TWI352068B - Ni-based lithium transition metal oxide - Google Patents

Description

1352068 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a powdery nickel-based lithium transition metal oxide which is substantially not manufactured in a low cost process. Further, a nickel-based lithium transition metal oxide is produced by reacting with an inexpensive precursor, particularly LbCO3, as a lithium source. This nickel-based lithium transition metal oxide does not contain LiWO3 impurities and has a low content of =

Solubility test and improve stability in the air. This nickel-based clock transition metal oxide powder is suitable as a cathode active material in a rechargeable lithium battery. The battery containing these cathode active materials exhibits high capacity, high cycle stability, greatly improved high temperature storage stability, and particularly good release and enhanced safety. Wind Cylinder [Prior Art] The cathode active material based on the salt plant has a good prospect of LiCo〇2 in the pool. The price of this dish is t (1) price and the acquisition of the catch / the following increase in the world's Co production Will continue to increase ^. 〇 2. In the battery of the battery 1 nickel demand (2) capacity continued to be mainstream. ϋ为铭矿量 has a greater development of the clock and knows that the price is lower than 1 and the people expect the price to rise. Another – too demanding, the larger market is expected to absorb the battery life of the growth order more easily, and the money is about 2 1352068 mAh/g, which exceeds LiCo02 (about 165 mAh/g). Therefore, commercial batteries with LiNi〇2 cathodes have an increased energy density despite the fact that the average discharge voltage and bulk density are small. However, the following serious problems have hindered the widespread and successful use of LiNi02-based nucleus active materials. (A) Price: It is generally agreed that high-quality LiNi02 cannot be produced by the simple method of manufacturing LiCo〇2, that is, the precursor of the precursor is simply solid-state reaction with LiCo02. In fact, the 'doped LiNi〇2 cathode active material, in which the necessary dopant is 面', the further dopants are Μη, A1, etc., via the likes of Li〇H*H2〇 The mixed transition metal oxide is reacted in an oxygen stream or a synthetic air (i.e., without C〇2) to be mass-produced. In addition, additional steps such as mid-stage cleaning or coating add to the cost of such methods. (B) Safety, Exhaust, Gelation, and Aging: %—Safety: The practicality of LiNi02 is delayed due to concerns about the safety of LiNi07 batteries. The safety of the cathode powder can be slightly increased, for example, by adjusting the cathode powder, or by optimizing the crystal form. Also, the battery design, adjustment, electrolyte, etc. can be used to enhance the safety of the battery. - Storage: The commercial utility of LiNi02 is particularly delayed due to the poor storage and the nature of the oversized basket. A serious problem that has not been solved so far is that excess gas is released during storage or circulation. Excess gas will activate The king valve will open the cylindrical battery and cause the polymer battery to expand. The present inventors have found that the content of the soluble test is related to the release of excess gas, in particular, the amount of U2C〇3 (known by pH titration) and the release of gas 6 1352068 during storage are closely related. Relevance. - Treatment: LiNi〇w Other - Item _ relates to the stability of the cathode material • (When exposed to air, when the gas is under the air, the 02 will quickly deteriorate) and the polymer ^ 'gelling (due to high yang, Lan P - PVDF masses begin to polymerize). These properties are a serious problem in the manufacture of batteries. Many advanced techniques focus on improving the properties of LiNi〇2 base cathode materials and the method of making LiNi〇2. However, the problems of high cost, expansion, poor safety, pH, etc. of manufacturing have not been fully solved. An example of this will be listed as follows: + USP 6, 〇4〇, 〇9〇 (T. Sunagawa et al., Sanyo) reveals a wide range of compositions, including nickel-based and high-profile LiM〇2, this material With - high crystallinity 'in lithium batteries containing electrolyte EC. The sample was manufactured in a small amount of ', using Li〇H*H2〇 as the lithium source. The sample was produced under a synthetic air mixture of oxygen and nitrogen. USP 5,264,201 (J. R. Dahn et al.) discloses a modified #LiNiCb that is substantially free of lithium hydroxide and lithium carbonate. For this purpose, a transition metal hydroxide and LiOH*H2 〇 are used as a clock source, and heat treatment is performed under an oxygen pressure of no c〇2, and the H2〇 content is additionally low. "Volatilized" out of excess • but “volatilization” is a laboratory-scale effect, not a large amount. USP 5,370,948 (M. Hasegawa et al., Matsushita) discloses a method for preparing Μn-doped LiNii_xMnx〇2 (x<45.45), wherein the manganese source is nitric acid, and the source is not a hydroxide or a sulphuric acid clock. . USP 5,393,622 (Y. Nitta et al. ' Matsushita) discloses a process for the preparation of LiNii-χΜηχΟ2 via two-step heating of 7 1352068, including pre-drying, conditioning and final heat. In the case of final heat in an oxidizing gas such as air or oxygen, this patent focuses on oxygen. The method disclosed uses very low temperatures of 55 〇 to 65 〇〇 c and is less than 800 ° C. At higher temperatures, the sample degrades dramatically. Excess lithium is used to make the final sample contain a large amount of soluble base (i.e., a compound of the bell). According to the study by the inventors of the present invention, the observed deterioration due to the presence of the lithium salt was melted between about 700 and 8 〇〇〇c, and the crystal lattice was collapsed. WO 9940029 A1 (M. Benz et al. 'H.C. Stack) discloses a complex preparation method which is very different from the one disclosed in the present invention. This preparation method involves the use of lithium nitrate and lithium hydroxide, and recovers the released nitride gas. The sintering temperature never exceeds 800 ° C and is usually much lower. USP 4,980,080 (Lecerf, SAFT) describes a process for preparing a LiNi〇2-based cathode from lithium hydroxide and a metal oxide at temperatures below 800 °C. In the prior art including the prior art, the LiNi〇2 cathode active material is usually produced by a high-cost method, particularly in a synthesis gas such as oxygen or a synthesis air stream containing no c〇2, and using LiOH*H2〇 , lithium nitrate, lithium acetate, etc., rather than the inexpensive, easy to handle Li2C〇3. Furthermore, the final cathode material leaves a high level of solubility due to thermodynamic limitations, derived from carbonate impurities present in the precursor. In order to remove this soluble base, additional steps such as cleaning, coating, etc. are required, which adds cost. Therefore, it is not necessary to use a LiNi〇2-based cathode active material, which can be manufactured in a low-cost manner from a non-precious precursor such as Li2C03, and has a low content of 8 1352068* content, which is exhibited as a commercial rechargeable lithium battery. Low expansion and improved properties, improved safety and high capacity. SUMMARY OF THE INVENTION The object of the present invention is to completely solve the aforementioned problems. According to the present invention, the foregoing or other objects are achieved by providing a powdered lithium transition metal oxide having a composition of the following formula 1, which does not substantially contain $Li2C03 impurities, and the self-mixing transition metal precursor reacts with Li2C03 in the air by solid state. Prepared:

LixMy02 (1) where MHVTuAk, 'where

The MhNintXNiwMiM/OaCOb condition is 0.65 S a+b 幺 0.85 ^ 0.1 < b <0.4; A is a dopant; • 0 < k <0.05; and x + y = 2 The condition is 0.95 < X < 1.05. * As defined above, the transition metal oxide in the powder consists of a combination of recording, fierce and initial, and has a high amount of nickel, and may further contain less than 5% of the dopant A, as the case may be. The nickel-based lithium transition metal oxide according to the present invention has an excellent stratified structure, and has high sintering stability and substantially no soluble alkali, thereby improving the safety and cycle stability of the cathode active material of the lithium secondary battery. Sex, anti-aging stability, and low gas release during storage. 1352068 Further, the lithium transition metal oxides of the present invention can be prepared in a relatively low cost manner using a mixed transition metal precursor and LizCO3 as starting materials under relatively unrestricted conditions. In the process for producing a lithium transition metal oxide, low-cost LhCO3 is used as a helium source, and an excess of lithium is not used, and heat treatment is preferably carried out in a reactor having a high air flow rate, preferably with a heat exchanger. I [Embodiment] The present invention will be described in more detail. The quantitative chemical LiNi〇2, whose transition metal is composed only of nickel and has a Li:Ni ratio of 1:1, does not exist or is extremely difficult to produce. Conversely, Lh-aNii+aOz lacking Li and doped LiNii zM"z〇2 (M"=c〇, Mn1/2Ni1/2, Al.·.), Li:]V [ratio, Easy to get. In the present invention, only the doped LiNi〇2 is operated, and for convenience of presentation, it is sometimes referred to as "LiNii zM"z〇2" or "doped LiNi〇2" in the present disclosure. . In general, the doped LiNi〇2 may be in the form of a stoichiometric chemical form or in the absence of Li. Therefore, in the present disclosure, the measurement chemistry: • or the Li-deficient form (Li: M < 1:1) is sometimes referred to as J; the amount of chemical LiNi〇2” and “Li^NihO2”. Compared with pure UNi〇2, D, the doped LiNiG2 has a lower tri-content, but the peak has a higher LiCo〇2 or LiMn〇2. In the present disclosure, the word "高·NiUNi〇2" represents the formula "LiNi^lVrzO2" where z is ο.? or higher. Because of its excellent electrochemical properties, it is advantageous to have a metered chemical curry that is 'but not lacking 4'. Samples lacking u have a divergence of 1352068 sub-mixes. The _ sub-mixed sample is the position where the transition metal cations occupy the clock in the crystal inspection and the economy. Li-deficient Li-Ni-oxides are not good because of the poor electrochemical properties caused by the high cation mixing. According to the present invention, the composition of the lithium transition metal oxide must satisfy the special conditions as defined in the above formula 1, which can be as follows or as shown in the first figure. (i) Nii-ab(Ni1/2Mn1/2)aCob and 0.65Sa+bS0.85 (ii) 〇.l<b$〇.4 _ (in) x+y=2 and 〇.95^^1〇 5 Regarding condition (i), when the content of trivalent nickel is excessively high, that is, a+b<〇.65'-doped LiNi〇2 cannot be prepared in a large amount in air, and

Ll2C〇3 cannot be used as a precursor (see Comparative Example 2). On the other hand, when the content of three <Beihan is extremely low, i.e., a+b> 0.85, the doped LiNiO 2 can be prepared in a large amount in air, and Li2C03 can be used as a precursor, however, it is prepared and doped. The volumetric capacity of LiNi〇2 is not competitive with LiCo02 (see Comparative Example 8). Regarding condition (ii), when the content of cobalt is excessively high, that is, b > 4.5, since the amount of cobalt in the horse increases the overall raw material price, and also slightly reduces the reversible capacity. On the other hand, when the content of cobalt is extremely low (b < 0.1), substantially sufficient rate performance and high power density of the battery are achieved at substantially the same time. Regarding the condition Wi), when the content of lithium is excessively high, that is, x > l. 〇 5 ' exhibits poor stability when circulating at a high voltage (U == 4.35 V), particularly. On the other hand, when the content of lithium is extremely low, i.e., χ < 0.95, a poor rate of energy is exhibited, and thus the reversible capacity is also lowered. As previously mentioned, the lithium transition metal oxide may further contain a small amount of 1,352,068. Typically, A1, Ti and Mg dopants are incorporated into the lattice structure. The low doping of these dopants (<5%) helps to improve general safety and storage stability with battery overcharge without significantly reducing reversible capacity. Other industries are known to have 3, 匸 & 21*, 8,? ,? , 6丨, etc., will not be incorporated into the lattice structure, but will accumulate at the grain boundaries or coat the surface. However, at very low doping levels (<1%), low concentrations of these dopants (<1%) may increase stability without lowering their reversible capacity. Thus, various dopants as described in the preceding φ can be used in the present invention. The lithium transition metal oxide of the present invention is subjected to solid state reaction in air in an inexpensive manner. The solid state reaction carried out in air is preferably carried out via a two-step heating procedure 'comprising: (1) between 70 and 950 ° C, a conditioning step under air circulation, and then (ϋ) at a temperature of 85 〇〇 (: and 1 Sintering step between 〇2〇qC. As a raw material for solid state reaction, use lithium carbonate (Li2CO3) and mixed transition metal oxide. Li/O3 is used as a lithium source. Mixed transition metal precursor _ includes (but is not limited to) For example, mixed hydroxides, mixed carbonates and mixed oxides. Here, "mixing" means that a plurality of transition metal elements are uniformly mixed under the original 'sub-level.' One of the features of the present invention is the use of inexpensive raw materials. Or use of raw materials produced in an economical way' and Li2c〇3, which was difficult to apply in the prior art, is used here. MOOH (M = Ni, Μη and Co) is a representative example of mixed transition metal precursors, prior art In the case of ^^;5〇4 and ]^^〇11, the excess ammonia is prepared as a mis-additive additive to obtain a high-density 12 surface: 'Ammonia in wastewater causes environmental problems and must be strict Regulation I see that LiNi02 can withstand the more intense burning, and the relatively low-density M〇〇h of the shell is made by a process that is less awkward and does not use ammonia (no ammonia process). When um〇2, ', 4mLi2c〇3 can not be used as a raw material for the production of the solution. Moreover, even 2^ knife solution will produce C〇2 and cause high-loss LiNi〇2 time division, this pair occurs: should be in the precursor The presence of impurities &&&<>>, while Ll2C〇3 is used as a raw material or as in the case of the present invention, the present invention does not occur anyway. The present invention is substantially free of Li2C〇3. In the disclosure, 'wide use of pH titration to discover or confirm a large number of real, 'fruit' includes the foregoing results. For example, pH titration is performed in the following manner: (4) cathode powder is immersed in 25, water, and fresh (four) is decanted The French word is private; ^ about 2G mlH liquid is separated, and then the clear solution is collected. Then, about 2 〇ml of water is added to the powder, stirred, decanted and collected. The infiltration and decantation are repeated at least twice. First, a total of 1 〇〇 (five) package δ / valley test clear solution was collected. Soluble The content is determined by titration. Add 0.1 Μ HC1 stream to the solution under stirring, and record the pH value as a function of time. The experiment is completed when the pH value is lower than ρΗ=3. Select the flow rate so that the titration takes 20~ 30 minutes. The content of soluble base is such that the value of ρ 低于 is lower than that of 5. The amount of soluble alkali obtained in a certain method is reproducible in this method, but does not depend on other parameters, such as the total time of powder immersion. There are two main sources of 'first, LiNi02 such as Li2C03 and LiOH impurities; the second 'LiNi〇2 surface ion exchanged alkali (H+ (water) order + u + 13 1352068 (surface, overall external) . The second contribution is almost negligible. As previously stated, the lithium transition metal oxide of the present invention is substantially free of Li2C〇3 impurities and only a small amount of soluble base. For example, the amount of the solubility test can be determined by using less than 20 ml of 0.1 M HCl to titrate 200 ml of the solution to a pH of less than 5, wherein 200 ml of the solution contains substantially all of the soluble base, which is repeatedly infiltrated and decanted. G lithium transition metal oxide derived. More preferably, less than 10 ml of 0.1 M HCl. φ In addition, the variation in the manufacturing scale of the doped LiNi〇2 also has an effect. Because the gas transmission kinetics at low partial pressures are very different, a few grams of sample in the furnace differ greatly from a few kilograms of sample. Especially in small quantities, Li will volatilize, while C〇2 will transfer very quickly 'but in a large number of processes' these processes slow down. In this way, the term "massive" in the present invention refers to a sample of 5 kg or more, because when the process is properly amplified, the same gas flow (W/kg sample) is applied to a 100 kg sample, and 100 kg is expected. The samples also have similar behavior. The lithium transition metal oxide of the present invention is preferably produced in a large number of processes, which is very important from a practical point of view. For the solid state reaction in the air above, 'injecting or withdrawing air into the reactor> 乂 achieves a rapid air circulation, which requires 2 m3 of air per kilogram of final lithium transition metal (at room temperature' Volume) 'at least 10 m3 of air is circulated through the reactor during the reaction. In a particular embodiment of the invention, a heat exchanger is used to preheat the incoming air prior to entering the reactor while cooling the effluent air.

In a preferred embodiment, the solid state reaction is subjected to at least two steps, including a temperature adjustment step between 700 and 950 ° C, wherein the transition metal precursor reacts with Li 2 CO 3 to form a LiM02 precursor, and at a temperature of 850 ° C. And a sintering step between 1020oC 1352068, in which a final LiM02 excellent stratified crystal structure is achieved; wherein, in the conditioning step, a large amount of air exceeding 2 m3/kg of LiM02 is passed into a reactor equipped with a heat exchanger for preheating air. . BEST MODE FOR CARRYING OUT THE INVENTION Now, the present invention will be described in detail with reference to the following examples. The examples are intended to be illustrative only and not to limit the scope and spirit of the invention. Comparative Example 1: pH titration of LbCCh impurities in commercial cathode materials I Two batches of "A" and "B" were used to pH titrate the same cathode active material provided by the same supplier. The composition of the cathode material was Li1.05M0.95O2 and M = (Mni/2Nii/2) 〇.83Co〇. This cathode material is used in a pilot plant battery. At the high temperature storage of these batteries, the battery containing the "A" batch released an unacceptable amount of gas, but the "B" batch did not. In addition, the two batches examined in their respective faces, such as crystal phase, BET surface area, crystal size, particle size, reversible capacity, rate efficiency, crystal structure, lattice parameters, cation mixing, etc., are identical. Or almost equal. φ However, the results of pH titration are quite different. In comparison, the pH side writing of the commercial sample "C" having a composition of LiNi]/3Mn1/3Co1/302 was also measured.

* Because the tester battery containing this sample shows a particularly low gas release. pH. The results of the titration experiment are shown in the second figure. Referring to the second figure, sample "A" showing strong gas release contains an excess of soluble base. Sample "C" with additional stability is substantially free of soluble base. The shape of the soluble base can be obtained from the shape written on the side of the pH titration. Referring to the third figure, Li2C03 will show two plateau areas, but LiOH has only a single plateau area. Therefore, the soluble base of sample "A" is mainly identified as Li2C03. Sample "B" <9) 1352068 A base containing a small amount of LhCO3 type and a small amount of a base of the type 11 may be derived from a surface molecule or an ion exchange reaction of lithium with water and the outermost region cathode particles. The knowledge about soluble inclusions is a powerful tool to guide the development of cathodes with enhanced storage stability. However, in order to define what kind of solubility is present, it is important to measure the pH side. For example, it is not recommended to measure pH side writing only in Ep 1 317 〇〇8 A2 (S. Miasaki, Sanyo), because only a small amount of φ quantity of Li0H type impurities (very harmless) will cause significant and harmful effects. It

A higher positive yang value is obtained for the LhCO3 impurity. Therefore, this experiment clearly shows how useful pH titration is to get information about the solubility test. Comparative Example 2: Thermodynamic stability of high Ni LiNiO. In this experiment, the thermodynamic stability of commercial 1% LiNi〇2 was investigated. The composition of the mouthpiece 疋LiNiojCoo^MnojC^ ' can also be expressed as LiNi χΜχ〇 2 and χ = 0.3, that is, M = Mn1/3Ni1/3Co1/3. • Thermodynamic stability is measured by heating the aforementioned cathode material in air. Each 50 g sample was heated to 5 Torr. (: (48 h), 750. 〇800oC, 850°C, 900〇C and 950°C (36 h). Perform X-ray analysis to obtain high-resolution detailed lattice parameters. Rietveld actuarial analysis (Rietveld refinement) Cationic mixing was obtained. The crystal phase was measured by field emission electron microscopy (FESEM). All samples were heated to Tk750 〇C ' X-ray analysis showed continuous deterioration of the lattice structure (increased cation mixing, lattice constant, and reduction) c:a ratio). In the air containing micro-C〇2, the decomposition of 'high-Ni LiNi〇2 will follow the reduction of trivalent nickel as shown in the table 1352068 « Table.

LiMUi02 + C02 -> α Li1.xM1+xl--〇2 + b Li2C〇3 + c 〇2 f In this process, the titer of U2C〇3 impurity is established by the titration of PH. In the fourth graph, the micrograph of the commercial sample received is compared to the same sample heated to 850 °C. Referring to the fourth figure, it is heated to > (4). The sample of ^ has collapsed. In an additional experiment, at 9〇〇. At the time of €, it was observed that the first-order particle element was completely disintegrated into a single primary crystal. 'In general, the commercial LiNi〇2 cathode material is thermodynamically unstable during heating in air. In particular, U2C〇3 is formed and stunned to separate the grain boundaries, so that the primary particles lose contact and the secondary particles collapse. 3 Therefore, when there is a small amount of partial pressure of C〇2 in the air, it is impossible to manufacture Li_Ni_ oxide with high Ni content due to thermodynamic constraints, that is, LiNihMxO2 in air, X > 〇.7 . This experiment also confirmed that it is impossible to use UAO3 as a precursor in the traditional process, because the decomposition of U2C〇3 will form LiM〇2 and release C〇2' even if it is kinetically hindered at low partial pressure. Block further decomposition.曰 fe- comparison. Example 3: * In this experiment, it was investigated whether a high-Ni LiNi02 can be obtained in a large number of ways, both chemically and without impurities, via a simple method involving solid-state reaction with oxygen. In the prior art method, as a precursor for preparing a LiNi〇2-based cathode, LiOH*H2〇 and a Ni-based transition metal hydroxide are generally used. However, both precursors typically contain carbonate impurities. Technical grade LiOH*H2〇 usually contains more than 1% of LbCO3 impurities, and Ni(〇H)2 also 17 1352068 contains C〇3 anions because it is made of Ni-based salts (such as Nis〇4) and such as NaOH. The alkali-based coprecipitation is carried out, wherein the technical grade Na〇H contains NazCO3 and the CO3 anion is more easily inserted into the Ni(〇H)2 structure than the 〇H anion. When the precursor mixture is conditioned under oxygen, lithium hydroxide and The transition metal hydroxide reacts to form Lii-xM1+x〇2, but all of the carbonate impurities are trapped as Li2C〇3 impurities. Further, when conditioned under oxygen, the decomposition rate of Li2c〇3 impurity 并 is not sufficient, and at 8 〇〇 °C, the stoichiometrically high 丨UN丨2 is very unstable. As a result, LLCO3 does not decompose but is additionally formed as will be explained below. Thus, the pH titration of the commercial high-seven i LiNi〇2 composed of LiNi〇.8Co〇2〇2 is as shown in the fifth figure. The curve (A) in the figure shows that the obtained drip 疋 curve (B) of LiNi〇.8Co〇.2〇2pH was heated at 8 ° C for 24 hours in a pure oxygen stream. The curve (C) is the copy of the curve (A), which can better show the similarity of the shape between the curve (A) and the curve (B). The flow rate is greater than 2 1 / min and the sample weighs 4 〇〇 鲁 g. Analysis by pH side shows that the content of Li2C〇3 is exactly the same before and after the heat. Obviously, the LhCO3 impurity did not react at all but formed a small amount of Li2〇 (a slight decrease in the Li content in the crystal structure of *LiNi〇2, observed by observation. A slight increase in cation mixing, a slight c:a ratio The reduction was confirmed by a slight decrease in the unit lattice volume obtained by X-ray analysis. The conclusion is that the conventional method (heating Ni(OH)2 and LiOH*H2〇) does not produce a large amount of chemically and impurity-free LiNi〇2 with a "general" oxygen flow or synthetic air. Here, the "normal" oxygen flow means a gas flow of less than about 1 m3 per kilogram of cathode material reactor in the reaction. When 18

LiNi〇2 contains significant curry 3 impurities, or when it is avoided, % LiNi〇2 will become lithium-deficient (ie, cation mixing). This is for Li2C〇3 coexisting with “A. C〇2 ^衡二压1^ "X" is strongly increased, so the inverse kinetics towards the metering chemical LiNi〇2 is limited by the reason for the poor transmission of CO 2 gas at low pressure: only when there is enough lack of correction, ie When "x" is large enough, the higher % equilibrium partial pressure causes C〇2 to be clearly transported away from the sample, allowing Li2C〇3 (C03 anion impurity derived from the precursor) to be effectively decomposed. Otherwise, such as the prior art improvements, the process cost can be increased by inputting more oxygen or synthesizing air at a lower temperature. The middle cleaning process in the hot zone is 2 effective removal of unreacted Li2C03, but it will also increase the process cost considerably: -Ni LiNiO, empty _ 稳宏么商问-Ni LiNi〇2 in exposure to wet The results of pH titration before and after air are shown in the sixth graph. The commercial UNi〇2 series LiAl0.02Ni0.78C〇〇2〇2, the extra 3 has less than 1% bismuth compound, and the results of the sixth graph show that the storage 'solubility test content is particularly low. It is expected that the sample is a manufacturer's Z-pure pure insulator (ie, no c〇3 anion) under oxygen, or at least two steps are used to make an inter-panel cleaning procedure to remove Li2〇^Li. 〇H: Quality. It is possible to add hydrazine to form a highly stable BaC〇3 to capture the remaining C〇3 anion, which is a costly process. When the remaining one is exposed to the air, a considerable amount of soluble alkali is mainly 142 (: 〇3 starts ^ / into. The result shows that commercial LiNi 〇 2, even if the initial Li 2 c 〇 3 impurities contain less than 'in the air instability And decomposed at a considerable rate, and a considerable amount of LUCO3 impurities were formed during storage. 1352068 Comparative Example 5: Commercial film f high-NiLiNiO? air test Another commercial high-Ni LiNiCb having a LiNio.g Mno.os CoiusO2 sample composition. The preparation method of the sample includes surface coating of a1p〇4, _, moderate heat treatment, which is a high-cost process. The coating may be immersed in a dip-coating process, and the side effect is to dissolve excess Li2C 〇丹In the heat treatment, 'AIPO4 reacts with excess lithium to form .. Al2〇3 (or LiA102). Therefore, the Li2C〇3 content of the sample is low, and the surface of the cathode is deficient in lithium. The test results confirm the polymer battery. The lower swellability. The pH titration results confirmed the initial low content of U2C〇3 (0·1M HC1 per 1 〇❿ ^ ml), which is very similar to the comparison of the fresh sample of the curve of Example 4 (A). Record two sets of storage in similar comparative example 4 The profile of the pH after the wet chamber. A slightly lower Li2C〇3 (8〇~9〇 formation rate compared to Comparative Example 4 was observed. The results show that the high-Ni LiNi〇2 coating does not increase storage in the air. Stability, in addition, such as the stability of the cycle stability and rate performance; poor properties 'may be the cause of lithium-deficient surface. Bay FeL compared with Example 6: charging high-NiLiNiO; ^ ^ full DSC measurement results in the first Figure 7. When measuring, the cathode is the button battery of the coffee (and the anode is the bell metal). After charging, the D is decomposed and inserted into the fully sealed DSC tank, and the person is electrolyzed. The cathode always contains (4) ~ mail 'and electrolyte The amount is approximately the same. Then the 'exothermic reaction system is mainly the cathode limiter (only part of the electrolysis f can be completely burned out of all the oxygen of the cathode). The Dsc measurement is performed at a thermal efficiency of 0.5 K/min. In (A) modified by A1/Ba, UNi〇2 and (B) to 20 1352068

In both AlP〇4-coated LiNi〇2, a strong exothermic reaction occurs at a relatively low temperature. (A) The heat in the middle discharge exceeds the limit of the device, and the total amount of heat release is large, and more than 2000 kJ/g is large, indicating that the commercial high-Ni LiNi〇2 is not safe. While there are many prior art and patents that further attempt to increase the performance of high-Ni LiNi〇2, these methods are expensive and often insufficient. Otherwise, there is a disclosure to encapsulate high _Ni LiNi02 with SiOx protective film (H. • Omanda, T. Brousse, C. Marhic, and D. M. Schleich, J.

Electrochem. Soc. 151, A922, 2004), but its electrochemical properties are very poor, and in this regard, the inventors of the present invention have studied sealing via LiP03 glass. Even if a complete particle coating is achieved, the air stability is not significantly improved and the electrochemical properties are poor. Comparative Example 7: Electrochemical 輋 of commercial high-NiLiNiO, the results of electrochemical test properties of different high-Ni LiNiO 2 materials were compiled in Table 1 below. The test was carried out at 60 ° C and C/5 charge and discharge rates. Charging voltage • 4.3 V. Referring to Table 1, except for the sample (B), the cycle stability was poor. The poor cycle stability of sample (C) may be caused by a surface-deficient clock (previously known in the prior art literature for cation mixing of lithium nickel oxide (ie lack of lithium) • poor power retention). Samples (A) and (B) are all metered chemically, but only sample (B) is low in Li2C〇3 content. The presence of Li2C03 does not cause the exhaust to decay (maybe at 4.3V, Li2C03 slowly decomposes and the crystal lattice loses electrical contact). Therefore, the problems of safety, poor air stability, high Li2C03 impurities and high process cost have not been solved in the prior art methods.

21 A 1352068 <Table 1> High-State LiNi〇2 Electrochemical Properties (60oC, C/5-C/5, 3.0-4.3V) (A) LiNi〇gCo〇.2〇2 (B) via Al/Ba - Modified (C) coated A1P04 Described in Comparative Experiment 3 Comparative Experiment 4 Comparative Experiment 5 Metrology Chemistry Li: M Metering Stoichiometric Chemistry Surface Li Li2C03 Impurity High and Low 25 °C Capacity 193, 175 mAh/g 195, 175 mAh/g 185, 155 mAh/g C/10, C/1 capacity loss 30% per 100 cycles 11% per 100 cycles per 100 cycles &gt; 30% Comparative - Example 8: Commercial low-Ni LiNiO Xuan Jin. Test commercial LiM02 'JV^NiwMn^h.xCox, X is 0.17 and 0.33 respectively. The crystal phase densities are about 4 7 and 4 76 g/cni3, respectively. Both materials have a discharge capacity of 157 to 159 mAh/g at a C/10 rate (3 to 4.3 V).

The LiCo02 crystal phase density was 5.04 g/cm3 and the discharge rate was 157 mAh/g. When x = 0.17, the volumetric capacity of the cathode corresponds only to a density of 93% LiCo02, and the density of the Ludx x = 0.33' cathode corresponds only to 94%. Therefore, it can be confirmed that the material volume capacity of the material having a low nickel capacity is not good. Example 1: Sintering Stabilization • The mixed hydroxide MOOH was used, and its niobium was Ni4/]5 (Mn1/2Ni1/2) 8/15. 〇〇. 2 as a transition metal precursor for the preparation of nickel-based LiM02. The composition of the final LiM〇2 transition metal is marked with an asterisk in the first figure. The mixed hydroxide was mixed with LifO3 (metering stoichiometry: Li: M = 1.02:1) to prepare an intermediate sample, and the resulting mixture was heated to 700 °C in air. Intermediate samples (about 50 g each) are different under normal air, 700 to 10 °C

22 1352068 Sintered at temperature for 15 hours. Increased sintering stability was observed at all temperatures. The secondary particles remained unchanged, and no disintegration into single crystals was observed in Comparative Example 2. The grain size increases as the sintering temperature increases. X-ray analysis showed that all samples had a well-layered crystal structure. The unit lattice volume did not change significantly with increasing sintering temperature, confirming that there was no significant oxygen deficiency, a significant increase in cation mixing, and no substantial lithium volatilization. The best electrochemical properties are obtained in a sample sintered at about 900 ° C, preferably having a BET surface area of about 0.4 to 0.8 m 2 /g. The obtained crystal phase data are shown in Table 2 below, and the FESEM micrograph is shown in the eighth chart. This experiment shows that despite the use of Li2C03 and sintering under air, LiM〇2 with excellent stratification structure and metering chemistry is obtained, and further, excellent air sintering stability is obtained. <Table 2> Crystal phase data sintering temperature (A) 850 ° C (B) 900 ° C (C) 950 ° C (D) 1000 ° C Unit lattice volume 33.902 A3 33.905 A3 33.934 A3 33.957 A3 Normalization c: a Ratio c:a/24A〇.5 1.0123 1.0124 1.0120 1.0117 Cationic mixing from Rietveld actuarial analysis 4.5% 3.9% 4.3% 4.5% Comparative Example 9: Sintering stability of high Co samples using mixed hydroxide MOOH, M = Ni0.25 (Mn1/2Ni1/2) mCosm as a precursor. The content of trivalent nickel in LiM02 is almost the same as in Example 1 23 1352068. A survey as in Example 1 was conducted. Basically, the sample can be sintered in the air without obstruction. The crystal phase data is organized in Table 3 below. It seems that the sintering stability is very close to the LiNi02 (M = Ni4/15 (Mn1/2Ni1/2) 8/15C〇〇.2 obtained in Example 1. It is expected that the high cobalt amount will hinder the cation mixing, but surprisingly the cation mixing Very similar or higher. Unfortunately, because of the high cost of cobalt raw materials, high cobalt samples are more expensive. In addition, additional electrochemical tests show that the reversible capacity is lower than in Example 1. Therefore, the range of the composition cannot Too much cobalt is as shown in the first figure, which is a preferred range for the present invention. <Table 3> Crystal phase data sintering temperature (A) 900 ° C (B) 950 ° C (C) 1000 ° C unit cell volume 33.445 A3 33.457 A3 33.514 A3 Homogeneous c:a ratio c:a /24λ〇.5 1.0144 1.0142 1.0154 Cationic mixing from Rietveld actuarial analysis 3.3% 6.3% 6.6% Example 2: Lithium chemical dose range is different Li: Deuterium ratio The sample was prepared from MOOH of Ni4/15 (Mn1/2Ni1/2) 8/i5CoG.2. Li2C03 was used as the lithium source. Seven samples, each weighing about 50 g, had a Li: Μ ratio of 0.925 to 1.12. Between the two steps, the sample is first conditioned at 700 ° C, and then sintered at 910 ~ 920 ° C. Under normal air There is heat treatment, and then the electrochemical properties are tested.24. The crystal phase data is provided in Table 4. The unit lattice volume changes smoothly with the Li:Μ ratio. The ninth graph is the crystal phase diagram, and all the samples are arranged on a straight line. The tenth graph shows the results of pH drop & the amount of soluble time increases slightly with the ratio of Li : μ 'but the total amount of soluble test is less. The solubility test is probably from the surface test (ion father change), instead of the comparison example 1 The decomposition of Li2C03 impurities was observed. This experiment clearly shows that the cathode material is within the metrological chemistry range, and an extra clock is inserted into the crystal structure. Therefore, 〇2 (: 〇3 does not exist in the second phase) f Using Li2C03 as a precursor and sintering in air, a metered chemical sample without LiAO3 impurities can be obtained. &lt;Table 4&gt; Crystal phase data sample ABCDEFG Desired Li:M ratio 0.925 0.975 1.0 1.025 1.05 1.075 1.125 Unit lattice volume 34.110 A3 34.023 A3 33.968 A3 33.921 A3 33.882 A3 33.857 A3 33.764 A3 c:a ratio 1.0117 1.0119 1.0119 1.0122 1.0122 1.0123 1.0125 Cationic mixing 8.8% 6.6% 6.7% 4.0% 2.1% 2.5% 1.4% ' At Gas using a large number of products prepared • a group of about 5 kg of LiM〇2. The precursor is Li2C〇3 and mixed hydroxide 1^0011, and the niobium is Ni4/15 (Mni/2Ni1/2) 8/15c〇(). Preparation method ‘ There are three conditioning steps. Heat to 70 ° C to prepare a U: precursor with a 1:1 ratio. The furnace is a chamber furnace with a volume of about 20 liters, and the sample is placed on a high temperature steel plate. The precursor was sintered at 9 〇〇〇c for 10 hours, and air was blown into the furnace during sintering, and air exceeding 1 〇 m3 was blown into the furnace during sintering for 25 hours. The unit lattice constant was obtained by X-ray analysis after sintering and compared with the target value. The target value is the unit lattice volume of the sample of Example 2 with the best electrochemical properties. The pH titration of the sintered sample showed a side note very close to the sample of Example 2 (E), demonstrating that the 5 kg sample is substantially free of Li2C03 impurities. A small amount of Li2C03 was added to ensure that the target unit lattice volume was reached after the final sintering. The final conditioning was carried out at 900 ° C in air. The ICP analysis confirmed that the final stoichiometric ratio of Li to lanthanum was very close to 1.00. The unit cell volume falls in the target zone. Figure 11 reveals the SEM micrograph of the resulting cathode material, while the twelfth map is the Rietveld actuarial analysis. Referring to these figures, the sample has high crystallinity and excellent stratification. pH titration confirmed that there was no Li2C03 impurity. Less than 10 ml of 0.1 M HC1 is used to titrate 10 g of the cathode to pH below 5, corresponding to a content of Li2C03 impurity of about 0.2% by weight or less. Therefore, this experiment shows that the quantitative chemical LiM02 is NiwisCMniuNimh. A large straight sample of /isCooj, without Li2C〇3 impurities, can be obtained by solid state reaction of mixed hydroxide with Li2C03. However, it is necessary to drive the general air into the furnace to support the transmission of gas. #鲛Example 10: No air was blown. The same method as in Example 3 was used to prepare LiM〇2 in excess of 5 kg, except that air was not blown into the furnace during sintering, and there was a limit through the opening of the furnace door of about 10 cm in diameter. The air circulation. After sintering, a unit cell volume was obtained by X-ray analysis. This unit lattice volume is slightly lower than the target, meaning that the LiM02 phase is slightly deficient in Li and confirmed by pH titration. Specifically, it is necessary to titrate the sample to a pH below 5, which corresponds to a significant content of about 1% by weight of the Li2C03 impurity, in excess of 26's 1352068 50 ml of 0·1Μ HC1. Therefore, this experiment shows that the natural circulation of air is insufficient and the lack of artificial air flow causes the reaction to be incomplete, making the unreacted Li2C03 a impurity. Example 4: The exchange of air into a large number of reactors at T = 800 to 900 °C consumes φ extra energy, in which case hot air is released into the environment after the reaction. The air flow per kilogram of sample requires at least 2 m3, preferably 1 〇 m3. 2 m3 corresponds to about 1.5 kg at 25 °C. The heat capacity of the air is approximately 1 kJ/kg °K and the temperature difference is approximately 800K. Therefore, at least 33 kWh per kilogram of final sample is required to heat the air. If the air flow is 10 m3, it takes about 2 kWh. Therefore, the extra heat energy cost usually accounts for about 2 to 10% of the total cathode sales. The use of heat exchangers to exchange air significantly reduces the extra heat energy costs, and crying with heat exchange also reduces the temperature gradient in the reactor. To further reduce the temperature gradient, it is recommended to provide multiple air streams simultaneously into the reactor. Compound _5: A large number of battery test 2 • Quantitative chemical LiM02, M=Ni4/15(Mni/2Ni1/2)8/15Co〇2, base. This is free of yttrium (7)3 impurities, as disclosed in Example 3. LiM〇2, electrochemical properties were tested in the form of a button cell with lithium metal as the anode. The cycle was carried out between 3 and 4 3 V, mainly at 25 ° C and 60 ° C with C/5 as the charge and discharge rate (1 C = l5 〇 mA / g). An improved cycle stability was observed as compared with the high NiLiNi〇2 cathode material of Comparative Example 7. The crystal phase density of LiM〇2 based on nickel was 4.74 g/cm3 (LiCo〇2: 5.05 g/cm3). At C/20, the discharge capacity exceeds 27 1352068 over 170 mAh/g (LiCo〇2: 157 mAh/g). As a result, the volumetric capacity was higher than that of LiCo02, which was significantly higher than that of the lower Ni cathode material of Comparative Example 8. In Table 5 below, the total electrochemical properties obtained are listed. In the thirteenth figure, the resulting voltage side write, discharge curve, and cycle stability are disclosed. &lt;Table 5&gt; Electrochemical properties of LiNi02 Capacity retention after 100 cycles (inferred value) C/5-C/5 cycle, 3.0-4.3V First charge capacity 3.0-4.3V, C/10 discharge capacity 25°C 60 °C 25°C, C/1 25°C, C/20 60°C, C/20 &gt; 96% &gt; 90% &gt; 190 mAh/g 152 mA/g 173 mAh/g 185 mAh/g

Example 6: DSC of a large number of samples The safety of the metrology chemistry 1^1^02 was tested by DSC measurement, and the enthalpy was Ni4/15(Mn1/2Ni1/2)8/15Co0.2, as disclosed in Example 3 Li2C03 Impurity of LiM〇2. The results are shown in Figure 14. Referring to Fig. 14, the total heat capacity is low, and the temperature at which the exothermic reaction starts is high. Therefore, the safety is greatly improved as compared with the high Ni cathode material of Comparative Example 6. The polymer thunder of the large sputum sample. The quantitative chemical LiM02' is NiN4/15(Mn1/2Ni1/2)8/15C〇0.2, as in Example 3, it does not contain Li2C03 impurity, and the 383562 polymer of the experimental plant The battery was tested for electrochemical properties. The cathode was mixed with 17% LiCoO 2 and the cathode slurry 28 1352068 was a slurry based on NMP/PVDF. Additions for the purpose of preventing gelation are not added, i.e., prevention of increased viscosity. No gelation was observed during the preparation of, for example, the coating. The anode is a MCMB' electrolyte that is a standard commercial electrolyte and contains no additives known to reduce excessive expansion. The fifteenth figure shows the cycle stability at 25 〇C (〇·8 c charge, 1C discharge '3~4V, 2V). Additional cycle stability was achieved at room temperature (91 〇/〇 at C/1 rate after 300 cycles). The formation of the impedance is small, and the cycle stability is super. The more similar the LiC〇〇2 battery. This can be explained by the comparable, large:!: irreversible capacity of high NiLiNi02, additionally providing the clock consumed during the anode SEI cycle. Also measure the amount of gas released during storage. After 4 hours of 完全^ full charge (4.2 V) storage, only a very small amount of gas was released, as shown in Fig. 16, only a slight increase in thickness was observed. The increased thickness is between or less than the expected value of a good LiCo〇2 cathode under similar conditions like a battery. This test provides a very satisfactory result about the stability and storage properties of 1^102, 14 = Ni4/15 (Mn1/2Ni1/2) • 8mC〇Q·2 ', making this cathode material for LiCo〇2 Very competitive. Impedance of sample voids * Measured chemically, nickel-based, as in Example 3, UMOX without Li2C03 miscellaneous, its air stability, and is compared with high nickel LiM02. Three pH titration measurements were performed. In the first measurement, fresh samples were measured. The content of glutamine in the mouth can be. In the second and third measurements, the amount of soluble alkali in the storage &amp; sample was measured. The sample was stored in a humid battery containing a large amount of hydrocarbon 29 1352068 air at 60 ° C for 17 hours or three days. Figure 17 shows the results. LiM〇2 with M=Ni4/15(Mn1/2Ni1/2)8/15Co〇.2 (Example 7 '17th) and high nickel samples (Comparative Example 4, Figure 6) are stored in the same humid chamber in. Referring to Fig. 17, LiM02 of M = Ni4/15(Mn1/2Ni1/2)8/15Co〇.2 is more stable in air. Its decomposition kinetics is about 1/5 of that of a high nickel sample. Here, by careful X-ray examination, the φ wave of Li2C03 impurity in the high nickel sample was shown, but the diffraction peak of Li2C03 was not observed in LiM〇2 of M^NU/MMnmNimh/bCoo.2. Example 9: Unstable transition metal precursor The mixed hydroxide used in Example 3 had a high tap density (&gt; 2.0 g/cm3) from MS04 and NaOH in excess ammonia (error) Coprecipitation was prepared by adding 'additives'. Ammonia in wastewater causes environmental problems and must therefore be strictly controlled. Therefore, the use of ammonia should be avoided to reduce process costs. However, it is impossible to have a less expensive ammonia-free process to produce a high density of mixed hydroxide. Under controlled pH conditions, a mixed MOOH of more than 1 kg was prepared by co-precipitation of MS04 with NaOH at 80 ° C with M = Ni4/15 (Mn1/2Ni1/2) 8/15C〇Q.2. A mixed hydroxide having a narrow particle size distribution is obtained. The resulting hydroxide has a knock-tightness of about 1.2 g/cm3. These hydroxides produced via less expensive processes are suitable for use in LiM〇2 to withstand more stringent sintering conditions, i.e., they have surface sintering stability. The MOOH prepared in an ammonia-free process was used as a precursor for the production of 1 kg of LiM〇2 in a two-step conditioning process at a sintering temperature of 930 °C. The preparation procedure was carried out under air and the lithium source was LUCO3. Figure 18 illustrates the precursor hydroxide = 舆 final LiM 〇 2 sample. Due to the strict sintering, the grinding step is required to cause some particles to be broken, but the particles do not disintegrate as high Ni_LiM〇2 (Example 2). The properties (pressure density, soluble alkali content) of the obtained powder were tested. 25 〇c and 6 使用 were used in the button cell (Li anode) (3C cycle test electrochemical properties, the properties of which are very close to those disclosed in Example 5. This experiment shows that due to its excellent sintering stability, it can be LiM〇2 based on • Non-expensive process with open space and U2C〇3 and low-cost mixed hydroxide with low density. iAlO : Visibility of pH titration is tested by ΡΗ titration test 5 g commercial metrology chemistry High Ni LiM02 (Μ~NiojCow) ('Sample A') and Example 5 of 5 g metering chemistry of LiM〇2^^^(10)(iv) 'Heart to' sample is similar to the above procedure. Firstly by repeated infiltration and The solution was decanted to obtain 1 〇〇ml of solution, and then the pH side of the solution was monitored by titration of 〇1M HCl until the pH was less than 3. The amount of 0.1 MHC1 reaching PH=5 was 23 m^3 w. The titration was 1 〇g. The 20〇1111 solution obtained by the cathode reaches 1)11 is 5 of 11 (the amount of 1 is doubled. In this experiment, the result of pH titration is the amount of 1^1 (ml) required to titrate 1〇g of the cathode. Indicates that each is 46 and 6 ml/10 g. The reproducibility of the experiment is good. When the cathode powder is in the solution decantation period Infiltration for a longer period of time, similar experiments will give the same amount. It is important to know how much solubility test is in the solution, which is measured by pH titration of the remaining powder. After the solution is separated, the cathode powder is immersed in The pH side of the resulting slurry in 100 ml of water was obtained by adding 0.1 M HCl. In 31 1 1 352 068 Sample A, approximately 20 ml of 0,1 M HCl was used per 10 g of cathode to bring the pH to less than 5. On the one hand, sample (B) uses less than 1 ml (per μg). Thus, in sample A, there is about 67% soluble alkali in the solution, but in sample B, there is more than 80% solubility in the solution. Also whether the survey results are related to the titration rate. If the HC]b is extremely slow (ie, the titration is more than 5 hours), the deviation on the pH side mainly occurs when the pH is less than 5, and these deviations may be due to slow Ion exchange process (H+ of the solution UV solid UV However, the general rate of this process can be: slightly (ie, minutes). Experiments have shown that the solubility test is more reproducible. During the repeated decantation of the solution, the test is easy to dissolve. Therefore, in essence ^ soluble (four) in solution (four), Especially when the total amount of soluble base is not too high

The preferred embodiment of the invention is not to be construed as limiting the scope of the invention. Η [Simplified description of the drawings] The foregoing and other objects of the present invention, together with the accompanying drawings, will be easier to clarify: from the bottom of the object, compared with the (four) base (four) metal oxide map: The solubility test of the commercial cathode material of Comparative Example 1 was compared. H; The third figure is a legend of the standard postal code for the soluble test Li0H.H20 Yucheng 03. The fourth panel is a FESEM micrograph of a commercial high-off LiNi02 of Comparative Example 2, wherein (A) is FESEM of the obtained sample, and (B) is FESEM of the sample after heating to 850 ° C in air. The fifth figure is a comparison of the standard pH drip of the commercial high-Ni LiNi02 of Comparative Example 3, where (A) is the obtained sample, and (B) is the sample after heating to 8 〇 ^ C in an oxygen atmosphere, (c) For the control group. The sixth figure is a decomposition rate diagram of the commercial high _Ni LiNi02 of Comparative Example 4, which was stored at 9 〇〇/ in air at 60 °C. The humidity chamber was titrated with pH, wherein (A) was the obtained sample, (B) was the sample stored in the humidity chamber for 17 hours, and (c) * was the sample remaining after 3 days in the diffuser chamber. The seventh figure is a comparative example of the DCS measurement of Example 6, wherein (A) is commercially available with A1/Ba adjusted LiNi02, and (B) is commercially coated with A1P04.

LlNl〇2 ' where the Dcs burn test is to measure the safety of the sample and the stability of storage. The eighth picture shows the nickel-based LiM02 after sintering in Example 1.

FESEM micrograph (X 2000); A) 850oC, (B) 900oC, (C) 950oC * and (D) l〇〇〇〇c. ‘The ninth figure is a crystallographic diagram of Example 2 with different Li:M ratio samples. • Figure 10 is a sample pH titration of a sample with different Li:M ratios for Example 2. Tenth - Figure is an SEM micrograph of the cathode active material of Example 3. Figure 12 is a Rietveld actuarial analysis of the sample X-ray diffraction pattern of Example 3. Figure 13 is a graphical representation of the electrochemical properties of the recording-based LiM〇2 prepared in air using LhCO3 in Example 5, where (A) is a graph of voltage side write rate performance at room temperature (cycle U7). (B) is at C/5 rate, 25. (: and C〇. The legend of the underlying stability of the ring (3.0_4.3V)' (C) is written on the discharge side of cycle 2 and cycle 31 of the cycle of (9)% cycle (C/10 rate). The fourteenth figure is the result of the DCS safety test of the high-Ni LiNi〇2 of Example 6. ". The fifteenth figure is the result of the electrophysical property test of the polymer battery of Example 7. The sixteenth figure is the example 7 A legend of a polymer battery that expands during high T storage. Figure 17 is a graph of air stability measured by pH titration of a large number of samples of Example 8, wherein (A) is a fresh sample and (B) is a storage 17 After the hour, ° (C) is the sample after 3 days of storage. The eighteenth figure is the microscopic legend of the precursor SEM (χ 5000) and the final cathode material of Example 10, where (Α) is not responsible The precursor of the ammonia-free process has a low density, and (Β) is LiM〇2 which is made from Li2C〇3 as a precursor in air. [Main component symbol description] None.

34

Claims (1)

1352068 X. Patent application scope: j Bulletin revised version Date of revision: 2011/8/9 1. A powder lithium transition metal oxide having the composition of the following formula (1), which does not contain LLCCO3 impurities and is in the air The mixed transition metal precursor prepared by the intermediate is prepared by solid state reaction with LizCO3, wherein the mixed transition metal precursor is a mixed hydroxide, a mixed carbonate or a mixed oxide, and the mixed transition metal precursor The transition metal element contained is homogeneously mixed at the atomic level: LixMy02 (1) where M = M'i-kAk 'where MSNiba-JNimMnWaCob, the conditions are 〇.65Sa+bS〇.85 and 0.1Sbs〇.4; A is a dopant; 0 is &lt;0.05; and x + y = 2 is 0.95SXS1.05, wherein the oxide contains a small amount of soluble salts, and is added to 200 ml by adding less than 20 ml of 0·1M HC1 The solution reaches a pH of less than 5, and the solution contains substantially 10 g of all the solubility of the lithium transition metal oxide. The solution is obtained by repeated infiltration and decantation of the lithium transition metal oxide. 2. The lithium transition metal oxide according to claim 1, wherein the solid reaction in the air is performed by one of two steps: (1) one of the conditioning steps between the temperature of 700 and 950 ° C, air circulation And then (ii) at a temperature of 850 ° C and 1020. (Sintering step: 35 1352068 Revised revision date: 2011/8/9 3. Lithium transition metal oxide according to claim 1 of the patent scope, wherein the mixed hydroxide MOOH (M=Ni, Μη) And Co) is obtained in an ammonia-free process. 4. The lithium-transition metal oxide as in claim 1 of the patent range, wherein the necessary amount of 0.1 M HC1 having a pH of less than 5 is 10 ml. A lithium transition metal oxide of the first aspect, wherein the oxide is produced by a large amount of bismuth under high-speed air circulation. 6. A lithium transition metal oxide as in claim 5, wherein for high-speed air circulation In other words, at least 2 m3 of air (volume at room temperature) per kg of the lithium transition metal oxide is driven into or out of the reactor. 7. Lithium transition metal oxide according to item 6 of the patent application, wherein each kilogram The final clock transition metal oxide is driven into or out of the reactor by at least 1 〇m3 of air. 8. The lithium transition metal oxide of claim 5, wherein a heat exchanger is used to enter the air. Reactor Preheating the inflowing air while cooling the effluent air. 9. The lithium transition metal oxide of claim 1 wherein the solid state reaction is carried out via at least two steps, including between 7 Torr and 950 ° C. a conditioning step, wherein the transition metal precursor reacts with Li2c〇3 to form a LiM〇2 precursor; and a sintering step between the temperature 850oC and 1020oC, wherein a fine layered crystal structure of LiM02 is prepared therein. During the conditioning step, a large amount of air exceeding 2 m3/kg of LiM02 was passed into the reactor equipped with a heat exchanger to preheat the air.