CN102891299A - High-rate lithium ion battery cathode material and preparation method and application thereof - Google Patents
High-rate lithium ion battery cathode material and preparation method and application thereof Download PDFInfo
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- CN102891299A CN102891299A CN2012103359801A CN201210335980A CN102891299A CN 102891299 A CN102891299 A CN 102891299A CN 2012103359801 A CN2012103359801 A CN 2012103359801A CN 201210335980 A CN201210335980 A CN 201210335980A CN 102891299 A CN102891299 A CN 102891299A
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention discloses a lithium nickel cobalt manganese oxide sosoloid material and a preparation method thereof, and application of the lithium nickel cobalt manganese oxide sosoloid material serving as a cathode material of a high-rate and high-capacity secondary battery and a super capacitor. The chemical formula of the material is Li1+sigmaNixCoyMn1-x-yO2, wherein sigma is more than 0.0 and less than or equal to 12, x is more than 0.0 and less than or equal to 0.6, y is more than or equal to 0 and less than 0.5, and 1-x-y is more than 0.0 and less than or equal to 0.5. The invention also discloses a preparation method for the material. The method comprises the following steps of: preparing a precursor by a coprecipitation method; and obtaining the material by two-step solid phase sintering. The invention also discloses the material serving as the cathode material and application of the current lithium ion battery in compatibility with a mixed super capacitor. Compared with the prior art, the lithium nickel cobalt manganese oxide sosoloid material has the advantages that high-rate and high-capacity high charging and discharging cyclic performance is realized, and industrialization is easy to implement; discharging is executed by 1.6A/g(10C) current; a complete charging and discharging cycle is executed for more than 60 times within 2.5 to 4.3V; and the final discharging is 120mAh/g higher than the capacity. The material obtained by the invention can be used in the conventional lithium ion battery market and can be used for power supplies of an electric tool, an electric automobile and an intelligent power grid.
Description
Technical field
The invention belongs to electrode material field and electrochemical energy storage field, be specifically related to a kind of lithium nickel cobalt manganese oxide solid-solution material and preparation method thereof, and as the purposes of the positive electrode of high magnification high-capacity secondary battery and ultracapacitor.
Background technology
The energy is the engine of national economy, and new energy development is determining the autonomy of the future economy.The energy comprises fossil energy and clean energy resource, along with fossil energy because of it non-renewable and problem of environmental pollution, the utilization of clean energy resource is current forefront, most crucial global problems.Because clean energy resource is not had continuity aborning usually, such as solar energy, wind energy, be limited by region and weather, so the energy storage technology is critical support technology indispensable in clean energy resource and the industry thereof.Electrochemical energy storage technology take lithium ion battery and ultracapacitor as representative is widely used in the fields such as information, the energy, traffic, military affairs, being known as to change the disruptive technology of world's (energy) general layout, and their application in electric automobile, intelligent grid get most of the attention.
Lithium ion battery also possesses the advantages such as memory-less effect, self discharge be little except having high-energy-density, become the first-selection of electric bicycle, Prospect of EVS Powered with Batteries.But present lithium ion battery high rate performance is relatively poor (only 3C) generally, so that discharge and recharge overlong time.Low range causes the large current amplification ability of battery, and electric automobile is difficult to obtain the great current powers such as acceleration, climbing and drives function; The thermal runaway security risk that large electric current ability to bear is poor also can aggravate power supply and discharge large electric current the time, and directly cause falling sharply of battery actual life.Present ultracapacitor has the advantages such as fast charging and discharging (high magnification), high power density, high security, long circulation life, but its operating voltage generally is no more than 3V, and energy density is generally very low, is difficult to support the electronic continuation of the journey requirement of long duration distance.
Positive electrode is that lithium ion battery and hybrid super capacitor (are called again lithium-ion capacitor, or electric chemical super capacitor) most important part in is the key factor of capacity, multiplying power, security performance, cycle-index, useful life and the product price etc. of restriction lithium ion battery and capacitor.Conventional batteries stored energy capacitance (energy density) and charge-discharge velocity (power density) relation of being inversely proportional to namely discharge and recharge faster (high rate capability), and storage or the energy that discharges are just fewer.Therefore, the electrochemical energy storage field is in the urgent need to developing a kind of high magnification, high power capacity, good, the with low cost positive electrode of chemical property.Existing anode material for lithium-ion batteries is optimized emphasis and the focus that modification is electrochemical energy storage technical research and exploitation in the global range.
Positive electrode commonly used mainly contains cobalt acid lithium (LiCoO at present
2), nickle cobalt lithium manganate ternary material (LiNi
1/3Co
1/3Mn
1/3O
2), LiMn2O4 (LiMn
2O
4), LiFePO4 (LiFePO
4) etc.Cobalt acid lithium technology is the most ripe lithium-ion electric pool technology of the first generation, the leading position in baby battery market, but because its limitation in being used particularly is subjected to the expensive impact of cobalt, in recent years replaced by compatible with it ternary material technology.The most ripe with the LiMn2O4 technology at present in Prospect of EVS Powered with Batteries, but its reversible capacity is lower, and actual only have about 110mAh/g, and easily recurring structure phase transformation in circulation, causes capacity to fall sharply; And the LiFePO4 technology fails to obtain the approval of international electric automobile market because being subjected to its low-work voltage and low range performance impact always, and its battery performance leeway of having improved without technology.Existing nickle cobalt lithium manganate technology is unstable because of the lattice micro-nano structure of prepared ternary material, fail safe is relatively poor, application in the electrokinetic cell field is restricted, and laboratory scale to prepare the process of high-quality ternary material very complicated, at the order that the needed various element of its patent (200480035045.7) specific embodiments mixes and grinds, significantly improved the industrialization cost such as 3M company.At present the multiplying power level of international market lithium-ion electric pool technology generally only reaches discharge in 3C(20 minute), can not satisfy the needs of power type and long-life type battery, seriously hindered the development of the energy storage technologies such as lithium ion battery and the utilization of clean energy resource.
Summary of the invention
The object of the invention is to provide a kind of high magnification (10C), high power capacity, chemical property lithium nickel cobalt manganese oxide solid solution cathode material good, with low cost and preparation method thereof, and its purposes in secondary cell and ultracapacitor.The present invention reacts and solid phase reaction Comprehensive Control element proportioning, grain morphology by wet-chemical, thereby makes the positive electrode with stable micro-nano structure; The reversible capacity of this positive electrode between 2.5-4.3V is higher than 160mAh/g, and first charge-discharge efficiency is higher than 98%, and the reversible capacity of 10C is higher than 120mAh/g.The specification requirement of the electrochemical applications of positive electrode of the present invention and existing lithium ion battery and ultracapacitor is compatible, has solved the technical bottlenecks such as multiplying power, capacity, circulation and fail safe of lithium ion battery as the high current charge-discharge that electrokinetic cell is used, lithium-ion capacitor faces when using as energy storage device.
First aspect present invention provides a kind of lithium nickel cobalt manganese oxide solid solution anode material for lithium-ion batteries, and its chemical general formula is: Li
1+δ Ni
xCo
yMn
1-x-yO
20.0＜δ≤0.12,0.0＜x≤0.6,0≤y＜0.5,0.0＜1-x-y≤0.5 wherein.
Described solid solution cathode material has stable micro-nano structure in electrochemical applications: at room temperature be used for lithium ion battery, the reversible capacity between 2.5-4.3V is higher than 160mAh/g, and first charge-discharge efficiency is higher than 98%; With 1.6A/g (10C) current discharge, experience complete charge-discharge cycles more than 60 times, this solid solution not recurring structure phase transformation and circulation final state specific discharge capacity is higher than 120mAh/g.
The stable micro-nano structure that described solid solution cathode material has, its solid solution crystal grain comprises following four aspects:
A. solid solution crystal grain Xrd is characterized by single-phase layered crystal structure, has the international crystallography table space of space group R-3m(group No. 166) feature;
B. the solid solution grain morphology is the micro-meter scale offspring porous bulky grain spherical, subsphaeroidal, polyhedron shape that has of being reunited and being formed by a crystal grain of nanoscale;
C. solid solution crystal grain nanoscale crystal grain meso-position radius is of a size of the 100-800 nanometer;
D. the offspring particle meso-position radius of solid solution crystal grain micro-meter scale is of a size of the 1-50 micron.
In another preference, in the described solid solution cathode material chemical general formula, more preferably be 0.02≤δ≤0.09,0.2≤x≤0.6,0.1≤y≤0.4,0.1≤1-x-y≤0.4.
Second aspect present invention provides the preparation method of the described solid solution cathode material of a kind of first aspect present invention, comprises step:
A. nickel source material, cobalt source material, manganese source material are mixed with the transparent mixed aqueous solution without precipitation of soluble salt that concentration of metal ions is 0.1-1.8mol/L by nickel, cobalt, manganese mol ratio x:y:1-x-y in the chemical general formula with deionized water or distilled water;
B. place water-bath or oil bath thermostat to be incubated the obtained mixed aqueous solution of steps A, thermostat temperature is 25-95
0C, evenly add the precipitation reagent aqueous solution again in mixed aqueous solution, stir simultaneously, used mixer is electric mixer, magnetic stirring apparatus, agitator air, the mixer rotating speed is 150-3000 rev/min, and precipitation process finishes to obtain the suspension-turbid liquid of the aqueous solution, coprecipitate;
C. step B gained suspension-turbid liquid is filtered, be precipitated powder, clean powder more than three times with deionized water or distilled water; The suspension-turbid liquid filter method is one or more in centrifugal filtration, negative pressure leaching, the press filtration;
D. step C gained powder is placed in the drying box, drying box adopts infrared drying oven, vacuum drying chamber, air dry oven, microwave drying oven, at 80-160
0In the C temperature dry 6-24 hour, namely get presoma;
E. step D gained presoma and lithium source material are mixed to get drying composite by the mol ratio 1:1+ δ of transition metal Ni+Co+Mn and Li in the chemical general formula, or in deionized water and absolute ethyl alcohol, mix, drying obtains drying composite again, and drying composite was got mixture of powders in 0.1-24 hour with grinder grinding or ball mill ball milling;
F. step e gained mixture of powders is first at 300-550
0Under the C temperature constant temperature calcining 2-24 hour, more continuously with 1-12
0Speed was warmed up to 650-1100 in C/ minute
0C, calcining at constant temperature 4-24 hour again, cool to room temperature sieved and finally obtains oxide solid solution positive electrode of the present invention.
Described steps A. described in the nickel source material be in nickelous sulfate, nickel nitrate, nickel acetate, citric acid nickel, the nickel halogenide one or more; Described cobalt source material is one or more in cobaltous sulfate, cobalt nitrate, cobalt acetate, citric acid cobalt, the halogenation cobalt; Described manganese source material is one or more in manganese sulfate, manganese nitrate, manganese acetate, manganese citrate, the manganese halide.
The precipitation reagent aqueous solution is made with deionized water or dissolved in distilled water by in solubility precipitation reagent ammoniacal liquor, NaOH, potassium hydroxide, carbonic acid ammonia, sodium carbonate, potash, ammonium hydrogencarbonate, sodium acid carbonate, the saleratus one or more among the described step B..
In another preference, the presoma preparation method is among the described step D.: the gained powder was mixed with suspension-turbid liquid after step C was cleaned, at 100-300
0Mist projection granulating under the C condition, the preferred 150-220 of inlet temperature in the spray-drying process
0C obtains presoma.
Described step e. described in the lithium source material be in lithium carbonate, lithium sulfate, lithium nitrate, lithium acetate, lithium citrate, lithium hydroxide, the lithium halide one or more.
In another preference, two sections warm area sintering carry out under high temperature Muffle furnace, rotary furnace, tunnel cave or roller kilns Air atmosphere continuously in the described step F.
Third aspect present invention provides a kind of anode, and described positive electrode contains the described lithium nickel cobalt manganese oxide solid solution of first aspect present invention.
In another preference, the positive electrode active materials of described anode uses separately the described lithium nickel cobalt manganese oxide solid solution of first aspect present invention.
In another preference, the positive electrode active materials of described anode uses the described lithium nickel cobalt manganese oxide solid solution of first aspect present invention to combine such as anode material for lithium-ion batteries such as spinel lithium manganate, LiFePO4, cobalt acid lithiums with other.
In another preference, described anode also contains conductive agent and binding agent.
In another preference, described conductive agent is acetylene black, conductive black, carbon nano-tube, carbon fiber, Graphene.
In another preference, described binding agent is Kynoar (PVDF);
Fourth aspect present invention provides a kind of secondary cell, described secondary cell comprises positive electrode, negative material, barrier film, electrolyte and shell, wherein, described positive electrode comprises the described lithium nickel cobalt manganese oxide solid solution of first aspect present invention, and described secondary cell includes the described anode of third aspect present invention.
In another preference, described electrolyte is non-aqueous electrolytic solution or solid electrolyte.
In another preference, described negative material comprises native graphite, electrographite, carbonaceous mesophase spherules, carborundum, metal lithium sheet, lithium titanate or metal alloy.
In another preference, described barrier film is PP﹠amp; PE barrier film or fibreglass diaphragm.
In another preference, described shell is stainless steel box hat, aluminum hull or polyalcohol flexible packing.
Fifth aspect present invention provides a kind of lithium-ion capacitor or hybrid super capacitor, described capacitor comprises positive electrode, negative material, barrier film, electrolyte and shell, wherein, described positive electrode comprises the described lithium nickel cobalt manganese oxide solid solution of first aspect present invention, and described capacitor includes the described anode of third aspect present invention.
In another preference, described electrolyte is non-aqueous electrolytic solution or solid electrolyte.
In another preference, described negative material comprises the mixture of activated carbon, activated carbon and fake capacitance hopcalite, activated carbon and lithium metal particle or the mixture of activated carbon and high polymer coated metal lithium particle.
In another preference, described barrier film is PP﹠amp; PE barrier film or fibreglass diaphragm.
In another preference, described shell is stainless steel box hat, aluminum hull or polyalcohol flexible packing.
In another preference, described hybrid super capacitor adopts such as United States Patent (USP) (6222723), or United States Patent (USP) (7766981B2), or Subaru sandwich sandwich, or configuration shown in the Jsr Micro laminated construction.
Sixth aspect present invention provides the purposes of the described solid-solution material of a kind of first aspect present invention, for the preparation of the manufacturing of the described anode of third aspect present invention, the described secondary cell of fourth aspect present invention and the described ultracapacitor of fifth aspect present invention.
Major advantage of the present invention and good effect are:
1. solid-solution material of the present invention has good chemical property: have the high potential platform (2.5-4.3V) with the specification requirement compatibility of existing lithium ion battery and ultracapacitor, high reversible capacity (being higher than 160mAh/g), (first charge-discharge efficiency is higher than 98% to good circulation stability, circulate and have no obvious decay 60 times), high magnification excellent cycle performance (reversible capacity of 10C circulation more than 60 times is higher than 120mAh/g).
2. solid-solution material of the present invention is easy to large-scale industrialized production: owing to adopt controllable co-precipitation flow process, can obtain the solid solution cathode material that transiting metal nickel cobalt manganese evenly distributes, micro-nano structure is stable of atom level level, by the good control to process of lapping, can obtain subsphaeroidal, the polyhedral porous bulky grain of high density, Effective Raise the processing density of battery material, thereby improve volume, the mass energy density of battery and capacitor.Optimize the consumption that the element proportioning can effectively reduce expensive cobalt ions, namely reduced the consumption of expensive cobalt element, farthest reduce the cost of raw material.The various raw materials that adopt in the production and equipment are buied being easy on the market, are easy to realize the large-scale production of battery manufacture.Simultaneously, the present invention do not adopt among the multi-element composite material preparation method the technological means of the control crystal grain such as organic complexing agent, chelating agent, dispersant that generally use, without the compacting process, need not shattering process behind the sintering after grinding, directly final material.Therefore, preparation process environmental protection of the present invention, synthetic method are simple, very easily realize the serialization large-scale production.
3. adopt the anodal 10C lithium-ion electric pool technology that can obtain to have the high security high power capacity of solid-solution material of the present invention preparation, produce on power density and can reach 1600W/kg, energy density can reach the lithium ion battery of 245W/kg; Can produce the hybrid super capacitor that the operating voltage interval reaches 4.3V.The present invention drives the breakthrough of the leading energy storage technology-lithium ion battery of two class electrochemistry and hybrid super capacitor technology by a kind of breakthrough of positive electrode.Estimate not only in traditional lithium ion battery market, and be with a wide range of applications at electrokinetic cell and energy storage capacitor field.
Should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and can making up mutually between specifically described each technical characterictic in below (eg embodiment), thus consist of new or preferred technical scheme.As space is limited, this tired stating no longer one by one.
Description of drawings
Figure 1A has shown the x-ray diffraction pattern (Xrd) of the solid-solution material of embodiment 1 preparation.
Figure 1B has shown the primary particle scanning electron microscope (SEM) photograph (SEM) of the solid-solution material of embodiment 1 preparation.
Fig. 1 C has shown the offspring scanning electron microscope (SEM) photograph (SEM) of the solid-solution material of embodiment 1 preparation.
Fig. 1 D has shown the offspring agglomerated particle magnified sweep Electronic Speculum figure (SEM) of the solid-solution material of embodiment 1 preparation.
Fig. 2 A has shown the first charge-discharge curve of the secondary cell of embodiment 7 preparations.
Fig. 2 B has shown the charge and discharge cycles more than 60 times of the secondary cell of embodiment 7 preparations.
Fig. 3 has shown the 10C charge and discharge cycles of the secondary cell of embodiment 7 preparations.
Fig. 4 has shown that the hybrid super capacitor of embodiment 10 preparations is in the charge and discharge cycles of 1.5-4.3V.
Embodiment
The present inventor is through repeatedly experiment, and extensively and in depth research is by optimizing the element proportioning, adopt the excessive saturated lithium of lithium-transition metal mixing, thereby control the stability of oxide solid solution micro-nano structure, improved the high rate performance of battery material, finished the present invention.
Lithium nickel cobalt manganese oxide solid solution (Li 1+ δ
Ni x Co y Mn 1-x-y O 2 )
At present, the positive electrode on the market mainly contains cobalt acid lithium (LiCoO2), nickle cobalt lithium manganate ternary material (LiNi
1/3Co
1/3Mn
1/3O
2).Wherein, cobalt acid lithium cost is high, and fail safe, high rate performance is poor can not be used for electrokinetic cell; Ternary material generally has (333), and variants such as (523) can only be used for the following baby battery market of 3C multiplying power, generally can not use separately, and usually uses organic complexing agent etc. to improve its processing characteristics in the preparation process, brings environmental pollution.
Term used herein " lithium nickel cobalt manganese oxide solid solution " refers to comprise the crystal grain of lithium nickel cobalt manganese oxide, belongs to single-phase layered crystal structure.Described chemical formula is Li
1+δ Ni
xCo
yMn
1-x-yO
2Preferably, 0.0＜δ≤0.12,0.0＜x≤0.6,0≤y＜0.5,0.0＜1-x-y≤0.5; It more preferably is 0.02≤δ≤0.09,0.2≤x≤0.6,0.1≤y≤0.4,0.1≤1-x-y≤0.4.Lithium nickel cobalt manganese oxide solid solution is a class and existing cobalt acid lithium battery and the battery operated voltage platform of ternary material (2.5-4.3V) compatibility, has the high reversible capacity positive electrode of (being higher than 160mAh/g).
The preparation of lithium nickel cobalt manganese oxide solid solution cell positive material
Required lithium source material, nickel source material, cobalt source material, manganese source material, precipitation reagent and equipment all can be bought in market and obtain among the preparation method of the present invention.The experimental technique of unreceipted actual conditions is usually according to normal condition or the condition of advising according to manufacturer.
Described lithium source material is one or more in lithium carbonate, lithium sulfate, lithium nitrate, lithium acetate, lithium citrate, lithium hydroxide, the lithium halide;
Described nickel source material is one or more in nickelous sulfate, nickel nitrate, nickel acetate, citric acid nickel, the nickel halogenide;
Described cobalt source material is one or more in cobaltous sulfate, cobalt nitrate, cobalt acetate, citric acid cobalt, the halogenation cobalt;
Described manganese source material is one or more in manganese sulfate, manganese nitrate, manganese acetate, manganese citrate, the manganese halide;
Described precipitation reagent is one or more in ammoniacal liquor, NaOH, potassium hydroxide, carbonic acid ammonia, sodium carbonate, potash, ammonium hydrogencarbonate, sodium acid carbonate, the saleratus.
The invention provides a kind of method for preparing positive electrode of the present invention, comprise step:
A. nickel source material, cobalt source material, manganese source material are mixed with the transparent mixed aqueous solution without precipitation of soluble salt that concentration of metal ions is 0.1-1.8mol/L by nickel, cobalt, manganese mol ratio x:y:1-x-y in the chemical general formula with deionized water or distilled water;
B. place water-bath or oil bath thermostat to be incubated the obtained mixed aqueous solution of steps A, thermostat temperature is 25-95
0C, evenly add the precipitation reagent aqueous solution again in mixed aqueous solution, stir simultaneously, used mixer is electric mixer, magnetic stirring apparatus, agitator air, the mixer rotating speed is 150-3000 rev/min, and precipitation process finishes to obtain the suspension-turbid liquid of the aqueous solution, coprecipitate;
C. step B gained suspension-turbid liquid is filtered, be precipitated powder, clean powder more than three times with deionized water or distilled water; The suspension-turbid liquid filter method is one or more in centrifugal filtration, negative pressure leaching, the press filtration;
D. step C gained powder is placed in the drying box, drying box adopts infrared drying oven, vacuum drying chamber, air dry oven, microwave drying oven, at 80-160
0In the C temperature dry 6-24 hour, namely get presoma;
E. step D gained presoma and lithium source material are mixed to get drying composite by the mol ratio 1:1+ δ of transition metal Ni+Co+Mn and Li in the chemical general formula, or in deionized water and absolute ethyl alcohol, mix, drying obtains drying composite again, and drying composite was got mixture of powders in 0.1-24 hour with grinder grinding or ball mill ball milling;
F. step e gained mixture of powders is first at 300-550
0Under the C temperature constant temperature calcining 2-24 hour, more continuously with 1-12
0Speed was warmed up to 650-1100 in C/ minute
0C, calcining at constant temperature 4-24 hour again, cool to room temperature sieved and finally obtains oxide solid solution positive electrode of the present invention.
Wherein, among the described step D. presoma preparation method can also for: the gained powder was mixed with suspension-turbid liquid after step C cleaned, at 100-300
0Mist projection granulating under the C condition, the preferred 150-220 of inlet temperature in the spray-drying process
0C obtains presoma.
Anode
Anode of the present invention contains solid solution cathode material of the present invention.
Anode of the present invention can also contain conductive agent and binding agent, and wherein said conductive agent is acetylene black, conductive black, carbon nano-tube, carbon fiber, Graphene; Described binding agent is PVDF.
Preferred preparation method comprises step:
Positive electrode is evenly mixed in solution (such as n-formyl sarcolysine base pyrrolidones (NMP)) with conductive agent, binding agent respectively, regulate the mass ratio of suitable positive electrode, conductive agent and binding agent (such as 80-90:5-10:5-10, preferably 90:5:5,80:10:10 or 85:10:5), then apply compressing tablet on aluminium foil, oven dry, compressing tablet makes anode pole piece.
Secondary cell
Secondary cell provided by the invention comprises positive electrode and negative material, and wherein, described positive electrode comprises lithium nickel cobalt manganese oxide solid solution cell positive material of the present invention, and described power brick contains anode of the present invention.
Secondary cell provided by the invention also comprises barrier film, electrolyte, shell.
Described negative material is native graphite, electrographite, carbonaceous mesophase spherules, carborundum, metal lithium sheet, lithium titanate or metal alloy, and described barrier film is PP﹠amp; PE barrier film or fibreglass diaphragm, described electrolyte are secondary cell nonaqueous electrolytic solution commonly used or solid-state electrolytic solution.
Hybrid super capacitor
Hybrid super capacitor provided by the invention comprises positive electrode, negative material, barrier film, electrolyte and shell, wherein, described positive electrode comprises the described lithium nickel cobalt manganese oxide solid solution of first aspect present invention, and described capacitor includes anode of the present invention.
Described electrolyte is secondary cell non-aqueous electrolytic solution commonly used or solid electrolyte, or hybrid super capacitor non-aqueous electrolytic solution commonly used or solid electrolyte.
Described negative material comprises the mixture of activated carbon, activated carbon and hopcalite, activated carbon and lithium metal particle or the mixture of activated carbon and high polymer coated metal lithium particle.
Described barrier film is PP﹠amp; PE barrier film or fibreglass diaphragm.
Described shell is stainless steel box hat, aluminum hull or polyalcohol flexible packing.
Described hybrid super capacitor adopts such as United States Patent (USP) (6222723), or United States Patent (USP) (7766981B2), or Subaru sandwich sandwich, or configuration shown in the Jsr Micro laminated construction.
Unless otherwise defined, employed all specialties are identical with the meaning that scientific words and one skilled in the art are familiar with in the literary composition.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The usefulness that better implementation method described in the literary composition and material only present a demonstration.The above-mentioned feature that the present invention mentions, or the feature that embodiment mentions can combination in any.All features that this case specification discloses can be in any combination and usefulness, and each feature that discloses in the specification can replace with any alternative characteristics of identical, impartial or similar purpose that provides.Therefore except special instruction is arranged, the feature that discloses only is the general example of equalization or similar features.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example is usually according to normal condition or the condition of advising according to manufacturer.
Embodiment 1: take by weighing nickelous sulfate, cobaltous sulfate, manganese sulfate by nickel, cobalt, manganese molar ratio 0.35:0.33:0.32, the adding deionized water fully dissolves and is mixed with the clear solution that ion concentration is 1mol/L, places water-bath constant temperature 70
0C slowly evenly adds the sodium hydroxide solution with concentration again, stirs simultaneously, rotating speed is 600 rev/mins, until add sodium hydroxide solution, reaction gained suspension-turbid liquid color no longer changes, stop to add NaOH, after continuing at the uniform velocity to stir more than 30 minutes, finish coprecipitation reaction.To react suspension-turbid liquid and get the co-precipitation solid by centrifugal filtration, repeatedly refilter 4 times with washed with de-ionized water after, put into air dry oven, in 120 ℃ lower dry 16 hours, get presoma.After the taking-up presoma and lithium hydroxide are pressed the 1:1.1 mixed in molar ratio, be put in the planetary ball mill ball milling 8 hours, grind the even drying composite that gets.Mixture is placed high temperature Muffle furnace, heat up with the 10 ℃/min rate of heat addition, be warmed up to 450 ℃ of roastings 12 hours, continue to be warming up to 900 ℃ of roastings 16 hours with the 12 ℃/min rate of heat addition.Naturally take out mixture after the cooling, products therefrom is the Li that makes
1.07 ± 0.01Ni
0.34 ± 0.02Co
0.33 ± 0.02Mn
0.32 ± 0.020
2Solid-solution material.The stoichiometric proportion of lithium, nickel, cobalt, manganese metal ion can be confirmed described chemical formula by the ICP elementary analysis in the solid-solution material.
The x-ray diffraction pattern of gained solid-solution material (XRD) is shown in Figure 1A, and the single-phase layered crystal structure feature of space group R-3m is obvious; A crystal grain of solid-solution material evenly is distributed on the 100-200 nanometer shown in the SEM of Figure 1B; The secondary agglomeration particle of solid-solution material evenly is distributed on the 2-10 micron shown in the SEM of Fig. 1 C; The secondary agglomeration particle enlarged drawing of solid-solution material such as the SEM of Fig. 1 D show subsphaeroidal feature, and the porous feature is obvious.
Embodiment 2: take by weighing nickel nitrate, cobalt nitrate, manganese nitrate by nickel, cobalt, manganese molar ratio 0.45:0.23:0.32, the adding deionized water fully dissolves and is mixed with the clear solution that ion concentration is 1mol/L, places water-bath constant temperature 60
0C slowly evenly adds the sodium carbonate liquor with concentration again, stirs simultaneously, rotating speed is 1200 rev/mins, until add sodium carbonate liquor, reaction suspension-turbid liquid color does not change, stop to add sodium carbonate, after continuing at the uniform velocity to stir more than 60 minutes, finish coprecipitation reaction.Presoma and lithium hydroxide are pressed the 1:1.09 mixed in molar ratio.All the other are identical with embodiment 1, and its x-ray diffraction pattern (XRD) and SEM figure are similar to Figure 1A-1D.
Embodiment 3: take by weighing nickel acetate, cobalt acetate, manganese acetate by nickel, cobalt, manganese molar ratio 1.0:1.0:1.0, the adding deionized water fully dissolves and is mixed with the clear solution that ion concentration is 1mol/L, places water-bath constant temperature 60
0C slowly evenly adds the sodium bicarbonate solution with concentration again, stirs simultaneously, rotating speed is 1200 rev/mins, until add sodium bicarbonate solution, reaction suspension-turbid liquid color does not change, stop to add sodium acid carbonate, after continuing at the uniform velocity to stir more than 60 minutes, finish coprecipitation reaction.Filter, clean coprecipitated product four times, be configured to suspension-turbid liquid, get presoma by spray drying granulation.Presoma and lithium carbonate are pressed the 1:1.09 mixed in molar ratio.All the other are identical with embodiment 1, and its x-ray diffraction pattern (XRD) and SEM figure are similar to Figure 1A-1D.
Embodiment 4: embodiment 1 prepared solid-solution material is evenly mixed in n-formyl sarcolysine base pyrrolidones (NMP) solution with conductive agent acetylene black, binding agent Kynoar (PVDF) respectively, the mass ratio of solid-solution material, acetylene black and binding agent is respectively 85:10:5, then apply compressing tablet on aluminium foil, oven dry, compressing tablet makes the anode pole piece.
Embodiment 5: the preparation of anode pole piece is with the preparation method of embodiment 4 anode pole pieces, and different is that solid-solution material is the solid-solution material of embodiment 2 preparations.
Embodiment 6: the preparation of anode pole piece is with the preparation method of embodiment 4 anode pole pieces, and different is that solid-solution material is the solid-solution material of embodiment 3 preparations.
Embodiment 7: with embodiment 4 gained anode pole pieces, with metal lithium sheet be negative pole, the ethylene carbonate of 1mol/L lithium hexafluoro phosphate and carbonic acid two
The solution of methyl esters is as electrolyte, and the polyethylene of 20 micron thickness is barrier film, is assembled into CR2032 type button secondary cell.Fig. 2 A charges with 0.2C for this button cell, the first charge-discharge curve of 1C discharge, and the embodiment 4 anodal first charge-discharge efficiencies of visible embodiment 1 gained solid-solution material made are higher than 98%, and the reversible capacity of specific discharge capacity is higher than 160mAh/g; Fig. 2 B is the 0.2C charging between 2.5-4.3V of this button cell, and the 1C discharge cycles is more than 60 times, and reversible capacity has no obvious decay.As seen, embodiment 1 gained solid-solution material has good electrochemistry cycle performance as anode material for lithium-ion batteries, with can produce the lithium ion battery that energy density reaches 245W/kg.
Fig. 3 charges with 1C for this button cell, and the 10C discharge cycles is more than 60 times, and reversible capacity has no obvious decay, and charge and discharge cycles final state specific discharge capacity is higher than 120mAh/g.As seen, embodiment 1 gained solid-solution material has good 10C high power charging-discharging cycle performance, with can produce the lithium ion battery that power density reaches 1600W/kg, realize the 10C lithium-ion electric pool technology of high security high power capacity.
Embodiment 8: the preparation of secondary cell is identical with embodiment 7, and different is to replace embodiment 4 gained anode pole pieces with embodiment 5 gained anode pole pieces.The chemical property of this button cell is similar to Fig. 2 A-2B and Fig. 3.
Embodiment 9: the preparation of secondary cell is identical with embodiment 7, and different is to replace embodiment 4 gained anode pole pieces with embodiment 6 gained anode pole pieces.The chemical property of this button cell is similar to Fig. 2 A-2B and Fig. 3.
Embodiment 10: with embodiment 4 gained anode pole pieces, with activated carbon be negative pole, the ethylene carbonate of 1mol/L lithium hexafluoro phosphate and carbonic acid two
The solution of methyl esters is as electrolyte, and the polyethylene of 20 micron thickness is barrier film, is assembled into CR2032 type button hybrid super capacitor.Fig. 4 is the electrochemical properties of this button capacitor, can work in the 1.5-4.3V interval.
Embodiment 11: the preparation of hybrid super capacitor is identical with embodiment 10, and different is to replace embodiment 4 gained anode pole pieces with embodiment 5 gained anode pole pieces.The chemical property of this hybrid super capacitor is similar to Fig. 4.
Embodiment 12: the preparation of hybrid super capacitor is identical with embodiment 10, and different is to replace embodiment 4 gained anode pole pieces with embodiment 6 gained anode pole pieces.The chemical property of this hybrid super capacitor is similar to Fig. 4.
All quote in this application as a reference at all documents that the present invention mentions, just as each piece document is quoted separately as a reference.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned instruction content of the present invention, these equivalent form of values belong to the application's appended claims limited range equally.
Claims (9)
1. high multiplying power lithium ion battery positive electrode lithium nickel cobalt manganese oxide solid solution, its chemical general formula is: Li
1+δ Ni
xCo
yMn
1-x-yO
2Wherein 0.0＜δ≤0.12,0.0＜x≤0.6,0≤y＜0.5,0.0＜1-x-y≤0.5 is characterized in that this solid solution has stable micro-nano structure in electrochemical applications; At room temperature be used for lithium ion battery, reversible capacity between 2.5-4.3V is higher than 160mAh/g, first charge-discharge efficiency is higher than 98%, and with 1.6A/g (10C) current discharge, experience complete charge-discharge cycles more than 60 times, this solid solution not recurring structure phase transformation and circulation final state specific discharge capacity is higher than 120mAh/g.
2. the stable micro-nano structure of lithium nickel cobalt manganese oxide solid solution according to claim 1 is characterized in that, solid solution crystal grain comprises following four aspects:
A. solid solution crystal grain Xrd is characterized by single-phase layered crystal structure, has the international crystallography table space of space group R-3m(group No. 166);
B. the solid solution grain morphology is the micro-meter scale offspring porous bulky grain spherical, subsphaeroidal, polyhedron shape that has of being reunited and being formed by a crystal grain of nanoscale;
C. solid solution crystal grain nanoscale crystal grain meso-position radius is of a size of 100 nanometers～800 nanometers;
D. the offspring particle meso-position radius of solid solution crystal grain micro-meter scale is of a size of 1 micron～50 microns.
3. lithium nickel cobalt manganese oxide solid solution according to claim 1 is characterized in that: 0.02≤δ≤0.09,0.2≤x≤0.6,0.1≤y≤0.4,0.1≤1-x-y≤0.4.
4. lithium nickel cobalt manganese oxide solid solution claimed in claim 1 is as positive electrode, can with non-aqueous electrolytic solution or solid electrolyte, and negative material is together, forms the application in the lithium rechargeable battery.
Lithium nickel cobalt manganese oxide solid solution claimed in claim 1 in preparation lithium-ion capacitor (being called hybrid super capacitor not only but also be called electric chemical super capacitor) as the application of positive electrode.
6. the preparation method of lithium nickel cobalt manganese oxide solid solution claimed in claim 1 is characterized in that, comprises following six steps:
A. nickel source material, cobalt source material, manganese source material are mixed with the transparent mixed aqueous solution without precipitation of soluble salt that concentration of metal ions is 0.1-1.8mol/L by nickel, cobalt, manganese mol ratio x:y:1-x-y in the chemical general formula with deionized water or distilled water;
B. steps A is made mixed aqueous solution and place water-bath or oil bath thermostat to be incubated, thermostat temperature is 25-95
0C, evenly add the precipitation reagent aqueous solution again in mixed aqueous solution, stir simultaneously, used mixer is electric mixer, magnetic stirring apparatus, agitator air, the mixer rotating speed is 150-3000 rev/min, and precipitation process finishes to obtain the suspension-turbid liquid of the aqueous solution, coprecipitate;
C. step B gained suspension-turbid liquid is filtered, be precipitated powder, clean powder more than three times with deionized water or distilled water, the suspension-turbid liquid filter method is one or more in centrifugal filtration, negative pressure leaching, the press filtration;
D. step C gained powder is placed in the drying box, drying box adopts infrared drying oven, vacuum drying chamber, air dry oven, microwave drying oven, at 80-160
0In the C temperature dry 6-24 hour, namely get presoma;
E. step D gained presoma and lithium source material are mixed to get drying composite by the mol ratio 1:1+ δ of transition metal Ni+Co+Mn and Li in the chemical general formula, or in deionized water and absolute ethyl alcohol, mix, drying obtains drying composite again, and mixture was got mixture of powders in 0.1-24 hour with grinder grinding or ball mill ball milling;
F. step e gained mixture of powders is first at 300-550
0Under the C temperature constant temperature calcining 2-24 hour, more continuously with 1-12
0Speed was warmed up to 650-1100 in C/ minute
0C, calcining at constant temperature 4-24 hour again, cool to room temperature sieved and finally obtains oxide solid solution positive electrode claimed in claim 1.
7. the preparation method of lithium nickel cobalt manganese oxide solid solution claimed in claim 6, it is characterized in that: described lithium source material is one or more in lithium carbonate, lithium sulfate, lithium nitrate, lithium acetate, lithium citrate, lithium hydroxide, the lithium halide; Described nickel source material is one or more in nickelous sulfate, nickel nitrate, nickel acetate, citric acid nickel, the nickel halogenide; Described cobalt source material is one or more in cobaltous sulfate, cobalt nitrate, cobalt acetate, citric acid cobalt, the halogenation cobalt; Described manganese source material is one or more in manganese sulfate, manganese nitrate, manganese acetate, manganese citrate, the manganese halide; Described precipitation reagent is one or more in ammoniacal liquor, NaOH, potassium hydroxide, carbonic acid ammonia, sodium carbonate, potash, ammonium hydrogencarbonate, sodium acid carbonate, the saleratus.
8. the preparation method of lithium nickel cobalt manganese oxide solid solution claimed in claim 6 is characterized in that, the gained powder was mixed with suspension-turbid liquid after step C was cleaned, at 100-300
0Mist projection granulating under the C condition, the preferred 150-220 of inlet temperature in the spray-drying process
0C obtains presoma.
9. the preparation method of lithium nickel cobalt manganese oxide solid solution claimed in claim 6, it is characterized in that: two sections warm area sintering of described step F carry out under high temperature Muffle furnace, rotary furnace, tunnel cave or roller kilns Air atmosphere continuously.
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|---|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3991359B2 (en) * | 2003-11-20 | 2007-10-17 | 日立金属株式会社 | Cathode active material for non-aqueous lithium secondary battery, method for producing the same, and non-aqueous lithium secondary battery using the cathode active material |
| CN101202343A (en) * | 2006-12-15 | 2008-06-18 | 中国电子科技集团公司第十八研究所 | Lithium ion battery positive pole material cobalt nickel oxide manganses lithium and method for making same |
| CN101840787A (en) * | 2010-05-18 | 2010-09-22 | 东莞新能源科技有限公司 | Method for manufacturing positive pole plate of lithium-ion capacitor and lithium-ion capacitor using same |
| CN102522537A (en) * | 2011-11-25 | 2012-06-27 | 李溪 | Simple method for preparing manganese-based laminated anode material with high electrochemical performances by metal-doping |
-
2012
- 2012-09-12 CN CN201210335980.1A patent/CN102891299B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3991359B2 (en) * | 2003-11-20 | 2007-10-17 | 日立金属株式会社 | Cathode active material for non-aqueous lithium secondary battery, method for producing the same, and non-aqueous lithium secondary battery using the cathode active material |
| CN101202343A (en) * | 2006-12-15 | 2008-06-18 | 中国电子科技集团公司第十八研究所 | Lithium ion battery positive pole material cobalt nickel oxide manganses lithium and method for making same |
| CN101840787A (en) * | 2010-05-18 | 2010-09-22 | 东莞新能源科技有限公司 | Method for manufacturing positive pole plate of lithium-ion capacitor and lithium-ion capacitor using same |
| CN102522537A (en) * | 2011-11-25 | 2012-06-27 | 李溪 | Simple method for preparing manganese-based laminated anode material with high electrochemical performances by metal-doping |
Non-Patent Citations (3)
| Title |
|---|
| M.-H. LEE等: "Synthetic optimization of Li[Ni1/3Co1/3Mn1/3]O2 via co-precipitation", 《ELECTROCHIMICA ACTA》, vol. 50, 11 September 2004 (2004-09-11), pages 939 - 948 * |
| 吴英华等: ""层状锂离子正极材料Li1+x(Co0.2Ni0.4Mn0.4)O2的结构和电化学性能的研究"", 《化学世界》, no. 1, 31 December 2008 (2008-12-31) * |
| 王金龙等: ""锂离子电池正极材料Li1+ xNi1/3Co1/3Mn1/3O2的合成"", 《材料热处理学报》, vol. 33, no. 5, 31 May 2012 (2012-05-31) * |
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