CN1284756A - Active positive-pole material for lithium ion secondary cell and its preparation and use - Google Patents
Active positive-pole material for lithium ion secondary cell and its preparation and use Download PDFInfo
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- CN1284756A CN1284756A CN99113982A CN99113982A CN1284756A CN 1284756 A CN1284756 A CN 1284756A CN 99113982 A CN99113982 A CN 99113982A CN 99113982 A CN99113982 A CN 99113982A CN 1284756 A CN1284756 A CN 1284756A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The active positive pole material of the present invention has the general expression of Li1+xNiyCo1-yO2+z, where x is between 0 and 0.2, y between 0.6 and 0.9 and z between 0 and 0.2. It is prepared through the processes of mixing and grinding lithium containing compound, cobalt containing compound and nickel containing compound; molding the mixture into honeycomb lump; and sintering the lump in oxygen containing atmosphere. Compared with available solid material made through pressing, the present honeycomb material has more contact with oxygen and thus high electrochemical performance.
Description
The present invention relates to be used for positive electrode active materials and the manufacture method and the purposes of lithium rechargeable battery, specifically, the present invention relates to be used for the Li of lithium rechargeable battery
1+yNi
yCo
1-yO
2+zPositive electrode active materials (wherein 0＜x＜0.2,0.6≤y≤0.9,0≤z≤0.2) and manufacture method and purposes.
Lithium rechargeable battery have the life-span long, specific capacity is high, do not have advantages such as " memories ", thereby be widely used in various small portable apparatus, as mobile phone, portable computer etc.
At present, the positive electrode active materials of widely used lithium rechargeable battery has LiCoO
2LiCoO
2Near discharge platform (to lithium) 3.8-4V, theoretical specific capacity is 274mAh/g.During use, in order to prevent electrolytical decomposition, charging voltage is limited near the 4.3V (to lithium):
Therefore its actual specific capacity is about about 140mAh/g.Because Co
3+In air when heating more stable, therefore think LiCoO
2Be than the material that is easier to synthesize.The specific descriptions of this positive electrode active materials can be referring to United States Patent (USP) 3,945, and 848 and 4,340,652.But because the price of cobalt is more expensive, the cost of the feasible positive electrode active materials that makes thus is higher.
LiNiO
2It is the positive electrode active materials of the superior another kind of lithium rechargeable battery of chemical property.Its specific capacity is up to 274mAh/g.The embedding voltage range of taking off of lithium is 3.4-4.2V, and its price only is 1/3 of a cobalt.But, because Ni
3+At high temperature unstable, synthetic LiNiO
2The time, Ni is often arranged
2+Supervene.These Ni
2+Remove and to capture in the lattice Ni of 3b position on the nickel dam
3+Outside the position, also invade and occupy the locational Li of 3a in the lattice in the lithium layer
+The position forms the ion mixed layer, and its molecular formula can be expressed as:
[Li
+ 1-dNi
2+ d]
3a[Ni
3+ 1-dNi
2+ d]
3b[O
2- 2]
6c
Its consequence is the locational Li of 3a
+Content reduce, also increased the active Ni of non-electrochemical simultaneously
2+Content, make reversible capacity reduce.Because Ni
2+Ionic radius (r
0=0.068nm) greater than Ni
3+Ionic radius (r
0=0.056nm), so Ni
2+Existence make the nickel dam spacing increase, stability of structure is affected, the cycle performance of material degenerates.
LiNiO
2And LiCoO
2Have and α-NaFeO
2Identical cube rock salt crystal structure.Be closs packing with the oxonium ion in the lattice, Li
+, Co
3+Or Ni
3+Be on the closely packed octahedral position of oxonium ion.At LiNiO
2In mix the Co atom, form Li
1+xNi
yCo
1-yO
2+z, in the whole interval of y=0 to y=1, can form good solid solution and keep crystallographic system constant.Co
3+Ratio of ionic radii Ni
2+And Ni
3+All little, Co when high temperature is synthetic in oxygen-containing atmosphere
3+Good stability, Li
1+xNi
yCo
1-yO
2+zIn Co
3+Account for the 3b position, can effectively suppress Ni
2+The antiposition ion, reduced the thickness of nickel ion layer simultaneously, play rock-steady structure thereby improve cycle characteristics.
Tsutomu Ohzuku etc. are at Electrochimica Acta vol.38, and No.9 discloses a kind of Li of using in 1993
2CO
2, CoCO
3And NiCO
3Compressing tablet prepares LiNi
yCo
1-yO
2The method of composite oxides.But the lithium battery that the composite oxides that make with this method constitute its capacity when y＜1 is not more than 150mAh/g.
Therefore, need a kind of positive electrode active materials that is used for lithium rechargeable battery of exploitation with higher chemical property and moderate cost.
The purpose of this invention is to provide a kind of have higher chemical property and the moderate positive electrode active materials that is used for lithium rechargeable battery;
Another object of the present invention provides a kind of manufacture method that is used for the positive electrode active materials of lithium rechargeable battery.The lithium rechargeable battery that the positive electrode active materials that makes in this way constitutes has good charge-discharge characteristic.
Further object of the present invention provides a kind of lithium rechargeable battery that makes with positive electrode active materials of the present invention.
The invention provides a kind of general formula that is used for lithium rechargeable battery is Li
1+xNi
yCo
1-yO
2+zPositive electrode active materials, 0＜x＜0.2,0.6≤y≤0.9,0≤z≤0.2 wherein is characterized in that it makes with following method:
(a) a certain proportion of lithium-containing compound, cobalt compound and nickel compound containing are mixed and grinding;
(b) mixture that obtains is molded into cellular block of material;
(c) with described block of material sintering in oxygen-containing atmosphere.
It is Li that the present invention also provides a kind of lithium rechargeable battery general formula that is used for
1+xNi
yCo
1-yO
2+zThe manufacture method of positive electrode active materials, 0＜x in the described general formula＜0.2,0.6≤y≤0.9,0≤z≤0.2, this method comprises:
(a) a certain proportion of lithium-containing compound, cobalt compound and nickel compound containing are mixed and grinding;
(b) mixture that obtains is molded into the piece material;
(c) with described block of material sintering in oxygen-containing atmosphere; And optional
(d) the agglomerate abrasive lapping that makes is pulverized, be molded into the step of cellular block of material and sintering again;
It is characterized in that the piece material that is molded into is cellular in step (b).
Below the present invention will be described in more detail.
Fig. 1 is the used oxygen ultraviolet light active device of better example of the present invention;
Fig. 2 a is the typical x-ray diffraction pattern of comparative example 1 and comparative example 2 samples;
Fig. 2 b is the typical x-ray diffraction pattern of embodiment 14 samples;
Fig. 3 a is charge-discharge current potential-time (V (﹠amp of embodiment 4 products; Li)-t) graph of a relation;
Fig. 3 b is the specific capacity-cycle-index graph of a relation of embodiment 4 products;
Fig. 4 a is charge-discharge current potential-time (V (﹠amp of embodiment 2 products; Li)-t) graph of a relation;
Fig. 4 b is the specific capacity-cycle-index graph of a relation of embodiment 2 products.
The general formula that the present invention is used for the positive electrode active materials of lithium rechargeable battery is Li1+xNi
yCo
1-yO
2+z, 0＜x＜0.2,0.6≤y≤0.9,0≤z≤0.2 wherein, it makes with following method:
(a) a certain proportion of lithium-containing compound, cobalt compound and nickel compound containing are mixed and grinding;
(b) mixture that obtains is molded into cellular block of material;
(c) with described block of material sintering in oxygen-containing atmosphere.
Lithium-containing compound for the manufacture of positive electrode active materials of the present invention can be to be usually used in making lithium ion secondary The various lithium-containing compounds of battery, its example includes, but are not limited to lithium carbonate, lithium nitrate and lithia. Wherein Better be lithium carbonate and lithium nitrate, but because lithium nitrate at high temperature can be emitted nitrogen dioxide gas, pollute ring Therefore border, lithium carbonate preferably.
Cobalt compound for the manufacture of positive electrode active materials of the present invention can be to be usually used in making lithium ion secondary The various cobalt compounds of battery, its example includes, but are not limited to cobalt sesquioxide, cobaltosic oxide and nitric acid Cobalt etc. Better be cobalt sesquioxide and cobaltosic oxide, preferably cobalt sesquioxide.
Nickel compound containing for the manufacture of positive electrode active materials of the present invention can be to be usually used in making lithium ion secondary The various nickel compound containings of battery, its example includes, but are not limited to nickel sesquioxide and nickel nitrate etc. Better be Nickel sesquioxide.
When making positive electrode active materials of the present invention, earlier with a certain proportion of lithium-containing compound, cobalt compound and The powder ground and mixed of nickel compound containing, the particle diameter of described powder is without particular limitation, as long as this particle diameter is to reaching The object of the invention has no adverse effect and gets final product. But the particle diameter of these compounds is preferably the 1-20 micron.
According to required positive electrode active materials LixNi
yCo
1-yO
2+z, those of ordinary skill in the art can be easily Know the ratio between the consumption of lithium-containing compound, cobalt compound and nickel compound containing. And this area is general Logical technical staff is appreciated that by control sintering temperature and reaction atmosphere, can obtains required z value.
Subsequently, the stamping of powder through mixing is become cellular block of material. At an example preferably of the present invention In, the piece material that makes is the piece material of similar structure of honeycomb briquette. Then, with cellular block of material making oxygenous Carry out sintering in the atmosphere. The agglomerating plant that the present invention uses is equipment as known in the art, such as the SG2-3-12 type Muffle furnace (available from Shanghai Industrial pottery mechanical ﹠ electrical corporation), employed oxygen-containing atmosphere can be air, purity oxygen Or active improved oxygen. In order to increase contacting of reactant and oxygen, prevent the divalent metal nickel ion, institute Stating oxygen-containing atmosphere better is purity oxygen or active improved oxygen, preferably active improved oxygen.
Fig. 1 is the used oxygen ultraviolet light active device schematic diagram of better example of the present invention, described device bag Draw together oxygen air inlet 1, quartz socket tube 2 and oxygen gas outlet 3. The inner tube of quartz socket tube 2 is equipped with the strip purple Outer light pipe. Oxygen enters quartz socket tube 2 from oxygen air inlet 1 during use, is subjected to there the ultraviolet light pipe and sends The irradiation of ultraviolet light, form the mist of excitation state, ozone and the oxygen of various oxygen, described mist Enter sintering furnace through oxygen gas outlet 3.
The ultraviolet light pipe that fills in the inner tube of quartz socket tube 2 is without particular limitation. In an example of the present invention In, this ultraviolet light pipe is low pressure mercury lamp, the wave-length coverage of the ultraviolet light that it sends is 200-400nm.
The sintering temperature of preparation positive electrode active materials of the present invention is 500-900 ℃. If temperature is lower than 500 ℃, Then do not reach the purpose of sintering; If temperature is higher than 900 ℃, then the chemical property of product can descend. Better Sintering temperature be 650-900 ℃, be preferably 750-800 ℃. When heat-agglomerating, can earlier temperature be risen to 500-600 ℃, better rise to 550-600 ℃ and keep a period of time to remove the moisture in the raw material, simultaneously so that The fusing of lithium carbonate and decomposable process slowly carry out, and produce new inhomogeneous with the raw material that prevents from originally mixing The zone is warming up to subsequently sintering temperature again and keeps the regular hour in order to make the material tight burning in this temperature. But this substep temperature-rise period is optional. The time of sintering is different with the temperature of sintering. In general burn More high then required time of the temperature of knot is more short. Those of ordinary skill in the art can be easily according to the temperature of sintering Degree is determined the time of sintering. At 500-600 ℃, more fortunately under 550-600 ℃ the preheat temperature, preheating time Be generally 4-8 hour, be preferably 5-6 hour. Sintering time under described sintering temperature is generally 10-17 Hour, be preferably 13-15 hour.
In order to guarantee the homogeneity of product, when making positive electrode active materials of the present invention, can be cellular with what make The piece material is pulverized, and grinds, and is molded into cellular block of material and sintering again. These steps can repeatedly, repeat usually Two to three times, make the product that makes have the performance of homogeneous. Can cellular block of abrasive lapping powder will be obtained finally Broken, and make the positive pole of required lithium ion battery with conductive material and binding agent.
Positive electrode active materials L of the present invention
1+xNi
yCo
1-yO
2+zAdopt the powder solid phase reaction method to make.During fabrication raw material is fully mixed and grind after be molded into similar cellular structure, increased the contact area of reactant and oxygen, suppressed the formation of bivalent nickel ion, thereby obtained the good single-phase product of crystal structure.The lithium rechargeable battery that makes with positive electrode active materials of the present invention has high specific capacity and good charge-discharge performance.
To further specify the present invention by embodiment below.
Embodiment
In the following embodiments, use the performance of the positive electrode active materials that following measurement of test method makes.
The specific capacity method of testing
The sample that 85 weight % the following example are made adds in NMP (N-N-methyl-2-2-pyrrolidone N-(the N-methy1-2-pyrrolidinone)) solution with 10 weight % acetylene blacks and 5 weight %PVDF (polyvinylidene fluoride (polyvinylidene fluoride)), it is fully stirred into pasty state and be coated on the aluminium foil, form the thick film of about 0.1mm.Place vacuum drying oven 130 ℃ of bakings 12 hours, as positive pole on membrane aluminium foil; With the lithium sheet is negative pole; With EC (vinyl carbonate (ethylene carbonate)): DMC (dimethyl carbonate (dimethyl carbonate))=50: 50 (weight ratio), 1M LiPF6 (lithium hexafluorophosphate) is an electrolyte, constitutes lithium battery.
Charging and discharging currents size during test becomes according to the size of electroactive substance, is controlled near the 14mA/g.The about 0.2-0.4mA/cm of current density
2, voltage range is 4.3-2.5V, the ambient temperature of battery is 30 ℃.
The atomic composition ratio of metallic element
Adopt the Solaar 939 type Atomic Absorption Spectrometers of Britain UNICAM that Li, Ni and Co content are measured.The content of oxygen adopts deduction method to calculate and gets, and promptly is calculated as follows:
W
o=W
Always-W
Li-W
Ni-W
Co
Wherein, W
Always-sampling total weight when analyzing;
W
LiThe content of-lithium;
W
NiThe content of-nickel;
W
CoThe content of-cobalt;
More than 4 parameters be actual measurement weight, W
oFor the weight of oxygen, by W
o/ M
o(M
0Atomic weight for oxygen) can try to achieve the atom numerical value of oxygen in the product molecular formula.
Structural analysis
Adopt the DMAX-γ β type powder X-ray-optical diffraction instrument of Japanese motor of science to measure.Copper target k α 1/40kV/100mA, scatter slit 1 degree receives slit 0.3mm, sweep speed 4 degree/minute.
Preparation Li
1.02Ni
0.9Co
0.1O
2.05Positive electrode active materials
With 1.1 moles of particle diameters be 1 micron lithium nitrate, 0.45 mole of particle diameter be 10 microns nickel sesquioxide and 0.033 mole of particle diameter be 2 microns cobaltosic oxide (all available from Shanghai reagent two factories, analyze pure) fully mix, grind and be pressed into cellular porous block structure material with powder compressing machine (the 75yp-15z type is available from Tianjin Keqi High Technology Corp.).The piece material that obtains is placed sintering furnace (SG2-3-12 type, available from Shanghai industrial ceramics mechanical ﹠ electrical corporation) in oxygen atmosphere, heat with the heating rate about 3 ℃/min, with this piece material at 600 ℃ of constant temperature after 4 hours, be warming up to 780 ℃ and keeping under this temperature about 15 hours again, stop heating subsequently, make temperature reduce to room temperature naturally.Then carry out the second time and grind, grinding product is pressed into cellular porous block structure material after, heated at constant temperature is lowered the temperature about 15 hours subsequently naturally in 780 ℃ sintering furnace; Then the agglomerate material is ground for the third time, with press grinding product is pressed into cellular porous block of material, heated at constant temperature about 15 hours in 780 ℃ sintering furnace stops heating after being cooled to 300 ℃ with 1 ℃/minute speed, makes it to naturally cool to room temperature.
With the product that atomic absorption spectrometry obtains, the content of lithium is 1.02 as a result, and the content of nickel is 0.90, and the content of cobalt is 0.1, calculates to such an extent that the content of oxygen is 2.05.
Measure the specific capacity of the sample that makes with top described method, result's charge ratio capacity for the first time is 169mAh/g, and specific discharge capacity is 147mAh/g.X-ray diffraction pattern is shown in Fig. 2 b.By this figure as seen, (102) peak of the product that makes and (006) peak obviously separate, and (018) peak and (110) peak also obviously separate.
Preparation Li
1.03Ni
0.6Co
0.4O
2.03Positive electrode active materials
With 0.55 mole of particle diameter be 10 microns lithium carbonate, 0.3 mole of particle diameter be 1 micron nickel sesquioxide and 0.134 mole of particle diameter be 20 microns cobaltosic oxide (all available from Shanghai chemical reagent work, analyze pure) fully mix, grind and be pressed into cellular porous block structure material with 76yp-15z type powder compressing machine.Place SG2-3-12 type sintering furnace at ultraviolet light (low pressure mercury lamp in the piece material that obtains, heat with the heating rate about 5 ℃/min in the oxygen atmosphere that λ=200-400nm) activates, with this piece material at 600 ℃ of constant temperature after 6 hours, be warming up to 800 ℃ and keeping under this temperature about 13 hours again, stop heating subsequently and make temperature reduce to room temperature naturally.Then carry out the second time and grind, grinding product is pressed into cellular porous block structure material after, heated at constant temperature is lowered the temperature about 13 hours subsequently naturally in 800 ℃ sintering furnace; Then the agglomerate material is ground for the third time, with press grinding product is pressed into cellular porous block of material, heated at constant temperature is about 13 hours in 800 ℃ sintering furnace, stops heating after being cooled to 300 ℃ with about 1.5 ℃/minute speed, makes it to naturally cool to room temperature.
With the product that atomic absorption spectrometry obtains, the content of lithium is 1.03 as a result, and the content of nickel is 0.59, and the content of cobalt is 0.41, calculates to such an extent that the content of oxygen is 2.03.
Measure the specific capacity of the sample that makes with top described method, result's charge ratio capacity for the first time is 165mAh/g, and specific discharge capacity is 138mAh/g.Its charge-discharge current potential-time (V (﹠amp; Li)-t) graph of a relation is shown in Fig. 4 a, and specific capacity-cycle-index graph of a relation is shown in Fig. 4 b.X-ray diffraction pattern is similar to Fig. 2 b.
Preparation Li
1.01Ni
0.75Co
0.25O
2.01Positive electrode active materials
Press the identical method of embodiment 1, but being to use 1.1 moles of particle diameters is that 20 microns lithium nitrate, 0.375 mole of particle diameter are that the cobalt sesquioxide that 20 microns nickel sesquioxide and 0.125 mole of particle diameter are 1 micron prepares sample, the preheat temperature of using is 550 ℃, the time that keeps under this temperature is 8 hours, sintering temperature is 900 ℃, and sintering time is about 10 hours.The content of lithium is 1.01 in the sample that atomic absorption spectroscopy obtains, and the content of nickel is 0.75, and the content of cobalt is 0.25, and the content of the oxygen that calculates is 2.01.
The charge and discharge cycles result of the test: charging and discharging capacity is 180mAh/g for the first time, and specific discharge capacity is 143mAh/g.X-ray diffraction pattern is similar to Fig. 2 b.
Embodiment 4
Preparation Li
1.04Ni
0.9Co
0.1O
2.05Positive electrode active materials
Pressing the identical method of embodiment 1, is that 1 micron lithium carbonate, 0.45 mole of particle diameter are that the cobalt sesquioxide that 7 microns nickel sesquioxide and 0.05 mole of particle diameter are 5 microns prepares sample but be to use 0.55 mole of particle diameter.The content of lithium is 1.04 in the sample that atomic absorption spectroscopy obtains, and the content of nickel is 0.90, and the content of cobalt is 0.11, and the content of the oxygen that calculates is 2.05.
The charge and discharge cycles result of the test: charging and discharging capacity is 205mAh/g for the first time, and specific discharge capacity is 175mAh/g.It discharges and recharges current potential-time (V (﹠amp; Li)-t) relation is shown in Fig. 3 a, and specific capacity-cycle-index concerns that x-ray diffraction pattern is similar to Fig. 2 b shown in Fig. 3 b.
Preparation Li
1.05Ni
0.65Co
0.35O
2.19
With 0.55 mole of particle diameter be 8 microns lithia, 0.22 mole of particle diameter be 20 microns nickel nitrate and 0.12 mole of particle diameter be 20 microns cobalt nitrate (all available from Shanghai chemical reagent work, analyze pure) fully mix, grind and be pressed into cellular porous block structure material with 76yp-15z type powder compressing machine.The piece material that obtains is placed the heating rate heating of SG2-3-12 type sintering furnace about oxygen atmosphere is with 2 ℃/min, this piece material at 600 ℃ of constant temperature after 5 hours, is warming up to 650 ℃ and keeping about 24 hours under this temperature again.Stop heating subsequently, make temperature reduce to room temperature naturally.Then carry out the second time and grind, grinding product is pressed into cellular porous block structure material after, heated at constant temperature is lowered the temperature about 24 hours subsequently naturally in 650 ℃ sintering furnace; Then the agglomerate material is ground for the third time, with press grinding product is pressed into cellular porous block of material, heated at constant temperature is about 24 hours in 650 ℃ sintering furnace, stops heating after being cooled to 300 ℃ with about 1.5 ℃/minute speed, makes it to naturally cool to room temperature.
With the product that atomic absorption spectrometry obtains, the content of lithium is 1.05 as a result, and the content of nickel is 0.66, and the content of cobalt is 0.35, calculates to such an extent that the content of oxygen is 2.19.
Measure the specific capacity of the sample that makes with top described method, result's charge ratio capacity for the first time is 176mAh/g, and specific discharge capacity is 130mAh/g.Its charge-discharge current potential-time (V (﹠amp; Li)-t) graph of a relation is shown in Fig. 4 a, and specific capacity-cycle-index graph of a relation is shown in Fig. 4 b.X-ray diffraction pattern is similar to Fig. 2 b.
Embodiment 6
Preparation Li
1.19Ni
0.7Co
0.3O
2.09
Press the identical method of embodiment 5, but being to use 0.62 mole of particle diameter is that 1 micron lithium carbonate, 0.35 mole of particle diameter are that the cobalt sesquioxide that 1 micron nickel sesquioxide and 0.15 mole of particle diameter are 1 micron prepares sample, preheat temperature is 550 ℃, and sintering temperature is 750 ℃.The content of lithium is 1.19 in the sample that atomic absorption spectroscopy obtains, and the content of nickel is 0.70, and the content of cobalt is 0.31, and the content of the oxygen that calculates is 2.09.
The charge and discharge cycles result of the test: charging and discharging capacity is 195 mAh/g for the first time, and specific discharge capacity is 170mAh/g.It discharges and recharges current potential-time (V (﹠amp; Li)-t) relation is shown in Fig. 3 a, and specific capacity-cycle-index concerns that x-ray diffraction pattern is similar to Fig. 2 b shown in Fig. 3 b.
Comparative example 1
Prepare sample by embodiment 4 identical methods, kept 10 hours but after grinding for the third time, cellular sample placed under 950 ℃ the temperature.The content of lithium is 0.97 in the sample that atomic absorption spectroscopy obtains, and the content of nickel is 0.90, and the content of cobalt is 0.11, and the content that calculates oxygen is 1.92.
The charge and discharge cycles result of the test: the charge ratio capacity is 163mAh/g for the first time, and specific discharge capacity is 121mAh/g.Shown in X-ray diffractogram and Fig. 2 a.
Comparative example 2
Prepare sample by embodiment 4 identical methods, but sample is compression molded into real pellet shape.The content of lithium is 1.08 in the sample that atomic absorption spectroscopy obtains, and the content of nickel is 0.91, and the content of cobalt is 0.11, and the content that calculates oxygen is 1.94.
The charge and discharge cycles result of the test: the charge ratio capacity is 177mAh/g for the first time, and specific discharge capacity is 129mAh/g.Shown in X-ray diffractogram and Fig. 2 a.
See by top embodiment, with sample be pressed into cellular after sintering again, compare with the sample that is pressed into real core shape because sample inner core part can fully contact with oxygen, thereby greatly improved the chemical property of product.
Although in conjunction with non-limiting instance the present invention is had been described in detail, those of ordinary skill in the art can easily carry out various changes and modifications to the present invention under the prerequisite that does not depart from spirit and scope of the invention.Scope of the present invention comprises this changes and improvements.
Claims (15)
- One kind to be used for the lithium rechargeable battery general formula be Li 1+xNi yCo 1-yO 2+zPositive electrode active materials, 0＜x＜0.2,0.6≤y≤0.9,0≤z≤0.2 wherein is characterized in that it makes with following method:(a) a certain proportion of lithium-containing compound, cobalt compound and nickel compound containing are mixed and grinding;(b) mixture that obtains is molded into cellular block of material;(c) with described block of material sintering in oxygen-containing atmosphere.
- 2. positive electrode active materials as claimed in claim 1 is characterized in that described lithium-containing compound is selected from lithium carbonate, lithium nitrate and lithia; Described cobalt compound is selected from cobalt sesquioxide, cobaltosic oxide and cobalt nitrate; Described nickel compound containing is selected from nickel sesquioxide and nickel nitrate.
- 3. positive electrode active materials as claimed in claim 2 is characterized in that described lithium-containing compound is that lithium carbonate, described cobalt compound are that cobalt sesquioxide, described nickel compound containing are nickel sesquioxides.
- 4. positive electrode active materials as claimed in claim 1, the particle diameter that it is characterized in that described lithium-containing compound, nickel compound containing and cobalt compound is the 1-20 micron.
- 5. positive electrode active materials as claimed in claim 1 is characterized in that described sintering temperature is 500-900 ℃.
- 6. positive electrode active materials as claimed in claim 5 is characterized in that described sintering temperature is 650-900 ℃.
- 7. positive electrode active materials as claimed in claim 5 is characterized in that described sintering temperature is 750-800 ℃.
- One kind to be used for the lithium rechargeable battery general formula be Li 1+xNi yCo 1-yO 2+zThe manufacture method of positive electrode active materials, 0＜x in the described general formula＜0.2,0.6≤y≤0.9,0≤z≤0.2, this method comprises:(a) a certain proportion of lithium-containing compound, cobalt compound and nickel compound containing are mixed and grinding;(b) mixture that obtains is molded into the piece material;(c) with described block of material sintering in oxygen-containing atmosphere;It is characterized in that the piece material that is molded into is cellular in step (b).
- 9. method as claimed in claim 8 is characterized in that earlier temperature being risen to 500-600 ℃ when sintering carries out preheating, rises to sintering temperature with temperature subsequently again.
- 10. method as claimed in claim 9 is characterized in that earlier temperature being risen to 550-600 ℃ when sintering carries out preheating, rises to sintering temperature with temperature subsequently again.
- 11., it is characterized in that it also comprises as any one described method among the claim 8-10:D) the agglomerate abrasive lapping that makes is pulverized, be molded into the step of cellular block of material and sintering again.
- 12. method as claimed in claim 8 is characterized in that described sintering temperature is 500-900 ℃.
- 13. method as claimed in claim 12 is characterized in that described sintering temperature is 650-900 ℃.
- 14. method as claimed in claim 12 is characterized in that described sintering temperature is 750-800 ℃.
- 15. the lithium rechargeable battery that makes with the described material of claim 1.
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| CNB991139828A CN1156928C (en) | 1999-08-16 | 1999-08-16 | Active positive-pole material for lithium ion secondary cell and its preparation and use |
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| CNB991139828A CN1156928C (en) | 1999-08-16 | 1999-08-16 | Active positive-pole material for lithium ion secondary cell and its preparation and use |
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