TW200843165A - Nanoscale ion storage materials - Google Patents

Abstract

Nanoscale ion storage materials are provided that exhibit unique properties measurably distinct from their larger scale counterparts. For example, the nanoscale materials can exhibit increased electronic conductivity, improved electromechanical stability, increased rate of intercalation, and/or an extended range of solid solution. Useful nanoscale materials include alkaline transition metal phosphates, such as LiMPO4, where M is one or more transition metals. The nanoscale ion storage materials are useful for producing devices such as high energy and high power storage batteries, battery-capacitor hybrid devices, and high rate electrochromic devices.

Description

200843165 27144pif IX. INSTRUCTIONS: FIELD OF THE INVENTION The field of the invention includes ion storage materials and, in particular, nanoscale ion storage materials suitable for use in devices such as batteries. [Prior Art] Ion storage materials are widely used in batteries and other electrochemical devices. A variety of ion storage materials are known, including alkali transition metal phosphates. The #-type compound typically has a crystal specific gravity value of from about 3 g/cm to about 5 g/cm and can be crystallized in a variety of structural types. Examples include olivine (AxMX〇4), NASICON (Ax(M,,M))2(X〇4)3), V〇P〇4,

An ordered or partially disordered structure of the LiVP04F, LiFe(P2〇7) or Fe4(P207)3 structure type, wherein A is an alkali ion and ruthenium, osmium, and iridium are metals. Many of these compounds have lower electron conductivity and ionic conductivity, which is lower than the ideal value for electrochemical applications. Many of these compounds have a limited range of soluble solutions. For example, there is a literature that states that LiFep〇4 has a very limited range of solid solutions at room temperature. "Nano crystals, ion storage materials have been reported in the literature. For example, Pr〇Sini et al. in "A New Synthetic Route for Preparing LiFeP04 with Enhanced Electrochemical Performance; * J. defeat & c., 149: A886_A89 ( (2〇〇2) describes LiFep〇4 as a nanocrystal having a specific surface area of 8.95 m ^ 2 /g. However, although these materials have been slightly improved, their scale is not large enough to have substantially different properties compared to their larger scale corresponding conventional ion storage materials (eg, approximate theoretical capacity at a high speed of 5C 200843165) 27144pif (near-theoretical capacity ) ° [Invention] A nanoscale ion storage material is provided that exhibits properties that are significantly different from their larger scale corresponding materials. For example, the disclosed nanoscale materials can exhibit increased electronic yield, improved electrical stability, increased intrusion rate, and expanded solid solution range. Acid practice, providing a clock transition metal phosphorus id4 It used as an ion-missing material, including at least two coexisting phases 'including a rich clock (-) phase, of which two phases are between _ ears = 77) The difference in the percentage of hoarding of Wuxi stalk A is less than about 6.5%. Two 5.75% of the salt material between the phases, in one or more embodiments. The two existing phases are crystalline, and the transition metal sulphate material has at least two cell boundaries of at least two of the unit cells of J. In one or more embodiments, the difference in the parameters is less than 3%. The difference is less than 4.7%, or the lattice parameter of all the main axes of Xiangyang I, the lattice parameter: any two of the two lithium transition metal phosphates = the lattice parameter, the multiplication = the difference is less than L6%, or any The maximum of 4 ^ of the two main lattice parameters is 1.55%, or the sum of any two main t products, U%, or

=5 %, or the difference between the lattice parameters of all the main 2 kg main crystals of the unit cell is smaller than the lattice of all the main axes = the difference of the parameters is less than 4.0%, or the crystal is - the difference between the two partial fragrant numbers is less than H 6 200843165 27144pif The difference between the sample product parameters is less than h35%, or the difference between the minimum product of any two crystal parameters is less than 12%, or the difference between the minimum product of any two main lattice parameters is less than 1.0% . In one or more embodiments, the difference between the maximum product of the lattice parameters of any two major axes of the lithium transition metal phosphate material is greater than 4.7%, or the difference between the maximum products of the parameters of any two major axes is greater than 48. The difference between the maximum product of %, or the crystal parameters of any two spindles, is greater than 4.85%. According to the Bayesian example, the nanoscale material has a plane formed by any crystallographic major axis that is measured to have an area change of less than about 1.6% or less than about h5% or less than about 14%. According to another embodiment, the plane developed by any of the crystal major axes does not have a strain of more than 8% or 75% or 6%. In one or more embodiments, the lithium transition metal phosphate material has a specific surface area of at least about 20 square meters per gram or at least about 35 square meters per gram or at least about 50 square meters per gram. In one or more embodiments, the lithium transition metal phosphate material is selected from the group consisting of: sapphire (AxMP〇4), NASICON (Ax(M', M") 2 (p〇 4) 3), VOP〇4, Livp〇4F, ❿ 办) or FeWPsO7) 3 ordered or partially disordered structure, where A is an alkali ion and Μ, M, and M" are transition metals. In one or more embodiments, the lithium transition metal phthalate material has a total composition Lii_xMP〇4, wherein μ comprises at least one first column selected from the group consisting of Ti, V, Cr, Μ, Fe, Co, and Ni Transition metal, and where X is used in the range of 〇 to 1. Μ can include; pe. The material may exhibit a solid solution in the range of 0 < χ < 0·3, or a stable solid solution in the composition range of 〇 between 〇 and 7 200843165 27144pif less than about 0·15, or The material exhibits a stable solid solution of X between 〇 and at least about 〇〇7 or within a composition range between 〇 and at least about 0.05, at room temperature (22-25 〇). The material may also exhibit a stable solid solution at low lithium contents; for example, where 1 < χ < 〇 · 8, or 1 < χ < 0·9, or ι < χ < 〇. In one or more embodiments, the lithium-rich transition metal phosphate phase has a composition of LiyMP〇4 and the clock transition metallosilicate phase has a composition • Ul-xMP〇4, wherein at room temperature (25 ° C) 0 .〇2<y<〇.2 and 〇.〇2>x>〇.3. In one or more embodiments, the material may exhibit a solid solution within the composition range of <χ<〇 ΐ5 and 0.02<y<0.10. In one or more embodiments, the solid solution of the lithium transition metal phosphate material comprises a ratio of the range of lithium composition defined by y + 。.

In one or more embodiments, the lithium transition metal phosphate material has a total composition, wherein μ comprises at least one first-column transition metal selected from the group consisting of τι, v, Cr, Μη, Fe, Co, and Ni, Its _ is x to 1 and z can be positive or negative. Μ includes Fe, z is between about 0^15 and -0.15. The material may exhibit a solid solution in the range of 〇<χ<〇15, or a stable solid solution in which the material exhibits a composition range between 〇 and at least about 〇〇5, or the material is at room temperature (22-25. 〇 shows a stable solid solution in the composition range between 〇 and at least about 〇·〇7. The material can also exhibit solid solution in the lithium deficiency scheme, for example, where xg0. 8, x^0.9, or x^〇95 〇S In one or more embodiments, the lithium transition metal phthalate material is in the form of a group selected from the group consisting of particles, aggregated particles, fibers, and coatings. 27144pif In one or more embodiments, the form has an average minimum cross-section of about 75 nanometers or less, or about 60 nanometers or less, or about 45 nanometers or less. In one embodiment, the lithium transition metal sulphate material is in the form of dispersed or aggregated particles, and the average crystallite size determined by X-ray diffraction is less than 800 nanometers, or less than about 600 nanometers, or less than about 500 nanometers. Or less than about 300 nm. In one or more embodiments, the form contains less than 3% by weight In substantially one or more embodiments, the lithium transition metal phosphate material is crystalline or amorphous. In one aspect of the invention, the cathode comprises a lithium transition metal phosphate material, for example, having a lithium transition metal phosphate material having a total composition of Ui_xMp〇4, wherein the lanthanum comprises at least one first transition metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, and Ni, and wherein X is used In the range of 0 to 1. The material may exhibit a solid solution in the range of 〇<χ<〇·3 or in the range of 0 < χ <0·15. An electrochemical cell containing the electrode is also provided. In one aspect, a nanoscale crystalline lithium transition metal sate is provided which becomes disordered after de-clocking or liquefaction, having a specific surface area of at least about 25 square meters per gram. In certain embodiments Forming a lithium deficient lithium transition metal phosphate. In another aspect of the invention, a transition metal sulphate in a lithium-defidem solid solution is provided, which is below 15 ° C The temperature is formed after lithiation, having at least about .25 Specific surface area of square meters / gram. 200843165 27144pif stone knot lithium transition metal sulphate for the order of the order of the first order of the order of the order of the sapphire or the M1 locus, or ..., see in order Lithium or Mi at the sapphire. The other sample towel provides a chain transition metal phosphate, 1 === 匕 匕 保留 保留 此 保留 保留 。 。 。 HI HI HI HI HI HI HI HI HI HI HI HI HI HI HI The battery contains a cathode electrode, an electrolyte that is in contact with the anode and the cathode and is separated, a cathode current collector H that is in electrical communication with the cathode, and an anode current collector that is in electrical communication with the anode. ^Thunder pool at least (four) G watt hour / kg (10) watts / liter) two exhibitions ^ at least about watt / kg (10) watts / liter) of the specific power, and the situation 'at at least about 90 watts / kg (18 watts watt hour / liters under the exhibition 2 at least about 13 GG watt / kg (鸠 / liter) of the specific power. ^ In some embodiments, the battery cathode comprises a nanoscale alkali transition metal phosphate having a specific surface area of at least about 25 square meters per gram. In some embodiments, the cathode comprises particles, fibers or coatings of nanoscale scale transition gold (tetra) acid salts having an average cross-sectional dimension of about 75 nanometers or less. In a particular embodiment, the cathode comprises a composition of the formula ,^_χΜΡ〇4, wherein M is one or more transition metals. The composition has a specific surface area of at least about 25 square meters per gram and exhibits a stable solid solution of X between 〇 and at least about 〇·〇3, and in some embodiments, X For a maximum of about 15. In a particular embodiment, the cathode comprises particles, fibers or coatings of the composition Lii x Mp 〇 4 wherein Μ is one or more transition metals. The particles, fibers 200843165 27144pif or coating have an average minimum cross-sectional dimension of about 75 nanometers or less, and the composition exhibits X between 〇 and at least the fishing rod at room temperature (22-25 ° C) A stable solid solution within the composition range between 3, and in some embodiments, X is at most 0.15. In one aspect, a lithium transition metal phosphate powder having a specific surface area of at least 15 square meters per gram and a lithium content ratio at room temperature (23. 〇) in a bulk form or a specific surface area less than about The lithium transition metal phosphate having the same composition prepared by the 1 〇 square meter/gram powder φ final form has a lithium content of at least 2 mol%. However, it should be understood that the powder can be used at any temperature' and the difference in bell content is determined relative to room temperature. In one or more embodiments, the powder has a specific surface area of at least 2 square meters per gram, or at least 25 square meters per gram, or at least 3 square meters per gram. In one or more embodiments, the lithium transition metal phosphate has a sapphire structure. _ In one or more embodiments, the lithium transition metal phosphate has a composition

Li^MPCU, wherein Μ is one or more first column transition metals, and may be, for example, at least Fe. In one aspect, a lithium iron phosphate composition for forming a single crystal phase of an olivine structure at room temperature is provided having a solid solution of LiixFeP〇4 wherein X is greater than 0.01. In one or more embodiments, X is greater than 0.02, or greater than 〇〇3, or greater than 0.04, or greater than 0.05, or greater than 〇〇6, or greater than 〇〇7, or greater than 〇·〇8, or greater than 〇· 〇9 or greater than 〇.1〇. 200843165 27144pif In one or more embodiments, the lithium iron phosphate has greater than 15 square meters per gram, or greater than 20 square meters per gram, or greater than 25 square meters per gram, or greater than 30 square meters / The specific surface area of grams. In a wicked sample, a minute iron phosphate composition is provided which has an olivine structure of a single crystal phase and a solid solution of LiyFeP04 at room temperature, wherein y is greater than 〇.〇1. In one or more embodiments, y is greater than 0·02, or greater than 〇〇3, or greater than 0.04' or greater than 〇·〇5, or greater than 0 06, or greater than Q Qy, bite greater than 0.08, or greater than 〇· 〇9 or greater than 〇.1〇. In one or more embodiments, the lithium iron phosphate has greater than 15 square meters per gram, or greater than 20 square meters per gram, or greater than 25 square meters per gram, or greater than 30 square meters per gram. Specific surface area. In one aspect, a lithium transition metal phosphate compound is provided, characterized in that 'the compound is at a constant potential when used as a lithium storage electrode in a counter-electrode (je) is a standard packaged battery of a bell metal In the potentiostatic intermittent titration (ΡΠΤ) program, the charging current is continuously reduced after charging at a constant overpotential of the open circuit voltage of 50 mV, and the open circuit voltage is charged to 5〇% of the charging state. The state of charge is measured and maintained for at least 12 hours. In one or more embodiments, the open circuit voltage is measured at 25 〇 under charge to 50% state of charge and held for at least 12 hours. In various embodiments, the open circuit voltage is in the range of about _2 〇 〇 to about %, such as 55. (:, or 45. (:, or 35X:, or 15. 〇, or 5 ° C , or 〇 ° C, or - KTC, or _2 〇. The 〇 is charged to 5 〇 % of the charge 12 200843165 27344 pif state and is measured after at least 12 hours. In - or more embodiments, the compound Lithium transition metal phosphate Li^MPC^, where] VI One or more first-column transition metals and X having a value between 0 and 1. In one or more embodiments, the lithium transition metal sulphate has a sacrificial structure. In one or more embodiments The compound is Lil-xFeP〇4, wherein Μ is one or more first column transition metals and X has a value between 0 and 1. In another aspect, a lithium transition metal phosphate compound is provided, It is characterized in that, when it is used as a storage clock in a standard electrochemical cell in which the opposite electrode is lithium metal, the compound is in the constant potential intermittent titration (ρΙΤΤ) procedure in the open circuit of the battery, M 5G millivolts. After the discharge at the superpotential, the pit is charged to the temperature of the cathode. After 12 hours, the temperature is measured. The open circuit voltage is about _ Cong to about hunger or 5t, or 〇t, or, / / or Pit, or pit, or hungry state and maintained for at least 12 hours after charging to 50% charge in one or more embodiments, 'salt LikMPCU, where M ^ / the compound is lithium transition metal phosphate A value between 0 and 1: one or more first-column transition metals and X with 200843165 27144pif in one or In one embodiment, the lithium transition metal phosphate has a sapphire structure. In one or more embodiments, the compound is LiixFep 〇 4, wherein Μ is or a plurality of first column transition metals and X has a 〇 Between 1

The method of "storing power storage 3 includes charging a battery according to - or a plurality of embodiments at a rate of at least 2 C, the c rate being an average c-rate of a current applied for a period of at least 5 seconds. Or a plurality of embodiments, the c rate is an average c rate of current applied for at least (7) seconds or at least 20 seconds or at least 30 seconds. The method of ageing and transmitting electrical energy includes making a according to - or a plurality of embodiments f&quot The battery is charged at at least a C rate and discharged at a rate of at least 2 C. - In - or in various embodiments, the method includes causing at least one of the lithium batteries according to one or more of the examples Redundant, or at least iqc, or at least 15C, or at least 20C c rate, or at least 3〇c, or at least a batch C rate or a C rate of at least 50C. The method of apricot includes The battery is charged according to one or more batteries at a rate of at least 5 C up to at least 50 C. The method includes discharging at a rate ranging from at least 5 C up to 50 C. 14 200843165 27144pif : [Implementation] Providing Nai Meter-scale ion storage materials and devices using such materials, such as batteries. It has been unexpectedly discovered that ion storage materials having sufficiently small dimensions and correspondingly high surface area to volume ratio or specific surface area provide corresponding to their conventional coarse crystals. Different physical properties of the material. In detail, although the above two are similar in total structure such as crystal structure type and basic atomic arrangement, after the completion of the system or the use of the system, the nanoscale material is composed and structurally The coarse-grained materials are different, and the nanoscale materials provide better electrochemical performance and performance than the coarse-grained materials. Due to the nanoscale material, such as the diameter of the equiaxed particles, the diameter or thinness of the nanorods P- or three-dimensionally small enough to have different deficiencies, thermodynamics, and mechanical properties. Nanoscale ion storage materials according to two embodiments as described herein for use in primary or primary animal batteries It has excellent electrochemical performance. The nanometer-scale materials especially provide a very high rate performance. The ratio of the inherent charging capacity to the energy density is large. The nature can be in the following states: 二 + · Preparation of the two states, heat balance or partial heat balance (for example, ::: 埶., learning device (including accommodating or assembly and used as a bipolar oximeter) Rechargeable.·Discharge cycle Nanoscale ion storage material can be the stress generated on the inner surface of the gentleman's clam or near the surface. “The size of the free surface or dimension is the free surface or inner surface of the material^ 15 200843165 27144pif

For a single crystallite or amorphous heterodule, the free surface defines the cross-sectional dimension that determines the nanoscale effect. For a particle comprising a plurality of crystallites, the free surface can also define a cross-sectional dimension, and if the dimensions described above are less than the dimensions described below, the rider has nanoscale properties. The size of the entire particle or aggregate can exceed these cross-sectional dimensions, but is the crystallite in the aggregate still? The cross-sectional dimension can be small enough to provide nanoscale properties. The above-described domain dimension is defined by the inner surface of the cluster (e.g., grain boundaries) and the spacing of the filaments. These materials are suitable for use in electrochemical devices where the towel crystallites have nanoscale properties and the #nanoscale material has at least a portion of the electrolyte phase accessible to the outer surface. “Unlike the simple U-information scale effects previously recognized in the art of battery materials, the nanoscale materials described herein are inherently different from larger-scale materials in thermal, mechanical, and academic terms. For example, the rate performance of the electrode material is at least partially limited to the solid state diffusion of ions in the storage compound. In such cases, the particles used or the thin film of the parent (in the case of a thin film battery) may be added. This is because, in terms of a fixed transmission coefficient or diffusion coefficient, the ratio between ^k is shorter and the charge/discharge rate is correspondingly faster. Although in the field of batteries, it is well known to those skilled in the art that this simple particle size effect is known (see, for example, Patent No. 5,910,382 is directed to the electrode active material LiFeP〇4; and Zhang et al., s〇Hd Μ-171:2 is called (=004) 'is about LlMn2〇4), but there is hardly any mention of scale reduction. The material has fundamental changes in other physical properties. ' 16 200843165 27l44pif As another example, the transmission in an electrochemical system is limited by the surface reaction rate. It has a finer particle size and corresponding Larger surface area materials have a larger area available for surface reaction. This simple relationship also does not mention fundamental changes in physical properties that occur at a particular scale. However, in addition to simple changes in available surface area, small scale materials Surface or interfacial chemistry can vary due to its size, potentially resulting in a fundamental improvement in the rate of surface reaction that is beneficial for rate capability (see, for example, Chiang, "Introduction and % 0verview: Physical Properties of Nanostmctured Materials,,, J. Electroceramics , 1:205 (1997), discusses the unexpected difference between nanoscale materials and their coarse counterparts, contrary to the expected differences based on well-known scale laws.

As described in more detail below, for ion storage materials based on alkali transition metal phosphates, we have discovered unique behaviors and compositions at the nanometer scale. Examples include olivine (AxMX04), NASICON (Ax(]Vr,M")2(X04)3), V0P04, LiW〇4F, LiFe(P2〇7) or %Fe4(P2〇7)3 A rice-scale ordered or partially disordered structure in which A is an alkali ion and M, m, and M are metals. When prepared in a conventional manner, many of these compounds have lower electron conductivity and alkali ion conduction. The rate, for electrochemical applications, benefits from its properties in the nanoscale state. In one or more embodiments, the nanoscale ion storage material has a chemical formula L1MPO4, wherein One or more transition metals. In certain embodiments, the 'nanoscale material is an ordered olivine (Ι^_χΜΧ04), wherein Μ is one or more of v, Cr, Μ, Fe, Co, and Ni, in lithium Insertion and 17 200843165 27144pif special properties can be obtained by increasing the amount of materials stored in the library. Based on the scientific principles implied by the behavior, the L'FeP〇4:B==nai characteristics are demonstrated in this paper. - under no scale, the material can be displayed without doping

In other embodiments, there are some lf consistent _ t at the Μ position, and in the Fe recording, the third generation transition of at least one selected from the group consisting of Ti, v, and Cr 4 Metal, where 60 and Ni are positive or negative. X is 〗 〖 and 2 can be material = Fe Ζ 介 _ 〇, between 15 m5 : No, <X<0.15 solid solution in the composition range. The nanometer-scale Phosphorus clock of the particle size of the iron is separated from the transmission electron microscopy image. See the transmission of Figure 23;; the wild and the two see the wild as the -, that is, the distribution of these elements to distinguish the surplus phase or particle. One or the other of the other materials may have properties different from those of the larger scale corresponding materials. For example, a solid solution non-stoichiometric with a coarse-grained material, a meter-scale material, and a larger range of solids, etc., 2008.13165 27144pif 』0,1,1011 nonstc)iehi deleted try), that is, retaining higher defect-containing properties It is measured by the usual knowledge library storage and chemical methods in the technical field to which the present invention pertains. When nanoscale ions are used, such as batteries or other electrochemical devices used as electrodes in the ancient charge μ = m scale _ compared to the neat lining storage material provides higher charge storage at the same charge or discharge rate. The nanoscale dimensions of the benefits described herein can be recognized by (10)eI>. Based on the following examples of the silk of the cap, the nanoscale and related 1/, the size dependence of the ion-immobilized compound, the non-stoichiometric can measure the gram of the heart = Φ 〇 c - the use of BE butyl specific surface area = == for example at least about 3. Square meters / 2 less than about 45 square grams, at least about 40 square meters / gram, as expected. Such as the 'gram or at least about 7 square meters of square meters known as Bruno-two people ET method" refers to the method of familiar with powder characterization techniques, 1 in 1 802 inch (BmnaUer, Emmett and Teller) illusion m mesh 1, (such as N2) at a certain temperature (such as 77 gas coverage rate ^ ^ surface] of the total amount of agglomerated carcass per unit area of the condensation sample. When releasing, the measured value of the calculated area and the known material specific gravity can be measured. If the material is of equal size, the ball is opened for 3 jobs and the spherical particle size is used for measuring the surface area. 19 200843165 27144pif II In the following axis, when the approximation material of the number average or average particle size is crystallization, the micro-eye: close. Further, when the invention is well known, the X-ray U plus J method 2: can be familiar with the technology 〇m' b, ^ 7x7177 The average diameter of the two. In some cases about 60 nm or not less or less, such as about 7 〇 nanometer or less, about 40 metre, or more, = 5G nano or more Small, about 45 nm or less, too small, or about 35 nm or less. Section two St:, cross-sectional size Here, the straight line is the straight line of the edge; Separate the centroid of the object (centered material can be extruded into a granular material, false, spherical shape, equivalent spherical particles for very thin but continuous film or:: two::: inch. Another - aspect 'path) is about small, also The size of the film can be obtained, the thickness of the film or the straightness of the fiber, etc. (less than 4 士 '2 f equivalent spherical particle size may not be enough to define, the height is not = inch =, the material will show special properties ). Product Possible - The value mentioned is large: but = still brother can be: 20 200843165 27144pif The smallest feature size of the nature of the described Nylon scale. For example, if the particles in the sample are homogeneous (for example, if the new size, the average size and aspect ratio of the rice rod or nanosheet are known, or even

The specific surface area of the specific surface area can be calculated from the particle shape of the Bikone. However, in the case of at least the surface of the granules, the nanoscale behavior can be observed if the Tit cross-sectional dimension of the powder, that is, the mean-average number is provided. The cross-sectional dimension of about Γ太^ is about 75 nm or less, for example, about 45 I, or 60 nanometers or less, about 50 nm or less, ten, ten or less, About 40 nm or less, or about 35 nm or less. =, can be measured by the method of rural production, including direct measurement by transmission or secondary micro-atomism. In this context, the initial dimensions are dimensioned by adsorbing a gas onto the exposed surface of the material. In the case of a substantially complete *, the day of the day, the size of the primary particle is the aggregate =. In the case of 7L fully dispersed individual crystallites, the primary particle size is a micro-size. In the case where the particles are joined as a sintered mesh or a porous assembly of particles, the thickness of the primary particle scale branch or the average spacing between the micropores leading to the outside of the assembly. In the case of agglomerated powders, the polyxides may have an average crystallite size of less than about - nanometer, or less than about - nanometer, or small nanometers, or less than about 3 nanometers. In some embodiments, the 'nanoscale material is a film or coating, including a coating on any of the particles' wherein the film or coating has about 1 nanometer or less 21 200843165 27144pif 45 Meters or less, about 40 nanometers: 2 small, about 50 nanometers or less, about 0.01 thickness of film or coating; method 1 or about 35 nm or less. 3 or other can be used to observe the film coating:: cut: including transmission electrons. Knowing, cross-section of the microscopy method in some embodiments, by conventional grinding) to reduce the particle size to the inch reduction method (such as the non-meter scale ion library material. Thus, as illustrated in the examples below, the method can be used for energy consumption of two degrees. Materials for the state include, but are not limited to, synthetic nanoscale wet chemical methods (such as co-precipitation = __ reaction, a method of combining, by using a homogenization, a mechanochemical reaction, or minimizing (to avoid particle coarsening) to form a crystallization temperature phase (also tending to coarsen the particles) Nanoscale materials. Excessive experiments can be performed according to special conditions without the need for those skilled in the art. σ衣知' In some embodiments, prepared by non-planar reaction or thermochemical method to dissolve The disordered increase of the chemist's shirt and the nature of the four-fold increase of the dopant' is because the material is synthesized in ^^etastable staterp, or because the kmetlcpathway to the final product is different from the conventional high-temperature process. The movement is essentially under the secret of electrochemistry In the Renaissance scale form: 2 22 200843165 27l44pif sequence and provides the benefits as described herein. Before obtaining the experimental results of the present invention, it is not known whether the nanoscale heterotic storage material will exhibit compared to its coarse crystal corresponding material. Fundamentally different physical properties 'I do not know which measurable physical properties will be different or what the dimensions of the difference can be achieved. Useful and advantageous features of nanoscale ion storage materials according to certain embodiments include (but not Limited to the following situations.

The material may be due to the presence of a higher concentration of mixed valence transition metal chickens in the solid solution, or electronic structure changes associated with the closer spacing between atomic processes providing higher electron carrier mobility, or both The electron conductivity of the increase is shown. The improved conductivity will typically have a value greater than about 1 〇-Siemens/cm (S/Cm). The material may have improved machine stability such as improved crack resistance due to its use as a phase change in the storage electrode during which it inhibits or retards. This improved electromechanical stability allows the material and the electrophysical material to be made higher in electrical power and longer in life. When the electrochemical cycle leads, the material can not exhibit a smaller molar difference between the phases, and the insertion and de-intercalation contribute to easier transformation. In the sub-time, the nanoscale (4) other things outside the particle or disorder 2::: = two _ cell wide particles (assuming each - unit cell image; 23 200843165 27) 44pif units) can have 1% no Order and flatten the given diffusion channel. Since it can be blocked from two 3 == order atom blocking 2 scattered or diffused out of the particle is almost no = the same degree of disorder is much larger than the shirt ^ ~ Huan, the pair has a partial channel. It can be measured by nanometer scale 2; it will stop entering and exiting large (for example, the extra disorder of the battery in the battery will transmit ions to the greater than ==

The storage is in the range of charge ion composition at higher charge and discharge rates, as described in the nanoscale scales corresponding to the same shots. At least one = = medium temperature, compared with the coarse crystal compound, the nanometer 匕: two =: the weight state exists. If it has been embedded in many ions: it is very embarrassing. _ Stoichiometry for Improved Ion and Electron Transport The present invention provides a nanocrystalline composition that is 'similar to a nominal 1 曰' before a given temperature group is red or two or more. The bulk crystal or coarse powder has a broader solid solution or defect, especially for LilxFepc>4, which is described in detail, and 'which should be apparent to those skilled in the art, for other ion storage. Similar results will be provided for the material. t Application As a non-limiting example, the conventional compound Lil xFep04 is known to exhibit a negligible solid solution non-stoichiometric x at room temperature, according to some publication 1 of about 0.002 (Delacourt et al., "Tw0-Phase vs · one_phase 24 200843165 27144pif

Li+ extraction/insertion mechanisms in olivine-type materials,'' Summary-200 (Abstract 200), 207th Meeting of The Electrochemical Society, Quebec City, CA, May 15-20, 2005 ;Delacourt et al,

The existence of a temperature-driven solid

LixFeP04 for 0 < x > l/5 Nature Materials^ 4:254-260 (2005)), in another publication, x is about 0.0475 (v·srinivasan anti]·Nwmm, Journal of the Electrochemical Society, 151 ·Α1517-Al529 (2004))' and in another publication, x is about 0.038 (A· Yamada, Η·Koizumi, Ν·Sonoyama and R· Kanno,

Electrochemical and Solid State Letters, 8: A409-A413 (2005)). In the decarburization compound Liyj?ej>〇4 which coexists with LUePO4, the allowable lithium concentration is even smaller. The characteristics are illustrated in the composition-temperature phase diagram of UFeKVFePQ4, which is not shown in Figure 3A. The composition of the phase with different bells = acid iron will vary with temperature, and at high temperatures, in the case of ancient times, most of the eight-part solids are stored in a wider range of clock concentrations. In general, _ is not used in the middle of the _ and in practical applications ... back to the temperature, for example less than about 100. Hey. Otherwise, what we mean is about _L unless otherwise stated. 〇〇C below and usually room temperature (22-25. The phase diagram in Figure 3A below shows that the temperature range is limited. Figure 3B shows the ion storage w port> the grain dry contour curve, and the proof The illustrative voltage, the group exists in the entire surface of the hand into a two-phase system. In the study ^ 25 200843165 27144pif + 'high stoichiometry by breaking down the clock composition into two substances === chemical composition of the compound Compounding " 4, to show the lack of solid solution non-stoichiometry. The two compounds due to the side microcrystal = stoichiometric uFH electron material rate. In the almost metamorphic position, the scatter coefficient may also be extremely low.曰曰 l square mu' ratio table (four) (by the law method _ greater than about 20 too "gram in the reading - more than about 30 square meters / gram of not meters,, mouth crystal Li" _xFeP 〇 4 and; [jf ρ〇 is one of X (and y). On, /...4 is not many times larger than the known compound, not at the temperature, UF p〇7 exhibits 0.05, 0.07, (U0, 〇15, Nw can be expanded by X or 0 1 u or even larger, and "0.〇5

Li pIpO ^ ^ ^^i^^Li, xFeP〇4 body. L 4B 4曰r: A significant solid solution curve 存在 exists at a temperature of less than about 50C. *=The material is transferred to the difficult voltage-composition. The flat area with significantly smaller Ff and j indicates that the two-phase system has a limited range. The slanting of the squadron is the solid solution of the two endmembers of the CCP. This idiom is the Lii_xFep〇 mountain - a nicknamed LiyFeP〇4 has a large tender X' and is in J With a large lithium excess y, the two coexisting fl LiFeP〇4^FeP0^ 0 ® ^ ^ t> ib dimers include larger non-stoichiometric turns. Higher child. ^ indicates a larger number at each point in the two-phase zone. 26 200843165 27144pif

Fe2 and Ff's Feng Shuang Office inlaid with a large amount of electronic conductivity. In addition, the ability to capture: the pair of songs: f can be used, and the uneven two-phase discharge is a difficult or more expensive. q[The material of the curve is used and the ion transmission rate can be improved by the battery technology ====== and f has been found by the skilled person to improve the transfer of the metal salt compound at n : s - fixed solid solution (lithium concentration), non-dimensional element in the material of the invention, not in the material For each component, the mouth is in the same phase as ρ χ * and the other is applicable to the r energy of the constituent system and also affects the disorder of the atomic hierarchy. =: under the _ and M2 money L;:, ri, in the order of the 撖 石 stone structure in the Li 々 F (four) nanoscale material will change (originally only by the order or ~ Ll 舆 Fe cation in two There can be no bits between the sites. m: (vacaney defect) will appear in - or two 曰 ^, solute cations (doping) are more soluble in the nano-knot::: ΐ ΐ: occupying it Sites that differ in conventional materials. The solubility of non-chemical sulphur or anions outside the oxygen sublattice of the crystal structure may also increase. In some embodiments, 27 200843165 27144pif The nanoscale ion storage materials described herein exhibit one or more of these variations in terms of defects or solid solutions. However, as shown by the experimental results presented herein, the presence of foreign metals or anions is not intended to create or define nanoparticles. The special properties of the crystalline state are necessary. The difference in physical properties exhibited by nanoscale materials according to one or more embodiments of the present invention compared to conventional coarse crystal corresponding materials can be readily determined by standard thermal and electrochemical Technical measurement, such as quantity Thermal method, cyclic volt-ampere method, galvanostatic intermittent titration (GITT) or potentiostatic intermittent titration method (pTT), for example, nanoscale materials for ion storage applications The improved performance can also be easily measured by formulating a nanoscale material in an electrode coating, constructing a non-aqueous electrochemical cell, and performing a charge-discharge test at various rates. The state of the expanded solid solution in the meter-scale material. For example, the nanocrystal φ compound Lh-xFeP〇4 can be tested in a non-aqueous electrochemical cell. The nanocrystal LUePCU is used as an anode electrode having a nanocrystalline electrode A lithium source (such as a 'bellbox) that has a much larger lithium content than a lithium-rich battery. The electrochemical cell structure is generally familiar with lithium-ion battery technology, called a clock half-cell (1 pool hai£-ceii). The battery is connected to a nanometer-scale ion storage material by using a conductive additive such as carbon and a polymeric binder. Usually, a microporous polymer separator is used, and a nanometer is used. The ion storage material electrode is separated from the inner metal opposite electrode. Then the non-aqueous lithium-conducting liquid electrolyte is poured into the battery. The charging and discharging rate of the electrode is relatively fast, so that the chemical behavior of the nano-scale material can be tested 28 200843165 27144pif. ί Γ:: Total lithium extracted from the nanocrystalline electrode after sub-charging == listening, first charging capacity and initial discharge: ^(d) lie in the secret « and after the assembly in the battery, there is a lithium deficiency. With the same clock The amount is small. Figure 5 illustrates the group II. The initial data records the discharge capacity of the first charge t at the c-rate. Please note that ΐ, high = = electricity is greater than the initial capacity by more than 11% 4 Please note rate: there; ^ 1, # > 90% of the discharge capacity, that is, after the high discharge speed 充电 charging and electricity, The test is carried out at a rate sufficient to slow down: the observation is independent of the battery structure = or = academic limit to reflect the result of the error. Those skilled in the art are familiar with such methods. It is observed in Heli and very acid bell iron that it is equivalent to the conventional or thick L_4 and even the large 'knife insert electrode material. Using a similar battery configuration, the resulting 仃 is greater than the first and subsequent discharges ^. The first charge is usually the same. The conventional material fish described in Figure 5 is a striking difference in the knot. First, the comparison of: == material is highlighted - some 10% lower than the daily capacity of the first day of charging capacity * the amount of discharge in 1 is decreasing as the discharge rate increases. Since the initial charge capacity of the south is generally relatively large, the nanometer scales 2008-04165165 27144pif points according to one or more embodiments of the present invention are counterintuitive. While it is generally desirable to have a higher initial extractable age for the lithiated electrode material, in the context of the present invention, the nanoscale = ability to hold a lithium solid solution results in a number of advantages as described herein that are sufficient to overcome The disadvantage of a slightly lower lithium capacity. ‘,, and

Moreover, as discussed later, the nanoscale material of the present invention maintains a non-stoichiometric amount of x = & y which is greater than or equal to the non-stoichiometric amount present in the material being produced. Accordingly, the materials of the present invention are prepared in an initial non-chemical basis, and are prepared from the first metered state to obtain the benefits described herein. As described earlier, one of the nanoscale ion storage materials of the present invention can be used in the form of a block or a ruthenium form having a ruthenium compound in the form of a solid or a ruthenium. Increase = the nature of the body range. As shown in Figures 5 and 19, it can be seen that the first and subsequent discharge capacities of the first capacitor material are relatively small. After the m treatment, the _solution is clearly present in the prepared material and has an expanded solid solution range. Therefore, the present invention also learns the phenomenon of measurement, in which the measurement in the synthesized state refers to the relative composition of the composition, Zhonghua::=;;;f ^ui-xFep〇4 ^ LiFeP^ Calling some other litnr chemistry has a sapphire structure or its 曰曰, ,,. Structure, or may be amorphous or partially amorphous. The material 30 200843165 27144pif may have a specific surface area of at least 15 square meters per gram, or more preferably at least 2 square meters per gram, more preferably at least 25 square meters per gram, or even more preferably at least 30 square meters / gram. The lithium non-stoichiometric enthalpy or y may be greater than at least 2 moles compared to the range of values occurring in the prepared material having the same composition but having a lower surface area form (eg, less than about 10 square meters per gram). Ear %, more preferably at least 4 mole %, and even more preferably at least 6 mole %. The range of lithium non-stoichiometry can be measured by methods well known to those skilled in the art, including electrochemical titration, the presence of non-stoichiometric lattice impurities and 1_1 or neutrons, or chemical analysis. The non-stoichiometry of the clock present in the starting material is advantageous; = conductivity and phase change rate, and thus beneficial to the effect of its nano-cell battery by measuring the balance of the nano-scale material The standard in the == 5 hills only the nanocrystalline material described herein is not chemically related to its coarse corresponding material. Those skilled in the art are aware that the chemical potential of an electroactive substance in one electrode (test electrode) is balanced by a battery having a high potential of a high reference state. 1 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋It is measured by the slow-carrying rate of the carbon-coated sulphuric acid iron material that can be obtained from commercial soil and the c/5 习 of the battery electric dust. The near-balance can be observed. The step-by-step method is to learn that the nanoscale material is relaxed by the independent measurement of the sample. 31 200843165 27144pif (r-n) to its equilibrium potential. It is known that nanoscale materials exhibit substantial charge capacity at continuously variable voltages (before reaching a relative 妓 voltage platform). The battery voltage of the conventional material does not have the mode, and conversely, the voltage platform is almost immediately reached after a small voltage increase. Figure 8 shows the c/刈 discharge curves for the same three samples. It can be seen here that at the beginning of the discharge, the two nano-scale materials exhibit a capacity mode of continuously varying voltage, showing that it has a solid solution in which the conventional material is substantially absent, and the two kinds of nanometers when the discharge is ^ The scale material shows a wide capacity mode of the continuously varying voltage of the solid solution. The examples demonstrate the effects illustrated by the respective plots of the nanoscale and the conventional lithium iron phosphate materials of Figures 3B and 4B. Still other electrochemical methods which can be used to demonstrate that the nanoscale materials of the present invention have an expanded solid solution scheme include GITT and ruthenium. In GITT, the open circuit voltage (OCV) measured after the electrochemical cell is near equilibrium shows compositional dependence (i.e., varies with state of charge or charge capacity), which is significantly different from conventional and nanocrystalline forms. The expanded solid solution Φ body range in nanoscale materials is shown by the region of composition X, in which OCV is not constant but varies continuously with composition. This means that although the X changes but the chemical potential of lithium is strange, it is a multiphase equilibrium. Those skilled in the art can perform the measurements to ± 0.002 volts or more to compare different materials and determine the X value of the boundary between the single phase solid solution and the multiple phases. For nanoscale materials, the composition of the single phase solid solution X is broader. A broader range of solid solutions in the nanoscale form can be obtained for any one or more of the individual phases exhibited by the compound, including the intermediate phase formed within the chemical range discussed herein. 32 200843165 27144pif The PITT method can be used not only to determine the battery voltage for electrochemical oxidation and reduction of electrode active compounds, but also to provide information on the rate and mechanism associated with the reaction. In PITT, the battery voltage gradually steps up or down and monitors the current when the battery is self-charged or discharged. Figure 9 shows the trace of voltage and current after charging in a PITT measurement of a conventional carbon coated lithium iron phosphate sample. At a voltage step of 10 millivolts (v〇ltage step), the current is observed while the battery is charging. It is worth noting that _, Φ has barely recorded capacity before reaching the voltage platform. At the same time, during charging on the voltage platform, the current slowly rises over a period of hours and then decays, showing the hysteresis phase transition kinetics during charging. In Fig. 1A, the PITT charging interval is displayed, and each of the batteries can be measured under each voltage step. It can be seen that at the platform voltage, almost no capacity is recorded when the voltage rises before large capacity is observed. The results of the same battery during the PITT discharge experiment are shown in Figure n, where the first voltage step is from a voltage of 3.8 volts to a voltage exceeding the battery open circuit voltage of 5 _ , measured at 50% state of charge. In this experiment, almost no battery discharge was observed until the PITT voltage was about 2 毫 mV below 〇cv. No. 1 of the nanoscale material of the invention behaves in a significantly different manner. Figure 12 shows a charged pITT experiment of a nanoscale Lio^FePO4 material in which substantial current (i.e., table *charge) is seen before the two phase platform voltage is reached. In addition, as seen in ® 9, the upward voltage can be observed immediately (rather than hours) from the maximum value into the child/melon attenuation. This means that it is easier in nanoscale materials. The phase transition of the deuterated LiyFeP〇4 phase is formed. Figure ls shows the capacity measured in the ριττ charging experiment period 33 200843165 27144pif battery under various voltage steps. It can be seen from Fig. i3 that the Γϋΐ is below the platform voltage. Please note that because Charging occurs only when n (four) is at or above the equilibrium light, and the result of (10) indicates that there is a composition of equilibrium voltage lower than the voltage of the two-phase platform. That is, the presence of the prover Lil_xFeP〇4. In FIG. Shows the result of the same battery during the period of ριττ ,, where the first step-step charging voltage reaches a voltage exceeding 5 mV (at 50% charge, measured) of the open circuit voltage of the battery. Here, when The voltage of ριττ still exceeds Ο.” The actual capacity measured by the pen volt %' is about 8 mAh/g. Since there is no driving force before the applied voltage is at or below the equilibrium voltage, the result is confirmed. In super Under the voltage of the platform voltage, there is a clock excess solid solution LiyFeP04. The difference between the nanoscale LiKxFeP〇4/LiyFeP〇4 and the conventional material can also be quantified by X-ray diffraction. In the nanoscale Lii_xFeP〇4, the composition The existence of different non-stoichiometric amounts is evidenced by a unique lattice constant (a, b and c in the orthorhombic unit cell) and a unique unit cell volume (given as the product of axbxc). LiFeP〇4 has a larger & and b lattice parameter than the crystalline Fep〇4 and a smaller c-crystal parameter than the crystalline FeP〇4. Therefore, when the lithium concentration varies between 1 and 0, between FeP〇4 The continuous solid solution has a continuous variation between lattice constant limits. Thus, the lattice constant of the material according to one or more embodiments of the present invention can be used to determine the corresponding non-stoichiometry of the coexisting phase. Performing the careful X-ray diffraction (careful X_ray de-addition) measurement of the material of the present invention under different lithiation states (different states of charge (SOC)) to complete the above-mentioned Fellowship 34 200843165, 27144pif, This uses the Rietveld fine algorithm (for familiarity with battery materials) Characterizing the method known to the skilled person for analyzing diffraction data) to obtain the crystal parameters & crystallization information. ', Figure 15 shows that at 50% SOC, obtained from a conventional carbon coated lithium iron phosphate material (Aldrich Chemical) a powder X-ray diffraction pattern. A bismuth powder is added to the sample as an internal standard for the X-ray peak position. Based on the = 绕 Com Comniittee on p〇wdef • Diffraction Siandards, JCPDS} The literature 〇 [〇8Wl73 = according to the visible peak of LiFeP〇4 olivine and the expected peak position of the phase. The peak of the olivine form of FeP〇4 can also be seen in Fig. 15, which replaces the position of the different composition listed in the JCPDS to some extent. • Figure 16 shows a powder X-ray diffraction pattern obtained from the nanoscale LiFyP〇4 sample of the present invention measured at 67% SOC. It can be seen that the 'work setting 〇 4, 契 / ePCU phase, many peaks are different from the corresponding positions in Figure 15. On the powder χ ray diffraction pattern that is read in a wide diffraction angle range of 15 to 135 degrees (the range of the skill in the art), the Rletveid algorithm is used to perform the material ray day and day. Accurate determination of constants. It is found that the nanoscale material according to one or more embodiments of the present invention has a lattice parameter value which is significantly different from the conventional t = when the two eucalyptus phases mentioned above are in a state of charge. The lattice parameters and unit cell volume are listed in the second, where the nanometer-scale lithium iron phosphate is carried out at 67% state of charge = with the literature (A·S·Andersson and J. 〇· Thomas, J·P〇wer o=rces :97-98:498 (2001)) Comparison of the conventional LiFep〇^ ϋ乂 测. For example, on the lithium-rich side of the phase diagram, a Lili_xFePC with a crystal lattice constant of a and b crystal 袼f which is smaller than the conventional LiFeP〇4 and a ratio l is known to be LiRep〇 is obtained. ) 4. Lack of _ solution spot 4

The WePOA phase coexists (LiyFeP〇4 has a larger lattice parameter than the well-known Fep〇4 = the secret of C. 4). The measurement confirmed that the corresponding value in the conventional LiFeK) 4 / FeP 〇 4 is large, but there is also a y car = ^ stoichiometry present in the (four) towel. _ =, the crystallite size of the non-meter scale sample is about 28 nm, which is close to the 36.1 nm calculated by the spherical particle size and confirms that the sample j is attributed to the nanometer scale of the __ microcrystal = Beiji Impurity or additive phase. ❿不❿% due to the south surface constant and unit cell volume Γ'--- Material a (A) • Ixiong · b (A) ---------- 10329 6.007 ^5i^xFeP04 10.288 5.991 9.814 5.789 -ii^LiyFeP〇4 9-849” 5.809 Table U deleted r ship, '% and LiyFep〇4 lattice

And the value of 3+ static full eyebrow my determines the ratio of > IV+/F^ atomic ^ in the material (in the case of iron, it is e) 'and the larger value indicates that the minority price JL has #t, #八二低X or y的知知麟^w辰度. This has an effect of increasing the electron yield of each phase, and thereby improving the electrochemical performance of the battery, as compared with having a white phase. In addition, the decrease in the lattice parameter of the Lil_xFeP〇4 phase (or any other component of the Fuli endmember) causes the multivalent transition metal ion to be closer to the effect in the structure, which also increases the obstinity by 4 degrees. Thus ^ the electronic transfer of the material, thus reducing the 4, _ or increasing the rape to increase the electronic conductivity. The lattice constants a and b of the missing clock Li]_xFeP〇4 are smaller than LiFep〇4, and the lattice constants a and b of the LiyFeP04 are larger than the secret 4. Therefore, in the nanoscale material of the present invention, the lattice parameter and the unit cell volume are the same as the material efficiency of the material frequency shifting. This is especially true under the *charge/discharge material. This is = also charge, and the discharge threat - phase formation of another phase of the ability to take two 妓 the phase of the lattice reduction (if crystallization) and the relative volume of the mismatch. ', the coexistence phase Li^FePCU and Li Fep〇 door 曰 积 报 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; It can be seen that the case of ¥^==〇 after charging can vary, and this can cause any difference between the hundred rates after the type of power. However, in order to facilitate the comparison with the intrinsic person of the discharge, the average knowledge between the two can also be utilized: the difference between the corresponding values of the volume or the unit cell volume, such as any lattice constant crystal 袼 constant The difference in percentage is the arithmetic mean of the a of the two samples for any two materials as described in II 2008 200843165 27144pif. Unless otherwise stated, this article calculates the difference in percentages in this way. For the nanoscale LiyFePCVLUePCU, the difference in lattice parameters is Δ & = 4.36%, Δ b — 3·07°/〇, Δ〇 = _1·75%, and the difference in unit cell volume is = 5.69%. In the comparison, for the conventional LiFePOVFePCU, the defined end elements are Aa = 5.11%, Δ!? = 3.68%, Ac = -1.93%, and Δν = 6.87%. We also measure the conventional material (Aldrich Chemical) in a 50% state of charge, and wherein the coexisting composition has a relatively small and permissible non-stoichiometric amount. Here, the difference is Aa = 4.91%, zib = 3.64%, Δ(:=: -2.03% and Δν = 6.52%. The unit cell and lattice parameter differences are summarized in Table 2. Although in Table 2 Not shown, but it is also easy to calculate the misfit strain that separates the two planes that make up LiyFeP〇4 and LUePO4. It is important that during the electrochemical cycle, two-dimensional features are observed. The interface must be introduced between the two materials to form another phase from one phase. As a result of the table 1, the plane formed by the principal axes a and b (this hand or static edge 襟indeX) plane is

The maximum area difference between LiyFeP〇4 and Li^FePO4, such as plane (or {101}) has the second largest difference, and the rainbow plane or ({〇11}) has the smallest difference. This means that the be plane is the best direction along which the -phase topology (t〇p〇taxiqing) grows to the other phase (or vice versa). Comparing the service scales in Table 1 with the conventional materials, the difference between the nanoscale materials is 7.43%, 2.62%, and 1.32%, and the conventional materials are 8 79% ^ and L76%, respectively. The secrets measured at 50% S0C were 8.55%, 2.88%, and 1%, respectively. Thus, according to a = 38 200843165 27144pif example, the nanoscale material of the present invention has a strain in area that is less than about =, i is smaller, u%, or less than about 1,4% of any crystal major axis. According to another embodiment, the strain from the plane formed by any of the crystal principal axes does not exceed 8% or 75% or 6 Å/〇. Table 2 ·: Crystalline parameters and unit cell data materials, (%) Ab (%) ^(%) ΔΥ (%) FeP〇4 ~^ 5.11 3,68 •1.93 6.87 Deficient Naihu LihxFePG^ Lithium-rich nano LiyFeP〇4 Τ Ί , "Pck'Dr'V / 51S1 L· \ 4.36 3.07 -1.75 5.69 (General) LiyFeP〇4 (General) 4.91 —---- 3· 64 —---- -2.03 6.52 As far as is known, the difference between the two is significant, which is attribution (GPa). If the so-called = about (10) gigapascals can be used to reduce the energy required for the other phase, and the self-phase transformation is formed (so-called "electrochemical grinding" mechanical fracture and defect invention Extraordinarily long. (10) can be reduced, so that this also recognizes that although the most granularity will not be achieved in the material of the present invention; see = say 'beyond the most visible blood, but can be familiar with 39 200843165 27144pif this technology has been Knowing the difference = the nanometer scale, when the degree is reduced, in any two: two: the range of I * non-stoichiometric X and y increases, and the difference between the coherent phase and the unit cell volume is also reduced. Small, that is, referring to Figure 4a = 4B 'the boundary of the two phases will move inward in terms of leveling, and move downwards at a temperature of ~1. For the particle size of the foot_fine, at room temperature, achievable Yuan Quan solid solution.

The cycle life of a word battery is generally defined as the number of hundred/discharge cycles in which the capacity of the battery is reduced to the initial value at a specified voltage range, chirp, and current rate. At a current rate of about 2 volts to 3 volts, including LiFeP〇4 sapphire and its known cathode activity (4) and refillable κΓο using the material to the initial value It has usually been shown to be smaller than the placket. In contrast, the materials and devices of the present invention have a capacity reduction of two, and the number of cycles before the coincidence exceeds 1000: owe, or even more than 2,000 in some cases more than 5 times. In the same electric range, under the light Z-six ί electric fan rate, for example, the 5C charging/discharging rate, the conventional material is usually less than about 500 times before the 80% of the initial value, according to the The materials and moving-rate cells of one or more embodiments of the present invention have many considerations, including, but not limited to, hybrid types, which require a charge rate charging within a voltage or capacity range that is less than a full cycle. Discharge pulse. Under the secrets, the material of the invention 200843165 27144pif and the cycle life of the device is quite long. A well-known pulse test protocol is the "HPPC" test defined by the United States Advanced Battery Consortium USABC. The materials of the present invention, when used in batteries that meet the specific energy and specific power requirements defined by USABC, are capable of exhibiting a cycle life of more than 150,000 cycles before the battery performance is below the applicable limits defined. It should be understood that during the dynamic process of embedding and insertion, the stress generated by the difference in lattice parameters may cause the cell parameters of the coexisting phase and the libraries X and y to temporarily deviate from their stable values. Nevertheless, after the material has been relaxed and partially equilibrated for a period of time, the above difference between the nanometer scale and the conventional material ^ is clearly seen, so that the two types of materials are clearly distinguished. When initially preparing materials and assembling electrochemical devices, the properties of materials including non-stoichiometric amounts of lithium may not be in their stable state. In the case of being used as a rechargeable battery, for example, the original lion, the material is important for the movement between the subsequent d and the d. Therefore, at least one of the device operating voltage limits is fully embedded and after (iv), and the miscellaneous material is in the pot charging state for at least 12 hours before the difference between the unit cell parameters and the lithium concentration is measured. In the embodiment of the invention, or in the plurality of embodiments, the range of the solid solution in each end phase is increased by the electrochemical cycle, and the battery causes the phase to be converted into another type = more j. This behavior appears when the impedance of the battery decreases with the charge/discharge cycle. He 2 according to the invention - or the materials of the various embodiments, because the material is j-scale 'and it has been engineered to have a smaller between two coexisting phases: the number of defects and the mismatch of the unit cell, so First, compared to #_, it makes the electrochemistry = 41 200843165 27144pif: the formation of another phase (and vice versa) is easy to minimize and make the phase change easy (10) The force is not known in the field of pool materials. The advantages of the filling discharge material, ^ a few rapid accumulation or shortened cycle life under angular temperature 哎 low vibration density of unwanted low energy density in the battery = avoid using high table on the battery electrode (especially on the anode side) Object, For example, the well-known cathode active materials UC002 and L ancestor 2, Xiangzhong and derivatives have safety concerns in the sorghum state, because their transition metals are present with high oxidation of 4+ money. Overcharging and/or overheating the rotor battery made of the cathode material, even if the active material is in a conventional form, causing thermal runaway, resulting in fire or explosion, and it is generally considered that the active material having a higher surface area exacerbates the above. Dangerous. At the same time, at high temperatures and for a long period of operation, the resistance of the clock ion battery using the cathode material rises due to the interface reaction which causes the power capacity to decrease. Therefore, the use of the material in the crystalline state of the nanocrystal is considered unwise based on safety and service life considerations. As another example, the cathode active material LiMn2〇4 is used in a high-power lithium ion battery, but the battery usually loses capacity permanently after use or storage, possibly with the turtle dissolved in the electrolyte and/or in the battery. The residual acid in the liquid electrolyte used is related to the protonation of the surface of the active material particles. Since the above effects are exacerbated in high surface area materials, conventional teachings have been made to avoid the use of nanocrystalline LiMn2〇4. The examples all suggest that the nanoscale particle size has some unfavorable properties. However, the use of the nanoscale ion reservoir 42 200843165 27144pif material described herein overcomes the above disadvantages while retaining the advantages of energy density and power density.

Compared with the conventional materials, the broader range of the solid solution of the nanoscale material of the present invention can be attributed to stress, including the stress generated by the rainy curved free surface combined with the surface tension of the material and when The stress caused by the coexistence of the two phases, and the regions of the respective phases each stress the region of the other phase. In addition, although not limited to any specific explanation, it is generally believed that the difference in the nature of the nanoscale-scale ion storage compared with the larger-scale subtractive material may be related to the change of the near-surface defect layer of the material_defect thermal state. Form related. The difference in physical properties and structure between the nanoscale and the conventional crystalline state is similar to the difference between the single-city knot (4) and the Lang form. In other words, 'there are significant differences between the two and the physical properties. Because (4) It can be regarded as not riding. s - the structure of the touch mode or theory, called the mechanism can be i2 =: or the nanocrystalline material of the plurality of embodiments, due to the difference in the free energy of the formation of lattice defects, and the grain boundary crystal The discontinuity of the ion co-secret, /, his surface, the surface can become enriched with one or more of the original; empty: 3 amount of surface charge and penetrate a short distance into the solid, The layer 'the (iv) charge layer contains a charged defect. ❹ 』 ” ” ” ” ” ” ” ” “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ phenomenon. (References, for example, Υ, Chiang, DR Bimie, III, and WD Kingery, Physical Ceramics: Principles for Ceramic Science and Engineering. Chapter 3, John Wiley & Sons (1997); Chiang et al., “Characterization of Grain Boundary Segregation in MgO,” J. dm. Ceram· &>c·, 64:383-89 (1981); Ikeda et al., "Space Charge Segregation at Grain Boundaries in Titanium Dioxide: Part I, Relationship Between Lattice Defect

Chemistry and Space Charge Potential/9 Jt Am. Ceram. Soc^ 76.2437-2446 (1993) ; Ikeda et al., “Space Charge

Segregation at Grain Boundaries in Titanium Dioxide: Part II, Model Experiments, ^ 1 Am. Ceram. Soc., 76: 2447-2459 (1993). We have observed non-stoichiometry in the experiment and the behavior of the nanocrystals affected by space charge in the material is consistent with the extended solid solution behavior. Therefore, although not limited by any particular theory, we have clarified the possible reasons for the described behavior. The starting point of the LiFeP〇4 olivine compound (which is then allowed to equilibrate its free surface with its environment) is considered. The surface is likely to become enriched with ions with the lowest defect formation (4) and/or with preferential movement to the table. In Li Gang 4, the energy and power of the separation are Considering that the ions are likely to be clocks, the formation of the rich clock surface will cause the lack of parts, where the missing corresponds to the age. For example, the pots (4) charge behavior, the loss is not evenly distributed in the whole 'two lithium The vacancies are preferentially concentrated on the surface of the space charge layer. The working range of the layer depends on the defect density under thermal equilibrium, the dielectric constant and temperature of the material. If the system is not in equilibrium, then * The layer garden is based on the pulsating dynamics of ions and defects. The spatial distribution of defects is shown in Figure 17. The spatial electrical range can range from about 1 to several nanometers. Vacancies or other defects ^ J The layer = empty may be many times larger than the concentration in the bulk crystal of the solid solution, and the surface concentration may be precipitated or phase separated. Therefore, for small enough nanoparticles, two nanofibers or films, the inside of the particle has Significantly higher than talent, face loss The particle is now expressed in a non-stoichiometric manner on the surface of the Li + Faraday behavior (Famdaic behavi〇r) fish ^ although the table time. X-ray diffraction measurement and electrochemical testing and learning == year-on-year In addition, it is possible to make the surface rotor easy to ==2 the adjacent medium of the electrolyte to react with the surface, or to reduce or discard the liquid == the substance reacts and evaporate it. In the case, 'has a better Particles or crystals have more bell defects, and the defects of the particle spectroscopy are still solid solution ς' under non-normal conditions, and the rate can also follow the diurnal conduction rate from the surface, and Sr only The particles provide higher electron entrapment than the internal two-particle surface electrons. It is unexpectedly found that the material that provides high charge rate performance is used for the material of the discharge rate and the material of the discharge rate. r#/ Political differences. In particular, the same: 'appears below its nature: === process (two extractions) or higher than the phase transition dynamics of its appearance: ί: two tables - face: 45 200843165 27144pif fine examples should recognize the temperature shown in 'this (four) _ towel's frequency The fine m-touch high-charge material and the standard with the performance as shown in Figure 包括 include the temperature _. In practice,

The temperature can vary widely, and can be varied, for example, due to resistance heating 2: or due to external heating or cooling, although it is well known to those skilled in the art that the standard test is performed and the ambient temperature is set. The effectiveness defines the appropriate material. - measuring the g-potential intermittent titration test (PITT). It is exemplified by the skilled person of the electrochemical and electric = two materials, and the cap electrochemical cell applies a small voltage increment = decrement (<Gl volt), and The current is measured after each voltage step. As previously indicated: the total current at a given voltage can be used as a measure of the stoichiometric range to establish a marriage, and the current rate can be used as a measure of material rate performance. Thus, as described in Example 5, the inherent rate performance of the material can be determined using PITT measurements. In many applications, the materials of the present invention have significantly different charge and discharge rate performance reports. For example, in hybrid electric vehicle (HEV) applications, it is not only necessary to transmit power at the speed of the battery during discharge, and high charge rate performance is required to capture a large amount of regenerative braking energy. Therefore, in the HEV practicality, the use of a battery that only provides a helium discharge rate without providing a high charge rate is considerably limited. As another example, a short charging time (fast charging rate) is quite advantageous for a two-line 46 200843165 27144pif mobile phone or laptop. The source can operate for hours to days, so the device is more battery-powered. Thus, a battery having only a high discharge rate that is generally slow to be able to be useful without high charge rateability, in at least some embodiments, has less than about 5% by weight or about 3 weights; == The ion is stored but provides additional electrical conductivity. The additional phase includes (_^addition phase (addltl〇nal = belonging to a genus axis), gold; = or == genus in this genus carbide-nitride or metal carbide 4 compound. In some 4 cases In the case of being used as a storage electrode, it is often formulated into an electrode by a standard method, including adding a plurality of polymerization agents and a small (four) 1 G weight% of a conductive additive such as carbon. In the case of the implementation, it is usually The electrode is applied to the gold from its two sides' and the thickness of the coating is squeezed to between 3 micrometers and about 2 micrometers, as appropriate, to provide about 0.25 milliampere-hours per square centimeter and about 2 milliamperes. The charge storage capacity between square centimeters. The electrode can be used as an electrode or a cathode electrode in a battery. Its performance can be evaluated, for example, by a coin-type battery or a so-called Swagelok battery type laboratory battery. , = using galvanostatic (constant current) or potentiostatic (constant voltage) or some combination of the two to test relative to the opposite electrode (when the nanoscale material is lithium storage material, a single layer of an electrode, usually lithium metal. In a constant potential condition The current rate can be interpolated as "c rate", where the rate is C/n, and η is the number of hours required to fully charge or discharge the battery between the selected upper voltage limit and the power 47 200843165 27144pif [lower limit] In some cases, when the anode electrode of the battery towel is used, the electrode is wound in a multi-layer laminated battery of a wire winding or stacking configuration, and a lithium gold 1 active storage clock electrode is used as a cathode electrode. , carbon, TM ^ ^ metal σ gold includes lithium active elements, such as A Bu Ag, B, Bi, Ga (3e hi ' Pb ' Sb, Si, Sn or Zn. Optional or design = polar material to achieve high rate performance The assembled f battery can use a porous electronic insulating diaphragm between the anode and the = material and a liquid, solid electrolyte. The battery can have an electrode formulation which is provided by the prior art to provide low battery impedance. Or physical = and,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, # ^ The average voltage displayed at the rate is about ^' 丨 smaller and lower Within the pressure range, with C/5 or]:= and the lower limit is about 5〇%, the rate is lower, the target is smaller, (ie, the power storage is low), and the lower limit is measured. Compared to the valley, the amount at the 5C rate == more than two J - in some cases, about m or two, force 95 / or greater qGC rate, electricity, in some cases about 85% Or more about 75/. or more about or more. 20C rate = (four)% or more, electrical storage can be about 60% or 48 200843165 27144pif in some cases 钧 70% or Bigger, for example: Na or bigger. At 35C rate, the power is saved: more f G% or more. At a rate of -. or more, in some cases, 4% or more, for example; , , or greater, or about 60. /〇 or greater. For,, spoon, 50/〇

ί - Some real complements, when the discharge rate is reduced at Μ or less, and ί ( should be placed at a degree) to substantially completely discharge, s, the nanoscale material described in this paper can be to the battery ten == Fineness) and specific energy (energy density). = less than about 10 watts / kg (2 at least about 5 (8) watts / kg (1 watt / liter) ratio of work t qH kg (190 watt hours / liter) than the energy of at least about kilograms 〇 80 watt hours / Liters of sheep, at least about 90 watts / watt / liter) ratio of power / kg (2500 to 々 5 watts 8 ^ 075 watts / liter) should understand the second: 丄 6: electric tile罙 2: (, ° watts 'liters) of the specific power. Significantly higher than the degree 6, the specific material and power density can be Z column non-limiting examples into - money material some real examples 1 , Wei = the following ratio of the starting material commission has a total composition of L_4 49 200843165 27144pif L12CO3 (Alfa-Aesar , 99.999%) 〇·739 g of iron (II) oxalate (Alfa-Ae$ar, 99.999%) 3.598 g of ammonium oxalate (Aldrich, 99.998%) 2.301 g

Although the basic component is known to be a starting material for synthesizing a conventional LiFeP〇4, here, by using high-purity acetone as a solvent (reagent grade, τ Baker), and using an extended mixture (exten (jed melon- The beer obtains a precursor by mechanical reaction of the released gas, and after firing, produces a low-carbon, very high specific surface area of nano-scale phosphate. The dry component is weighed and is high enough. The purity is mixed to produce a free-flowing suspension, and in a propylene can, the mixture is roll milled 2"4" using a cerium oxide grinding medium to obtain a (4) fine-grained precursor suspension. The precursor is sufficiently dried. And then heat treatment in a tube furnace with flowing argon (5G grade): first = down, time, and then in the boot ^ * BET method to measure the specific surface area and measured value of square meters / male 3 · 6 M/iLm 'calculated that the equivalent spherical disk two tables may be mainly attributed to the nano-scale citrate phase. The powder prepared by this order, such as the transmission electrons observed in Figures 1 and 2, has an average particle size close to that.球形 荨 面积 观 观 面积 面积 面积 面积 面积 面积 面积 面积 面积 面积 面积 球形 球形 球形 球形Having an electrode of the following fields,

Super Ρ Carbon Kynar 2801 bonded residual nanometer scale lithium iron phosphate powder 3.95 grams 〇 50 grams 0.55 grams 50 200843165 27144pif 7, butyrolactone (solvent) public and mixed to produce a free-flowing suspension, followed by aluminum foil Form a uniform casting. The coating was placed in a vacuum at 1〇〇-11〇. The underarm is dried, and thereafter, the thickness is about 100 μm, and it is pressed into a disc of a cm diameter as appropriate for use in a Swagelok or coin type battery. The electrode coating is assembled in a lithium half-cell using Swagelok or coin-type battery hardware: using microporous polymerization, membrane, lithium foil as the cathode electrode (the total lithium content is at least ten greater than the theoretical storage valley of the anode electrode) Double), and a conventional non-aqueous clock ion battery containing LiPF6 as a bell salt. Figure 18 shows the specific capacity of the if-scale lithium iron phosphate measured by Swagelok batteries. The ability of nanoscale materials to transfer the valley 1 under high charge or discharge is quite prominent. Here, the discharge power is used to interpret and the same wire as shown in Fig. 16 is the same as the C/5 rate in the current range of '2·0-3·8 volts. Percentage of capacity. At UC rate, the charge retention is 95.9%; 18C s296t1〇/V 9Cii#T 5 8δ·1%; 44C speed Ϊ ° °; at 31C rate, it is 75.6%; and f is known as ion storage material. The above values are extremely high == measured during the charge loop, indicating that the non-stoichiometric example of the prepared material has a total composition of "card scale material storage material, and its difference is preparation 51 200843165 27144pif larger batch and using different starting materials to prepare the composition: _ the following ratio of starting ti2 < f3 (SQM) 7 · 4337 grams (Elementis ^ 36.2696 grams, ammonium (H -) 22.5541 grams. Material tmr (four) capacity 11 and steel grinding media grinding start: and the final firing conditions are 7, c; =; there are 45.4 square meters, the ratio of grams to the surface; = rr. Combustion analysis shows that it has about =: Chen. Figure 5 The measurement shows the electrode and the half-cell of the battery as shown in the example. The hard body has a low discharge capacity: the second charge capacity is more brittle than the first prominent charge. For the three materials, it is observed that: = about 95%, under the rate Under the condition of electricity storage, the storage stability of the electricity is in the range of 66_72% tAl. The nanometer-scale ion storage material with the total composition of 敕石户二 and 1〇.95FeP〇4 was synthesized and tested, and the amount of scallops was adjusted to achieve the specified total composition. UFep〇4Li(4)**==BET method has 39 78 square meters / gram and 46.2 3 = gram ratio table _, corresponding to 419 nm and 361 respectively

;, the effect of spherical particles; ff. Combustion analysis showed that the two powders had U 52 200843165 27144 pif wt% and 3% wt% residual carbon concentration, respectively. Figures 7 and 8 show with Aldricli

The Company commercially available a carbon coated LiFePQ4 ratio with an average particle size of several microns and a very low rate performance, C/50 charge and discharge curves for the two samples. Due to the extremely high rate performance of the material, referring to Figure 19, the low catch rate charge/discharge curve is indicative of the near equilibrium voltage of the battery. It can be seen from the curve that during the continuous charge and discharge period, at least about 15% of the lithium non-stoichiometric X and at least about 1% of the: y are obtained. Figures 12-14 show the results of the ριττ 1 measurement of the nanoscale Li() 95FeP〇4 sample as previously described. During the single-stage discharge to over:, QCV 5 mV, at a C/50 catch rate, the total discharge capacity was measured at 4.5 mAh/g (38 volts to 2 volts) of 4.5%, indicating Under dynamic discharge conditions, a non-stoichiometric y greater than about 4.5% can be obtained. During a single-stage charge to a voltage less than 5 mV below 〇cv, a total charge capacity (2·9 volts to 3.8 volts) of 10.5 〇/〇 is measured, indicating that under dynamic charging conditions, there is greater than about 10.5. / non-stoichiometric X. In comparison, the y and X values calculated from the capacity of the comparative samples from Aldrich Chemical at and below 0 CV 5 mV are only 〇.7%.. 2 4 Figure 16 and Tables 1 and 2 show as previously described Nanoscale

The diffraction result of the X-ray powder of Li^FePO4 sample. Based on the Hietvdd actuarial calculation of the = product, the crystallite size is determined to be about 28 m, $ is close to the calculated equivalent spherical abundance and the high table product of the sample is shown: Nanoscale crystallites are not attributed to high surface area heterogeneous phase. ® 19 shows the test results for two lithium half-cells of the Swagelok hardware configuration as in Example 2. 53 200843165 27144pif (5) truthful full pure card degree storage material) anode electrode (cylinder clock leaving == performance) to construct winding = average diameter using graphitized mesophase carbon microbeads simulation:: 丄 can be the volume of the battery component And describe the performance of the battery, including a variety of C rate under the charge and the inside. Starting from a fully charged state of 3.8 volts and discharging to 20 volts of electric dance watt hour/kg (2 〇 5 watt hours / liter) of specific energy ~, 'spoon 500 watt / kg (10) watts / liter) of specific power, At least about watts, / kg (10) watt-hours / liter), at least about 1300 watts / kg (25 (8) watts / metric ton of power and at least about 85 watts / kg (175 ϋ: under) At least about watts of kilograms (3200 watts / liter): 匕 power. i higher than the shallow depth of discharge, the specific power and power density can be 39.8 :: 22: 1 has the composition LiFeP 〇 4 The specific surface area is the one in Example 2: the same as ί2 = two: material. In addition, the actual surface area of the material is 48.8 m ^ 2 / metric", where the difference is the final at _ ° C Firing. Based on the comparative purposes of 54 200843165 27144pif, a carbon having a specific surface area of 14 8 m ^ 2 /g from Aldricli Chemical Company commercial use as described in Example 3 was coated. LiFeP〇4 was prepared. All three materials were prepared. Tested in a Swagelok battery using the procedure of Example 1 in the electrode. At the 5 〇% state of charge, at the temperature of interest After waiting for at least 12 hours, measure the battery cv. Start with a full discharge or state of charge, and use a voltage step of 5 millivolts or 1 millivolt to perform the pITT measurement as previously described. Φ 9. It can be observed that the Aldrich sample is charged at room temperature (23 ° C) and its charging current is 'slowly rising' at any time for an overpotential of 5 volts relative to OCV, about 4 hours before falling again. A peak appears. In Figure 20, it shows its discharge behavior at 5 mV and room temperature (23 C). Similar behavior can be seen at constant pressure and overpotential (please note that in this article When referring to the discharge process, the term "overpotential," which means that the applied voltage is lower than 〇CV, is used, and the absolute value of the current rises slowly before falling again for several hours. The material shown in Fig. 6 The discharge capacity _c rate is known to be inferior to the present invention: a nanoscale ion storage material. Therefore, it is apparent from the results of the '々丨Li value in FIG. 9 and FIG. 6 and the result in FIG. Produces low rate performance with discharge. Hummer in Figure 2! to Figure 24 shows the corresponding ριτ day 21 of S9 8 square meters Tak and = square meters / gram of nanometer scale Li Gang 4 and Figure 22 shows 39·8 square eight to eight ancient At the same time, σ ▲ 默 放电 放电 放电 ▲ ▲ 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在55 200843165 27144pif and the voltage is stepped again and the 4^ dimension rises. However, in Fig. 22, it can be seen that the speed is reduced, and usually the sample rate is still significantly higher than this, clearly indicating that the rate and the discharge capacity are not high. . Due to the high discharge rate line rate behavior, the requirements and the ^ ^24 |M, 4〇 ^ conclusions were obtained. ^, and the similar results of the buckle, it can be concluded that the phase diagram in the same figure 3Α and 4Α implies that the lamp changes with temperature. In Figure 25, it shows the hunger and the secret sample and the nanometer. The ριττ result of the scale sample (complex 8 m ^ 2 / gram). In Figure 25, it can be seen that at the high temperature, the fine touch sample still shows that the current characteristics rise slowly in about 4 hours, showing poor charging rate performance. Figure 26 shows the behavior of the discharge rate of 45. (where: the breakdown of the absolute value of each voltage P from the jump is shown to show an improved discharge rate performance. Therefore, it can be seen that for the sample, at 45. The amount of energy that can be recovered at a high discharge rate can be significantly improved compared to room temperature, but the amount of energy that can be stored after high rate charging is substantially unimproved. In Figures 27 and 28, 48.8 squares are shown, respectively. PITT results for charging and discharging of nanometer-scale LiFeP〇4 with a metric/gram specific surface area. In comparison, the material exhibits excellent ττ characteristics of charge and discharge performance. 39·8 m ^ 2 / gram specific surface area Samples are visible the same 56 200843165 27144pif Therefore, this example shows that the charge and discharge capacities will be different at equal C rates. Secondly, at the same c rate, the charge capacity is usually lower, making it comparable to a battery that only needs to exhibit high discharge rate performance. The design of a high charge rate battery requires a set of identical choices.

By reading this disclosure, it will be apparent to those skilled in the art that the present invention may be embodied in other forms than those specifically disclosed. Accordingly, the particular embodiments described above are considered illustrative rainless and non-limiting. The scope of the present invention is as set forth in the accompanying claims, and is not to be construed as an example. 1: Brief Description of the Schematic Figure 1 is a transmission electron microscopy image of a nanoscale disk acid through a ferric ion storage material. 2A and 2B show dark field and bright field scanning transmission electron microscopy images of a concentrated nanoscale lithium iron silicate material, respectively. Figure 2C to Figure 2F show the elemental analysis of c, p, Fe and yt in the sample of Figure 2B. 4 MAP / t is a composition-temperature phase diagram of a conventional Lil_xFeP 〇 4 ion library material according to some embodiments. Figure. Figure 3B is a conventional or roughened LW?ep〇4 material

Li 2 is a nanometer sound according to an embodiment of the present invention [as a composition of the 84 ion storage material - temperature phase diagram. Scale @ Β is the voltage of the known or roughened LiixFep〇4 material _ composition curve 57 200843165 Z/I44pif Figure 1 shows the nanoscale scale yttrium phosphate in Example 2 at various c rates == line graph, the graph includes The initial first charge capacity and said that the human discharge capacity is more than 10% higher than the first charge capacity. 2 6 is the conventional discharge capacity of the coarse crystals at various c rates. = First: The first charge and discharge behaviors are known to be displayed and the discharge capacity of the curve is reduced compared with the first charge capacity. ^ is based on the balance of some real-time groups that are almost completely annihilated: =HxFeK)4 ion storage material relative to the equilibrium or near-equilibrium potential of the electrochemical standard 2 or reference electrode, room temperature in the material The range of the charging capacity of the region of the lower expanded body (4) =, , ^X shows that within this range, the open circuit is〇n=tvoltage, ocv) continuously varies with composition ^ FIG. 8 is a diagram illustrating A balance or near-balanced pair of cells that are almost completely de-radiated: ίίίί Li" ion storage material relative to a standard or reference electrode that reaches an electrochemical lit = a solid solution at room temperature in a nanoscale material The range is indicated by the range of charge capacity of the zone constituting X. Within this range, the composition of the open (OCV) It is continuously changed, rather than being ambiguous. Figure 9 shows the ριττ of a conventional carbon-coated lithium iron phosphate sample after charging. The trace of the electric current and the current. Figure 10 shows the capacity of the electric power during the charging experiment. The capacity of Figure 9 is shown below. Before the large capacity is observed at the platform electric dust, almost no electricity is recorded. 58 200843165 27144pif When the pressure rises Capacity. ^ Figure 11 illustrates 9 battery PITT discharge experiment, in which the first battery = jump from the 3. 8 volt charging voltage to more than the voltage measured at 50% state of charge I pool _ open circuit voltage 5 millivolts; the PITT voltage is low There was almost no battery discharge before Ocv was about 20 volts. Figure 12 shows the charging of the nanoscale Li〇.95F, eI>

It is clear that the solid current indicating charging is clearly visible before the two-phase platform voltage is reached. Figure 13 shows the measured capacity of the battery of Figure 12 for each voltage step during the ριττ charging experiment. Figure 14 shows the erbium discharge experiment of the battery of Figure 12, wherein the first voltage step is from a 3 volt volt battery to a voltage measured at 5 G% state of charge, an open circuit voltage of 5 millivolts; when PIT When the voltage is still above OCV5 耄, the measured substantial capacity is about 8 mAh/g. Figure 15 shows a powder X-ray diffraction pattern obtained from a conventional carbon coated lithium iron phosphate material at 5 〇 % s 〇 c. A powder X-ray diffraction pattern obtained from the nanoscale LiFeP(R) 4 sample of the present invention, measured at 67% soc τ, is shown. A schematic representation of the spatial distribution of space-electricity and defect of a nanometer-scale wheel material in accordance with certain embodiments. Figure 18 is not as good as the volume of Lithium Iron Phosphate. Only 之i's not a ruler. Three Lithium Figure 19 shows the test results using the Swagelok hardware half-cell as in Example 3. 59 200843165 Z7144pif Figure 20 shows the trace of voltage and current after discharge in the PITT measurement of the Aldrich sample described in Example 3, 23t. Figure 21 shows the traces of voltage and current after charging in the PITT measurement at 23t: nanoscale LiFeP04 (39.8 m ^ 2 / gram). Figure 22 shows the trace of voltage and current after discharge in the PITT measurement at 23t: nanoscale LiFeP04 (39.8 m ^ 2 / gram). Figure 23 shows the traces of voltage and current after charging in a PITT measurement of nanoscale LiFeP04 (48.8 m2/g) at 23 °C. Stomach Figure 24 shows the trace of voltage and current after discharge in the PITT measurement at 23t: nanoscale LiFeP04 (48.8 m ^ 2 / gram). Figure 25 shows the traces of voltage and current after charging in the PITT measurement of the Aldrich sample of Example 3 at 4.5T:. Figure 26 shows the traces of voltage and current after discharge in the PITT measurement of the Aldrich sample of Example 3 at 45 °C. Figure 27 shows the traces of voltage and current after charging in a PITT measurement of nanoscale LiFeP04 (49,8 m ^ 2 / gram) at 45 °C. _ Figure 28 shows the traces of voltage and current after discharge in a PITT measurement of nanoscale LiFeP04 (49.8 m2/g) at 45 °C. [Main component symbol description] None

Claims (1)

200843165 27144pif X. Patent application: 1. A kind of transition metal silicate powder with a specific surface area of at least 1:5 m ^ 2 / gram and a lithium content ratio at room temperature ( 23 ° C) The lithium transition metal phosphate composition in the form of a block having the same composition or having a specific surface area of less than about 10 square meters per gram of powder has a lithium content of at least .2 mol%. 2. The lithium phosin phosphate powder according to claim 1, wherein the powder has a specific surface area of at least 20 square meters per gram. 3. The lithium transition chlorinated acid salt of claim 1, wherein the powder has a specific surface area of at least 25 square meters per gram. 4. The lithium transition metal sulphate powder of claim 1, wherein the powder has a specific surface area of at least 3 square meters per gram. The lithium transition metal phosphate powder according to claim 1, wherein the lithium transition metal phosphate has an olivine structure. 6. The lithium transition metal phosphate powder of claim 5, wherein the lithium transition metal phosphate has a composition Li^MPCU, wherein the lanthanum is one or more first column transition metals. 7. The lithium transition metal phosphate powder according to claim 6, wherein the bismuth is iron. A lithium iron phosphate composition which forms a single crystal phase of an olivine structure at room temperature and which has a solid solution composition Li _xFeP04, wherein X is greater than 0·01. 9. The lithium iron phosphate composition of claim 8, wherein X is greater than 0.02. 10. The lithium iron phosphate composition according to claim 8, wherein x is greater than 0.03 in 61 200843165 27144pif. 11. The lithium iron phosphate composition of claim 8, wherein X is greater than 0.04. 12. The lithium iron phosphate composition of claim 8, wherein X is greater than 0.05. 13. The lithium iron phosphate composition of claim 8, wherein X is greater than 0.06. 14. The lithium iron phosphate composition of claim 8, wherein X is greater than 0.07. 15. The lithium iron phosphate composition of claim 8, wherein X is greater than 0.08. 16. The lithium iron phosphate composition according to claim 8, wherein X is greater than 0.09 〇 17. The lithium iron phosphate composition according to claim 8 wherein X is greater than 0.10. 18. The lithium iron phosphate composition of claim 8, wherein the lithium iron phosphate has a specific surface area greater than 15 square meters per gram. 19. The lithium iron phosphate composition of claim 8, wherein the lithium iron phosphate has a specific surface area greater than 20 square meters per gram. 20. The lithium iron phosphate composition of claim 8, wherein the lithium iron phosphate has a specific surface area greater than 25 square meters per gram. 21. The lithium iron phosphate composition of claim 8, wherein the lithium iron phosphate has a specific surface area greater than 30 square meters per gram. 22. A partially lithiated iron phosphate composition of the olivine structure, which is in the chamber 62 200843165 27144pif: a monocrystalline phase with an olivine green structure at a temperature and a phoenix solution group; >©4, wherein ;y is too much to view. For example, Mr. applied for a part of the arborite structure described in Item 22 of Wei Fanpan. Lithium iron phosphate combination Weng..., which is too ‘0:02. 24·If you apply for the part of the stone structure mentioned in the 22nd section of the patent scope, it is too 〇25. If you apply for the olivine knot in the 22nd item of Sai Li Fantu Part of the phosphorus: acid iron button compound, where y is greater than 0.04. 26 coffee to read zero _ Fan Figure 22: increase: the part of the sapphire structure of lithium sulphate - lithium strontium phosphate bismuth -, where: y is greater than Xie. 〇 5. 27. A partially lithiated ferric silicate composition according to the olivine structure of claim 22, wherein: y is greater than: 0.06. 28. For example, a partial lithiated iron phosphate composition of the olivine structure described in the 22nd patent, wherein y is too greater than 0.07. 29. A partially diskized scale of an olivine structure as described in claim 22: an acid iron composition wherein y is greater than 0 < 08. • 30. The olivine structure as described in claim 22 Partially lithiated iron silicate composition, wherein y is greater than 0.09. 3 L is a partially lithiated iron phosphate composition of the olivine structure as described in claim 22, wherein: y is greater than 0.10. The partially lithiated iron ruthenate composition of the olivine structure of claim 22, wherein the bismuth iron phosphate has a specific surface area greater than 15 square meters per gram. 33. as described in claim 22 Part of the olivine structure 63 200843165 z/J^pn 公 锂 锂 磷酸 磷酸 磷酸 , , , , , 射 射 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 大于 3 3 3 The olivine structure is acidified with eight hours of acid composition, and the frontal touch _ iron has a specific surface area greater than = ft / gram. Part of the 22-part olivine structure described above, the lithium iron phosphate has more than 30 square meters. 35. Lithium iron acid composition. The specific surface area of the front gauge / gram. 36·-the clock transition metal sulphate compound, characterized in that, in the case of the basin 6 and the counter electrode, the standard electrochemical cell towel used as the brain electrode, the potential intermittent drip (potentiostatic intermittent titration in the private sequence, in excess After the above-mentioned battery is charged at a constant voltage of 50 mV, the compound exhibits a continuously decreasing charging electric charge. The open circuit voltage is measured after being charged to 5 〇〇/〇 for at least 12 hours. 37. The clock transition metal phosphate as described in claim 36 of the claim, wherein the aforementioned open circuit voltage is measured at 251: after charging to 50% state of charge and remaining at least 12 hours. The lithium transition metal phosphate compound as described in claim 36, wherein the aforementioned open circuit voltage is in a temperature range of about _2 ° C to about 55 ° C 'charging to 50% state of charge and maintaining at least 12 39. The lithium transition metal phosphate compound according to claim 36, wherein the compound is lithium transition metal phosphate υμχΜΡ04, wherein Μ· is one or more A transition metal and X is a value between 64,200,843,165 billion and 1. 40. The range of the patent application The value between 1 and 1. The lithium transition metal silicate salt described in the above item has an olivine structure. Lithium transition metal salt ii-xFeP04, wherein X is a lithium transition metal phosphate compound, characterized in that it is used in a standard electrochemical cell in which the opposite electrode is lithium metal. As a storage electrode: in the constant potential intermittent determination (HTT) program, after discharging at a constant overpotential exceeding the open circuit voltage of 50 mV of the electric 'cell, the compound exhibits a continuously decreasing charging current, the aforementioned open circuit The voltage was measured after charging to 5 〇% of the state of charge and holding for at least 12 hours. 43. The lithium transition metal phosphate compound of claim 42, wherein the aforementioned open circuit voltage is 25. (:, Lithium transition metal phosphate compound according to claim 42 in the charging state to 50% state of charge and maintained for at least 12 hours. The aforementioned open circuit voltage is about -2 ( TC to about 55T: in the temperature range, after being charged to a 50% state of charge and maintained for at least 12 hours. 45. The clock transition metal sulphate compound of claim 42, wherein the compound is lithium Transition metal dish salt Li _xMP 〇 4, wherein Μ is one or more first column transition metals and x is a value between 0 and 1. 46. Lithium transition metal as described in claim 42 a phosphate compound, wherein the aforementioned clock transition metal sulphate® has an olivine structure. 65 200843165 27I44pit 47. The sulphate metal salt acid compound according to the above-mentioned item, wherein the aforementioned compound is LiixFeP〇4, wherein A value between 1 and '48. A clock battery comprising a bell transition metal salt salt compound as described in claim 1, 8, 22, 36 or 42. 49. A method of storing electrical energy, It contains The clock battery of the range of item 48 is charged at a rate of at least 2 C ^ C, and the aforementioned c rate is an average C rate of a current applied for at least 5 seconds. 5 · The stored electric energy as described in claim 49 The method comprises the steps of: (4) the battery according to claim 48 of claim 4 is charged at a rate of C to 5 C. 51. The method for storing electrical energy as described in the scope of the patent application, which comprises Charging under the CC rate of 10C as described in item 48. You Wang Wei 52. The method of storing electric energy as described in claim 49 of the patent application, including the request for the special (4) Charging at C rate. Method for storing electrical energy as described in item 49 of the patent scope, 2. 2 == Range The battery of the bell described in item 48 is at least 54. As described in claim 49 The 0C of the stored electrical energy includes ΪΪ1. The clock battery described in the patent scope is charged at a rate of at least 30 C. y 55. The method for storing electrical energy as described in claim 49, 66 200843165 27144pif Including the scope of the patent application The lithium battery of claim 48 is charged at a C rate of up to 40 C. 56. The method of storing electrical energy as recited in claim 49, which comprises storing the clock as described in claim 48 , and also charge at a C rate of 5 〇 C. H is also at least = · The method of storing electrical energy as described in Shenjing Patent Range No. 49: wherein the C rate is the average current of the current applied for at least 1 second. 盆 CC basin = · as described in claim 49 Method for storing electric energy The foregoing C rate is an average of currents applied for a period of at least 20 seconds = · Method for storing electric energy as described in claim 49 of the patent application = the aforementioned C rate is an average of currents applied for at least 3 G seconds A method of storing and transferring electrical energy, comprising charging a lithium secondary battery as described in claim 48, at a rate of at least 2 C2 C and discharging at a rate of at least 2 C. 61. A method of storing and transferring electrical energy as set forth in claim 6 wherein said charging comprises charging at a rate of at least 5 C up to at least 50 C. The method of storing and transferring electrical energy as described in claim 60, which comprises discharging at a rate ranging from at least 5 C up to at least 50 C. 67