: hot dip for about i hours, Heat to about 7 ° C at a rate of about 2 C / min and hot dip at about 7 ° C for about 2 hours. * Let the finished sample be naturally cooled to room temperature. Once cooled, grind for about 5 minutes. Any condensate is broken and sieved through a 27-inch sieve. XRD analysis shows that the prepared composition has a gradient morphology, and the visible impurities of the helmet are visible from the xrd image shown in Figure 5, which is shown as 5; Ear & coated Ι^·〇5Μ§0.〇25Νί〇2. Figure 4 is a SEM micrograph of this sample showing that the coated powder composition maintains a spherical morphology of about 1 〇//m. Table 1 lists the rate capability and first cycle efficiency of Li! 〇5Mg〇.〇25Ni〇2 core material coated with different yttrium-containing LiCo〇2 coatings. Figure 6_8 shows

LlC〇〇2 coated Lil 05Mg〇〇25Ni〇2 core layer composition discharge form, respectively, having about 5 mol% coating, about 1G mol% coating and about i5 g ear % coating showing lithium magnesium nickel The composition can be applied to a layer of about 15 moles of lithium cobalt oxide and maintains about the same electrochemical performance. Figure 11 is a comparison of the samples for this sample. The gradient is increased with the amount of LiCo〇2 coating. Lil 05Mg0 () 25Ni 〇 2 material, using the method of 23 1358148 and 7 'coated about 10% and about 15% Lico 〇 2 respectively. Study the increase in the degree of asymmetry in Bragg reflection, detect the gradient coating. Especially use The peak 104 at about 44.4 degrees in 2-0 (angle) shows the asymmetry of peak 104, how it increases continuously with the amount of LiCo02 (Fig. 11). The XRD pattern in Figure 11 is 2-0. Zero position and normalization of intensity 'to compare (shown on the right side of Figure 11). · Gradient coated samples were also electrochemically rated according to Protocol 1 for rate capability and first cycle efficiency, as listed in Table i.

Example 9: Comparing LiCoO, coated Li^NiO, core layer material to synthesize a three-gradient coated Li^sNiO2 material, using 5%, 1 分别, respectively, using the methods described in Examples 4 and 7, respectively. % and 15% LiC〇〇2. The coated samples were electrochemically tested for rate capability and first cycle efficiency as described above and in the protocol. The specific capacitance results listed in Table 2 show that the lithium cobalt oxide coated clock nickel oxide compound of the present invention has better or at least equivalent performance capabilities than the uncoated compound.

Fig. 9 shows a battery ASI of Ui〇5Ni〇2 material coated with Lico(R) 2, measured according to the above procedure 3. Figure 1 shows several ASI measurements of a battery using uncoated UMgNiO2 material. As shown in Figures 9 and 1 of the state, lithium-potassium oxide-coated lithium-nickel oxide batteries have potentials that provide power efficiency, even if they are better than batteries that use uncoated lithium-nickel oxide materials. Active material, including clock nickel oxide, clock magnesium

Nickel oxide, lithium cobalt oxide coated lithium magnesium nickel oxide, =ν1〇^〇0·15αι_ο2 (CAl5〇5 battery produced and sold by Japan TODA Co., Ltd.) and ΙΧ:ο〇2 (Japan Tokyo Chemical Industry Co., Ltd. The c_5 level pool 'the capacity scalar rate of the discharge rate of ic. The first I, with the coated and uncoated clock magnesium nickel oxide of the present invention = see the use of ^, oxide (four) pool has better performance. Figure 13 (d) line shows the present invention and the application of brittle oxide coated magnesium oxide oxide material, ^ compound material in the state of charge compared to the differential sweeping volume heat record 3

24 Uncoated and uncoated materials are more thermally stable. Everyone knows that the above parameters and shapes are just a few words. (4) 5=Special specific examples of Ming. For example, the invention of the ==j system may include particles that form a convenient package and a coating/or knives, such as, but not limited to, a panel, and a t- and/or third dimension. Further, the particle size range is 2, wherein the mixture may have the first type of particles, the third type is coated with the q2-type particle size ', and the second particle, for example, the coated two-loaded 'has a second particle size, so It should be noted that the foregoing specific only two, change; material and improvement. These changes, modifications 2: I, and are within the spirit and scope of the present invention. The present invention is directed to the various features, systems, or methods, and any combination of features, systems, and/or methods, and if the system or the two are inconsistent with each other, the invention is considered to be within the scope of the invention and Fan f. Use the first and second, even the third and the first === priority, before, after, order or temporary row 25 1358148 [Simplified illustration] Figure 1 is a photomicrograph showing the invention Representative of HtNl02 - or the typical _ nickel oxide composition of the above specific examples, Figure 2 is the x-ray diffraction pattern of the composition shown in Figure 1; Figure 3 is the different discharge of the material shown in Figure 1. The discharge pattern of the rate, Fig. 4 is a photomicrograph of the photomicrograph, showing the blood-type clock cobalt oxide gradient coating of one or more specific examples represented by about 5 ΙΧ: 〇02: Ι^0·025_2 Lithium magnesium nickel oxide composition; ,, Fig. 5 is a graph of the coating composition shown in Fig. 4; Fig. 6 is a graph showing the 4th riding with a different rate of about 5 moles of the layer; And the graph of the discharge morphology of the composition having a composition content of about 1 〇 mol % coating is shown in Fig. 4; = Fig. 4 has a coating of about 15 mol% as shown in Fig. 4 a graph of the discharge morphology at different rates of the composition of the content; Figure 9 is a diagram according to the invention - or the above specific examples, 3 is an area ratio impedance curve of a LiMga^NiO2 composition having a gradient of approximately 5 mol% 〇 (: 〇〇2 gradient coating) using a is and 18 s pulse wave; FIG. 10 is a specific example according to one or more of the present invention. , according to the procedure 3 using u and 18s pulse wave, the area ratio specific impedance curve of various LiMgQ () 25Ni 〇 2 composition; Figure 11 is a specific example of one or more according to the present invention, in the Lic 〇〇 2 composition = 5 Mo Ear %, 1G molar %, and 15 mole % gradient coating content (not amplified on the right side), showing a peak shape of the χ ray diffraction pattern; • Figure 12 is the use of (8) LiNi02, (b ) LiMgNi02, (6) about 5 mol%

LiCo02 coated LiMgoobNiC^ ' and (d) CA1505N (Japan TODA Gong 26 1358148) '々 at about 1C discharge cycle, battery capacity retention rate chart; Figure 13 is (8) LiMg0025NiO2, (b) about 5 mole% LiC〇02 coated LiMg〇.〇25Ni〇2 ' and (c) TODA NCA-02 electrodes, after about 4.2V charging (100% state of charge) and immersed in the electrolyte, the differential scanning calorimetry morphology curve Figure. [Main component symbol description]

27

Claims (1)

1358148 X. Patent application scope: 1. A composition, actually LixMgyNi02, where 0.9<χ<1.3 and 0.01<y<0.1, and 0.9<x+y<1.3. 2. For example, the composition of claim 1 of the patent scope, where 0.9 < χ < 1.1. 3. For example, the composition of claim 1 of the patent scope, wherein 0.02 < y < 0.05. 4. For the composition of claim 1 of the patent scope, where x = 1.05 and y = 0.025. Φ 5. A composition comprising: a core layer of the formula LixMgyNi02, wherein 0.9<x<1.3 and 0.01<y<0.1, and 0.9<x+y<1.3; and coating on the core layer The layer is of the formula LiaCob02, where 0.7<a<1.3 and 0.9<b<1.2. 6. The composition of claim 5, wherein 0.9 < a < 1.3 & 0.9 < b < 1.2. 7. The composition of claim 5, wherein the Co: Ni molar ratio is between about 0.01 and about 0.8. m 8. The composition of claim 5, wherein 0.9 < x < 1.1 and stomach 0.02 < y < 0.05. 9. For example, the composition of claim 8 of the patent scope, where x = 1.05 and y = 0.025. 10. An electrochemical cell comprising a cathode comprising a composition of the formula LixMgyNi〇2, wherein 0.9<x<1.3 and 0.01<y<0.1, and 0.9<x+y <1,3 . 11. For an electrochemical battery according to item 10 of the patent application, wherein 0.9<χ<1.1. 12. For an electrochemical cell according to item 11 of the patent application, wherein 0.02 < y < 0.05. 28 1358148 I3. An electrochemical cell according to claim 10, wherein X = 1 〇 5 and y = 0.025. 14. An electrochemical cell comprising a cathode comprising a granule comprising a core layer of the formula LixMgyM02, wherein 09<x<13 and 〇〇1<y<〇i, and 〇9<x+y<l_3' and The coating on the core layer is of the formula UaC〇b〇2 <1.3 and 0.9<b<1.2. ' 15. As for the electrochemical battery of claim 14th, i and o.〇2<y<a〇5, and 〇.9<a<13, and 〇9<1)', 匕 〆 〆 1.1 Η1 二ft? The electrochemical cell of the 15th patent range, where x=1.〇5 and y=0.025' and a=1, and b=〇.〇25. 17. A method of making a composition comprising: a mixture comprising a source, a source of a source, and a source of nickel; and sintering the mixed slag in an oxidizing atmosphere at a temperature and for a time sufficient to crystallize the mixture into a UxMgyNi〇2_ Where G9<x<H==;<0.1, and 0.9<x+y<L3. Mg (^ is the method of preparation of the 17th item, wherein the source includes the) lithium source includes LlN〇3 and Li〇H, and the nickel source includes the Ni (〇H) 2 ^ range of the 17th method, The temperature is between about 400 and the first soaking temperature of each H-shoot (10) mixture, on the about side. C and 500 21. The method of applying the patent scope 帛2〇, the first soaking temperature, after about 4 hours. 〇匕 维持 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. 22. The enthalpy rate is increased to the first - soaked melon sound 2, and the mouth is also mixed between 9 ° ° C. ", the first time, the package, the degree of the package, between about 00 (TC and 23. For example, the hiding of the 22nd item of the claim, the sintering also includes maintaining the second soaking temperature of 90) for about 4 hours. a method for preparing coated particles, comprising the steps of: providing a first mixture of compounds, including a lithium source, a magnesium source, and a nickel source, and sintering the first mixture in an oxidizing atmosphere at a first temperature and passing through the first One, between, is sufficient to crystallize the first mixture into a core particle of the formula UxMgyNi〇2, where 〇.9<χ<1·3 and 0.01<y<0> and 〇91<x+y<13; And the knee bath coats the core particles with the second mixture, including the compound, containing lithium and cobalt, and sputum, and the core particles are sintered at the second temperature, and the second period is sufficient to coat the coating day, /, It is LiaCob〇2, where 〇.7<a<1.3 and 〇9<b<l 2 . 25. The method of claim 24, wherein 〇9<χ<ι> and ^2<y< 0.05, and 〇9<a<13, and 〇9<b<i2. Society, 26=Please refer to the method of Article 24 of the patent scope, in which the first mixture is burned ^ - the mixture is heated to a first soaking temperature of 500 ° C at a rate of about 5 Torr per minute, and the second mixture is heated to a second soaking temperature per L, at about 00 (rc and 90 (the gate of the TC, The method of claim 26, wherein the first compound has a first soaking temperature for about 1 hour to about 6 hours, and the 筮-bubble temperature is maintained for about 丨 hours to about 8 hours. 28. The method of claim 24, wherein the coating comprises: - coating the coated core particles at about 2 per minute. 2: temperature, between about 1 and about rc. To the second change to the bubble knot, and then the particle '.352 = grain bubble temperature, _ WC (four) · / / area to the fourth dip 31. As in the patent application scope 3, the method of 1 knot 'including maintenance The fourth soaking temperature is about 1 hour, and the core is burned. 32. According to the method of claim 24, wherein the coated core pellet is sintered, the IJ58148 knot is included, and the coated core pellet is about every minute. The temperature of the bubble, between _ _ 〇 C and (four) ot. The sheep is heated to the fifth seven 33. If Shen Qing patent range of the first item, And including maintaining the fifth soaking temperature about (1), the core granules coated in the crucible 34. As claimed in the patent range 24 m_) 2, the lithium source includes Li 'where the source includes. LlUH and the nickel source includes Ni (OH) 2 35. A type of particle comprising a core material, wherein Mg and Li are mainly at a surname 曰; S has a composition 3b of the formula 1^Μ@02, and 0.01 <y<〇ff,. .曰曰上上3a' Ni is mainly in the middle of crystallography. The weight of the patent scope of the 37th of the teaching, in which the coating accounts for about 3 〇 31