CN106654222A - High-nickel cathode material, preparation method thereof and lithium ion battery - Google Patents
High-nickel cathode material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN106654222A CN106654222A CN201710029243.1A CN201710029243A CN106654222A CN 106654222 A CN106654222 A CN 106654222A CN 201710029243 A CN201710029243 A CN 201710029243A CN 106654222 A CN106654222 A CN 106654222A
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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
- H01M4/362—Composites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a high-nickel cathode material, a preparation method thereof and a lithium ion battery. A non-metal doping agent is added into a precursor of the high-nickel cathode material, and then a lithium source is added and sintered to obtain the high-nickel cathode material doped with a non-metallic element. According to the method, the doped element can be uniformly distributed in the material, the character on the surface of the material is improved, and the stability of a crystal structure is improved, so that the heat stability of the material is effectively improved, and the high-temperature cycle performance and high-temperature storage performance of the lithium ion battery are obviously improved.
Description
Technical field
The invention belongs to lithium ion battery manufacture field, be related to a kind of nickelic positive electrode and preparation method thereof and lithium from
Sub- battery.
Background technology
With becoming increasingly conspicuous the problems such as energy crisis and environmental pollution, develop continuable novel energy has become modern
The task of top priority of society, wherein lithium ion battery receive much concern as a kind of secondary energy sources of green.At present business-like lithium from
Sub- cell positive material mainly has the cobalt nickel lithium manganate ternary material of cobalt acid lithium, LiMn2O4, LiFePO4 and routine, but exists
Certain defect, it is impossible to meet the requirement of lithium ion battery higher energy density and other performance.And nickelic positive electrode is (such as x
>=0.7 Li (NixCoyAl1-x-y)O2, x >=0.4 Li (NixCoyMn1-x-y)O2) there is higher specific capacity, cater to market
Demand to high-specific energy battery, therefore obtain increasing concern.
But, on the one hand, nickelic positive electrode is higher due to the nickel content on its surface, at high temperature (>50 DEG C) Yi Yu electricity
Solution liquid reacts and produces HF, and the dissolving of transition metal ions is caused under the corrosion of HF, increases electrolyte/electrode interface impedance
Greatly, cycle life and the storage life of battery are reduced；On the other hand, the Ni for being formed after the de- lithium of nickelic positive electrode4+Stability compared with
, especially in the case of a high temperature, easily there is Ni in difference4+→Ni3+Reaction, while discharging oxygen, make cycle performance and the storage of battery
Sustainability can further deteriorate.These defects seriously constrain the large-scale promotion application in nickelic lithium ion battery.
Doping and surface coated method has been adopted to process nickelic positive electrode in this area, to improving electricity
The high temperature cyclic performance and high-temperature storage performance in pond.Adulterate at present the unit for generally adopting have Mg, Al, Ti, Ba, Cu, Zn, Fe,
V, Zr, Cr, La, Nb, Ga, F, S etc., wherein in addition to F and S is nonmetalloid, remaining is metallic element.However, doping
The compound adopted during metallic element itself or the oxide formed after being thermally decomposed often have higher fusing point, are unfavorable for
Doped chemical fully spreads in the material and is uniformly distributed, and does not reach preferably doping effect.Meanwhile, this metalloid element institute is right
The oxide answered is unfavorable for reducing the alkalescence that high-nickel material has in itself mostly in alkalescence or neutral, and it is in the lattice of material
In in the form of cation, it is less to the stabilization of oxygen anion in lattice, it is impossible to effectively improve the thermally-stabilised of material
Property.Therefore, it is necessary to provide a kind of significantly more efficient method to lift the heat endurance of nickelic positive electrode, it is solved in application
Present in high temperature circulation and high-temperature storage problem.Therefore, a kind of nickelic positive pole with excellent heat endurance how is obtained
Material becomes this area technical problem urgently to be resolved hurrily.
The content of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of preparation side of nickelic positive electrode
Method, to solve the technical problem of nickelic positive electrode heat endurance difference of the prior art, resulting nickelic lithium ion battery
With excellent high temperature cyclic performance and high-temperature storage performance.
To achieve these goals, present invention employs following technical scheme：
A kind of preparation method of nickelic positive electrode, comprises the following steps：
Nonmetal doping agent is added in the presoma of nickelic positive electrode, lithium source is added and is obtained with non-gold after sintering
The nickelic positive electrode of category element doping.
Methods described can be such that nonmetal doping element is uniformly distributed in the material, improve the property of material surface and improve
The stability of crystal structure, so as to effectively lift the heat endurance of nickelic positive electrode, and therefore significantly improves nickelic lithium ion
The high temperature cyclic performance and high-temperature storage performance of battery.
In the present invention, the nickelic positive electrode is Li (NixCoyMn1-x-y)O2, wherein 0.4≤x<1,0<Y≤0.4,
For example, x can be 0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85,0.9 or 0.95 etc., and y can be
0.08th, 0.12,0.2,0.26,0.33 or 0.4 etc.；Or, the nickelic positive electrode is Li (NixCoyAl1-x-y)O2, wherein
0.7≤x<1,0<y<0.3, for example, x can be 0.7,0.8,0.82,0.84,0.86,0.88,0.9,0.92,0.94 or 0.96
Can be 0.05,0.08,0.15,0.22,0.25 or 0.28 etc. Deng, y.
In a preferred technical solution of the present invention, the method comprising the steps of：
The presoma of nickelic positive electrode and nonmetal doping agent are scattered in into liquid phase medium, it is to be dried after, add lithium source,
Then sinter, obtain nickelic positive electrode.
In a preferred technical solution of the present invention, the method comprising the steps of：
The presoma of nickelic positive electrode, nonmetal doping agent and lithium source are scattered in into liquid phase medium, it is to be dried after, enter
Row sintering, obtains nickelic positive electrode.
In a preferred technical solution of the present invention, the method comprising the steps of：
The presoma of nickelic positive electrode, nonmetal doping agent and lithium source are sufficiently mixed, are then sintered, obtain nickelic
Positive electrode.
In the present invention, desired nickelic positive electrode is Li (NixCoyMn1-x-y)O2, wherein 0.4≤x<1,0<y
≤ 0.4, then the presoma of nickelic positive electrode is NixCoyMn1-x-yHydroxide, carbonate coprecipitation thing or oxalates it is common
One kind or at least two combination in sediment.The presoma of the nickelic positive electrode for example can be NixCoyMn1-x-y
Hydroxide, carbonate or oxalates co-precipitate, or NixCoyMn1-x-yHydroxide it is coprecipitated with carbonate
The combination of the combination of the combination of starch, hydroxide and oxalate coprecipitation thing, carbonate and oxalate coprecipitation thing, hydroxide
Combination of thing, carbonate and oxalate coprecipitation thing etc..
In the present invention, desired nickelic positive electrode is Li (NixCoyAl1-x-y)O2, wherein 0.7≤x<1,0<y<
0.3, then the presoma of nickelic positive electrode is NixCoyAl1-x-yHydroxide, carbonate coprecipitation thing or oxalates it is coprecipitated
One kind or at least two combination in starch.The presoma of the nickelic positive electrode for example can be NixCoyAl1-x-y's
The co-precipitate of hydroxide, carbonate or oxalates, or NixCoyAl1-x-yHydroxide and carbonate coprecipitation
The combination of the combination of the combination of thing, hydroxide and oxalate coprecipitation thing, carbonate and oxalate coprecipitation thing, hydroxide
Combination of thing, carbonate and oxalate coprecipitation thing etc..
In a preferred technical solution of the present invention, the presoma of the nickelic positive electrode is through preheating
Presoma.The atmosphere of the preheating be air, the temperature of preheating between 200～1000 DEG C, preheating when
Between be 1～30h.
The temperature of the preheating for example can for 210 DEG C, 255 DEG C, 283 DEG C, 330 DEG C, 392 DEG C, 452 DEG C, 530
DEG C, 608 DEG C, 677 DEG C, 720 DEG C, 780 DEG C, 855 DEG C, 890 DEG C, 914 DEG C or 990 DEG C etc..The time of the preheating is for example
Can be 1h, 2.2h, 3.5h, 4h, 5.5h, 7h, 11.5h, 15h, 18h, 22.5h, 27h or 29.5h etc..
In a kind of preferred technical scheme of the present invention, the nonmetal doping agent is that siliceous, phosphorous or boracic etc. is non-
One kind or at least two combinations in the compound of metallic element.The chemical combination of the nonmetalloids such as siliceous, the phosphorous or boracic
Thing is included but is not limited to：Lithium metasilicate, lithium metasilicate, ammonium silicate, metasilicic acid ammonium, esters of silicon acis, lithium phosphate, lithium hydrogen phosphate, di(2-ethylhexyl)phosphate
Hydrogen lithium, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphoric acid, pyrophosphoric acid, phosphorus pentoxide, lithium pyroborate, lithium metaborate, burnt boron
Sour ammonium, ammonium metaborate, boric acid, metaboric acid, pyroboric acid or diboron trioxide.Additionally, the nonmetal doping agent can also be upper
State in compound at least two combination.For example, the nonmetal doping agent can for lithium metasilicate, metasilicic acid ammonium, lithium hydrogen phosphate,
Ammonium dihydrogen phosphate, pyrophosphoric acid, lithium borate, pyroboric acid, or the combination of ammonium silicate and phosphorus pentoxide, the butyl ester of silicic acid four and three oxidations
The combination of the combination of two boron, ammonium dihydrogen phosphate and lithium metaborate, combination of pyrophosphoric acid, lithium metasilicate and ammonium metaborate etc..
Because the lithium salts itself that the dopant of the nonmetalloids such as siliceous, phosphorus, boron is formed after sintering is lived with electrochemistry
Property, and its specific capacity is close to the theoretical specific capacity of even above nickelic positive electrode, therefore the ratio of material is not resulted in after adulterating
Capacity is reduced.
In a preferred technical solution of the present invention, the consumption of the nonmetal doping agent is before nickelic positive electrode
Drive the 0.1%～10% of weight.For example, the dopant consumption can be forerunner's weight of nickelic positive electrode
0.1%th, 0.3%, 0.5%, 1.1%, 1.8%, 4%, 6.5%, 7.2% or 9.5% etc..
In a preferred technical solution of the present invention, the liquid phase medium can be in water, alcohol (ethanol) or glycerine
One kind or at least two combination.The combination for example can be the combination of water and alcohol, the combination of water and glycerine, alcohol and
The combination of glycerine, the combination of water, alcohol and glycerine.
In a preferred technical solution of the present invention, the consumption of the liquid phase medium is the presoma of nickelic positive electrode
1/10～10 times of quality.The consumption of the liquid phase medium for example can be 1/2 times of forerunner's weight of nickelic positive electrode,
2 times, 4.5 times, 7 times, 8.5 times, 9 times or 10 times etc..
In a preferred technical solution of the present invention, the scattered mode is magnetic agitation, mechanical agitation, ultrasound are shaken
Swing, the one kind in ball milling or three-dimensional hybrid.
In a preferred technical solution of the present invention, it is described be separated into it is fully dispersed.
In a preferred technical solution of the present invention, the drying is carried out in drying equipment, baking temperature be 40～
400 DEG C, drying time is 1～48h.The baking temperature for example can for 80 DEG C, 115 DEG C, 180 DEG C, 270 DEG C, 310 DEG C, 350
DEG C, 370 DEG C or 390 DEG C etc..The drying time for example can for 2.5h, 6h, 9h, 12h, 15h, 17h, 20h, 22h, 25h,
28h, 31h, 34h, 37h, 40h, 43h or 46h etc..
In the present invention, according to the presoma of nickelic positive electrode, nonmetal doping agent, liquid phase medium and the lithium for selecting
The difference in source, what is obtained after being dried both can be the presoma and nonmetal doping agent and/or the thing of lithium source of nickelic positive electrode
Reason mixture, or nonmetal doping agent are reacted with the presoma and/or liquid phase medium and/or lithium source of nickelic positive electrode
Mix products afterwards.For example, the nonmetal doping agent is lithium phosphate, and the presoma of nickelic positive electrode is NixCoyMn1-x-y
Carbonate, liquid phase medium is alcohol, then that obtain is Ni after being driedxCoyMn1-x-yCarbonate and lithium phosphate physical mixed
Thing.Again for example, the nonmetal doping agent is phosphorus pentoxide, and the presoma of nickelic positive electrode is NixCoyAl1-x-yHydrogen
Oxide, liquid phase medium is water.Because phosphorus pentoxide and liquid phase medium water react generation phosphoric acid, phosphoric acid further with portion
Divide NixCoyAl1-x-yHydroxide reaction generate NixCoyAl1-x-yPhosphate, therefore, be dried after obtain be
NixCoyAl1-x-yHydroxide and phosphatic mixture.
In a preferred technical solution of the present invention, the lithium source is lithium acetate, lithium sulfate, lithium hydroxide, lithium nitrate
Or the one kind in lithium carbonate or at least two combination.The combination can be for example the combination of lithium acetate and lithium sulfate, acetic acid
The combination of the combination of lithium and lithium hydroxide, lithium nitrate and lithium carbonate, the combination of lithium acetate, lithium sulfate and lithium hydroxide or nitric acid
Combination of lithium, lithium carbonate and lithium sulfate etc..
In a preferred technical solution of the present invention, the addition of the lithium source stoichiometrically 0.9～1.2 times
Add.The addition of the lithium source for example can be stoichiometrically 0.92 times, 0.97 times, 1 times, 1.06 times, 1.10 times,
1.15 times, 1.2 times of equal proportions additions.Presoma, nonmetal doping agent of the addition of the lithium source according to nickelic positive electrode
Or sintering process conditions (such as sintering temperature, time) factor is determining.Comparative example and embodiment in this specification is adopted
Lithium source addition be typical case and it is nonrestrictive.
In a preferred technical solution of the present invention, the atmosphere of the sintering be air, oxygen or nitrogen and oxygen with
The mixed gas of certain volume ratio mixing.The atmosphere of the sintering for example can be air, oxygen, or nitrogen and oxygen with
1:9、1:4、2:3、1:1、7:The gas of 3 equal-volume ratios mixing.
In a preferred technical solution of the present invention, the temperature of the sintering is 400～1000 DEG C, and the time of sintering is
4～48h.The temperature of the sintering for example can for 450 DEG C, 500 DEG C, 550 DEG C, 580 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 735
DEG C, 750 DEG C, 800 DEG C, 810 DEG C, 850 DEG C, 900 DEG C, 950 DEG C or 980 DEG C etc..The time of the sintering for example can for 5h,
7.5h, 9h, 13h, 18h, 25h, 29h, 33h, 40h, 45h or 48h etc..
The second object of the present invention is to provide a kind of preparation method using nickelic positive electrode as above to obtain
Nickelic positive electrode.The nickelic positive electrode obtained using the method has excellent heat endurance.
The third object of the present invention is to provide a kind of lithium ion battery, and the lithium ion battery is with as above nickelic
Positive electrode is used as positive electrode.Using the nickelic positive electrode as positive electrode, the lithium ion battery for obtaining has excellent
High temperature cyclic performance and high-temperature storage performance.
Compared with the prior art, the present invention has the advantages that：
(1) in the method for the present invention nonmetal doping agent presoma process finished product during add, without
Introduce when preparing presoma, it is to avoid nonmetal doping agent be co-precipitated with presoma or secondary precipitation complex processing requirements, side
Method is simple；
(2) nonmetalloid that preferably used of the present invention in the lattice of nickelic positive electrode with oxygen atom with covalent bond
Form combine, with higher bond energy so as to which crystal structure is more stable in the case of a high temperature, the oxygen in lattice is difficult to be taken off
The Ni formed under lithium state4+Aoxidize and separate out, so as to improve the heat endurance of material；
(3) lithium salts that the nonmetal doping agent that the present invention is preferably used is formed Jing after high temperature sintering is in neutral or weak base
Property, can generally reduce the alkalescence of nickelic positive electrode, and improve the property of material surface, so as to improve the high temperature circulation of battery
Life-span and high-temperature storage life-span；
(4) the nonmetal doping agent that preferably used of the present invention itself or the compound that formed after it is thermally decomposed with compared with
Low fusing point, is conducive to doped chemical fully to spread in the material and be uniformly distributed, so as to reach preferably doping effect.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, and in order to allow the above and other objects of the present invention, feature and advantage can
Become apparent, below especially exemplified by the specific embodiment of the present invention.
Specific embodiment
The illustrative embodiments of the disclosure are described in more detail below.Although hereinafter showing the example of the disclosure
Property embodiment, it being understood, however, that may be realized in various forms the disclosure and should not be by embodiments set forth herein institute
Limit.On the contrary, there is provided these embodiments are able to be best understood from the disclosure, and can be by the scope of the present disclosure
Complete conveys to those skilled in the art.Although it should be appreciated that those skilled in the art are not it is contemplated that in this theory
But it is expressly recited in bright book or records and realizes the present invention and be included in each in spirit of the invention, principle and scope
The method of kind, component and content.The all examples and conditional language quoted from this specification are all in order at what is illustrated and instruct
Purpose, with help reader to understand principle that inventor contributes to prior art and concept, and should be understood that and do not limit
The example specifically quoted from these and condition.Additionally, in order to be illustrated more clearly that, eliminate for known method, component and
The detailed description of content, not obscure description of the invention.It should be understood that unless stated otherwise, each embodiment described herein
In feature can be combined with each other.
Comparative example 1：
It is 5 by 100 parts of quality Ni, Co, the mol ratio of Mn:2:3 carbonate coprecipitation thing presoma and 32.36 parts of quality
Lithium carbonate (99.0%), mix 4h under the conditions of 25Hz in three-dimensional mixer, be subsequently placed in batch-type furnace 680 under air atmosphere
DEG C preheating 6h；960 DEG C of sintering 12h under oxygen atmosphere again are cooled to after room temperature, 400 mesh standard sieves are crossed after cooling, obtained
To conventional nickel-cobalt lithium manganate cathode material.The exothermic peak temperature of gained positive electrode is tested using differential scanning calorimetry (DSC)
Degree.By gained positive electrode, binding agent PVDF, conductive agent acetylene black in mass ratio 96:2:2 are carried out just in oily series solvent NMP
Pole dispensing, obtains uniform anode sizing agent, and the anode sizing agent for preparing is uniformly coated on plus plate current-collecting body Al paper tinsels, 120
DEG C, 130 DEG C, be separately dried 10 minutes in 128 DEG C of convective drying case after obtain positive plate, by compacted density 3.35g/cm3Will
Positive plate roll-in is standby.Positive plate is assembled into polymer soft-package battery by traditional manufacturing technique, test battery 45 DEG C, 3.0
Cycle performance under the conditions of～4.2V, 1C multiplying powers and full of the battery status change after lower 60 DEG C of storages of electricity condition 7 days.
Embodiment 1：
It is 5 by 200 parts of quality Ni, Co, the mol ratio of Mn:2:3 carbonate coprecipitation thing presoma and 1.8 parts of quality
Lithium metasilicate is added in the deionized water of 200 parts of quality, disperses 2h to obtain slurry under mechanical stirring；By gained slurry 120
12h is dried at DEG C, precursor mixture is obtained；The precursor mixture of 100 parts of quality is weighed, the carbon of 31.76 parts of quality is added
Sour lithium (99.0%), 4h is mixed in three-dimensional mixer under the conditions of 25Hz, be subsequently placed in air atmosphere in batch-type furnace it is lower 680 DEG C it is pre-
Burn and process 6h；960 DEG C of sintering 12h under oxygen atmosphere again are cooled to after room temperature, 400 mesh standard sieves are crossed after cooling, had
The nickel-cobalt lithium manganate cathode material for having element silicon to adulterate, also with DSC its exothermic peak temperature is tested.Subsequently by comparative example 1
The process conditions, use gained positive electrode makes the polymer soft-package battery of same model, equally tests its high temperature circulation
Performance and high-temperature storage performance.
Embodiment 2：
Nickel-cobalt lithium manganate cathode material is prepared according to identical constituent content in embodiment 1 and process conditions, simply by it
The quality of middle lithium metasilicate brings up to 3.6 parts from 1.8 parts, and the quality of lithium carbonate is reduced to 31.48 parts from 31.76 parts, obtains
Nickel-cobalt lithium manganate cathode material with element silicon doping, also with DSC its exothermic peak temperature is tested.Subsequently press comparative example 1
Described in process conditions, use gained positive electrode make same model polymer soft-package battery, equally test its high temperature and follow
Ring performance and high-temperature storage performance.
Embodiment 3：
Nickel-cobalt lithium manganate cathode material is prepared according to identical constituent content in embodiment 1 and process conditions, simply by it
The quality of middle lithium metasilicate is reduced to 0.08 part from 1.8 parts, and the quality of lithium carbonate brings up to 32.03 parts from 31.76 parts, obtains
Nickel-cobalt lithium manganate cathode material with element silicon doping, also with DSC its exothermic peak temperature is tested.Subsequently press comparative example 1
Described in process conditions, use gained positive electrode make same model polymer soft-package battery, equally test its high temperature and follow
Ring performance and high-temperature storage performance.
Embodiment 4：
Nickel-cobalt lithium manganate cathode material is prepared according to identical constituent content in embodiment 1 and process conditions, simply by it
The quality of middle lithium metasilicate brings up to 20 parts from 1.8 parts, and the quality of lithium carbonate is reduced to 29.13 parts from 31.76 parts, is had
The nickel-cobalt lithium manganate cathode material for having element silicon to adulterate, also with DSC its exothermic peak temperature is tested.Subsequently by comparative example 1
The process conditions, use gained positive electrode makes the polymer soft-package battery of same model, equally tests its high temperature circulation
Performance and high-temperature storage performance.
Embodiment 5：
It is 5 by 99.11 parts of quality Ni, Co, the mol ratio of Mn:2:3 carbonate coprecipitation thing presoma, 0.89 part of quality
Lithium metasilicate and 31.76 parts of quality lithium carbonate (99.0%) add 100 parts of quality deionized water in, under mechanical stirring
Dispersion 2h obtains slurry；Gained slurry is dried into 12h at 120 DEG C, precursor mixture is obtained, batch-type furnace is subsequently placed in hollow
The lower 680 DEG C of preheating 6h of gas atmosphere；960 DEG C of sintering 12h under oxygen atmosphere again are cooled to after room temperature, 400 are crossed after cooling
Mesh standard sieve, obtains the nickel-cobalt lithium manganate cathode material with element silicon doping, and also with DSC its exothermic peak temperature is tested.
Subsequently by process conditions described in comparative example 1, use gained positive electrode makes the polymer soft-package battery of same model, equally
Test its high temperature cyclic performance and high-temperature storage performance.
Embodiment 6：
It is 5 by 99.11 parts of quality Ni, Co, the mol ratio of Mn:2:3 carbonate coprecipitation thing presoma, 0.89 part of quality
Lithium metasilicate and 31.76 parts of quality lithium carbonate (99.0%), mix 4h under the conditions of 25Hz in three-dimensional mixer, then put
The lower 680 DEG C of preheating 6h of air atmosphere in batch-type furnace；Again 960 DEG C of sintering 12h under oxygen atmosphere are cooled to after room temperature,
400 mesh standard sieves are crossed after cooling, the nickel-cobalt lithium manganate cathode material with element silicon doping is obtained, also with DSC it is tested
Exothermic peak temperature.Subsequently by process conditions described in comparative example 1, the polymer that use gained positive electrode makes same model is soft
Bag battery, equally tests its high temperature cyclic performance and high-temperature storage performance.
Comparative example 2：
It is 8 by 200 parts of quality Ni, Co, the mol ratio of Al:1.5:It is hollow that 0.5 hydroxide precursor is placed in batch-type furnace
The lower 500 DEG C of preheating 7.5h of gas atmosphere, take the presoma of 100 parts of quality Jing preheatings after cooling, add 89.31 parts of quality
Lithium acetate (99.0%), mix 4h under the conditions of 25Hz in three-dimensional mixer, be subsequently placed in batch-type furnace 780 under oxygen atmosphere
DEG C sintering 10h, after cooling cross 400 mesh standard sieves, obtain conventional nickel-cobalt lithium manganate cathode material.Using differential scanning calorimetry
(DSC) exothermic peak temperature of test gained positive electrode.By process conditions described in comparative example 1, simply by compacted density from
3.35g/cm3Bring up to 3.55g/cm3Roll-in is carried out to positive plate, by traditional manufacturing technique polymer soft-package battery is assembled into, surveyed
Cycle performance of the examination battery under the conditions of 45 DEG C, 3.0～4.2V, 1C multiplying powers and full of the electricity after 60 DEG C of storages under electricity condition 7 days
Pond state change.
Embodiment 7：
It is 8 by 300 parts of quality Ni, Co, the mol ratio of Al:1.5:It is hollow that 0.5 hydroxide precursor is placed in batch-type furnace
The lower 500 DEG C of preheating 7.5h of gas atmosphere, take presoma, the phosphoric acid of 2.4 parts of quality of 200 parts of quality Jing preheatings after cooling
The lithium of hydrogen two, in adding the deionized water of 240 parts of quality, disperses under mechanical stirring 0.5h to obtain slurry；By gained slurry 130
20h is dried at DEG C, precursor mixture is obtained；The precursor mixture of 100 parts of quality is weighed, the vinegar of 88.96 parts of quality is added
Sour lithium (99.0%), 4h is mixed in three-dimensional mixer under the conditions of 25Hz, is subsequently placed in the lower 780 DEG C of burnings of oxygen atmosphere in batch-type furnace
Knot 12h, crosses 400 mesh standard sieves after cooling, the nickel cobalt lithium aluminate cathode material with P elements doping is obtained, also with DSC
Test its exothermic peak temperature.Subsequently by process conditions described in comparative example 2, use gained positive electrode makes the poly- of same model
Compound soft-package battery, equally tests its high temperature cyclic performance and high-temperature storage performance.
Embodiment 8：
Nickel-cobalt lithium manganate cathode material is prepared according to identical constituent content in embodiment 3 and process conditions, simply by it
In the lithium of phosphoric acid hydrogen two of 2.4 parts of quality be substituted for the lithium of phosphoric acid hydrogen two of 2.4 parts of quality and the pyroboric acid of 2.4 parts of quality, and acetic acid
The quality of lithium is reduced to 88.92 parts from 88.96 parts, obtains the nickel cobalt lithium aluminate cathode material adulterated with phosphorus and boron element, together
Sample tests its exothermic peak temperature using DSC.Subsequently by process conditions described in comparative example 2, use gained positive electrode makes phase
The polymer soft-package battery of same model, equally tests its high temperature cyclic performance and high-temperature storage performance.
The performance of the positive electrode prepared by above-mentioned each comparative example and embodiment and its lithium ion battery is carried out afterwards right
Than comparing result is referring to table 1.
The performance comparison table of positive electrode and its lithium ion battery prepared by each comparative example of table 1 and embodiment
As seen from the above table：
(1) heat endurance of the positive electrode prepared by embodiment 1, embodiment 2, embodiment 4 and embodiment 5 is better than
Positive electrode prepared by comparative example 1, the high temperature cyclic performance and high-temperature storage performance of its corresponding lithium ion battery are also intended to
The lithium ion battery being substantially better than prepared by comparative example 1；
(2) positive electrode and its lithium ion battery prepared by comparative example 1, embodiment 2, embodiment 3 and embodiment 4
Results of property understand, improve the consumption of nonmetal doping agent can further be lifted the heat endurance and its lithium of positive electrode from
The high temperature cyclic performance and high-temperature storage performance of sub- battery, but further improve the consumption of the dopant and can not significantly carry
The performance of high positive electrode and its lithium ion battery, rather than the consumption of metal dopant is too low, then almost do not have raising positive pole
The effect of the performance of material and its lithium ion battery；
(3) positive electrode prepared by comparative example 5, embodiment 1 and comparative example 1 and its performance knot of lithium ion battery
Fruit understands, in the situation by liquid phase medium is scattered in together with the presoma of lithium source and nickelic positive electrode and nonmetal doping agent
Under, its performance is better than positive electrode and its ion battery prepared by comparative example 1, and with the positive pole material prepared by embodiment 1
Material and its lithium ion battery performance substantially close to；
(4) positive electrode prepared by comparative example 6, embodiment 1 and comparative example 1 and its performance knot of lithium ion battery
Fruit understands that, in the case where liquid phase medium is not used, its performance is better than positive electrode and its ion-conductance prepared by comparative example 1
Pond, but the performance of the positive electrode not as prepared by embodiment 1 and its lithium ion battery is notable；
(5) positive electrode prepared by embodiment 7 and 8 is intended to be substantially better than the positive electrode prepared by comparative example 2, and its is right
The high temperature cyclic performance and high-temperature storage performance of the lithium ion battery answered also is intended to be substantially better than the lithium ion prepared by comparative example 2
Battery；
(6) positive electrode and its results of property of lithium ion battery prepared by comparative example 7 and 8 understands, while adding
Plus one or more dopant can further lift the heat endurance of positive electrode and its high temperature of lithium ion battery
Cycle performance and high-temperature storage performance.
Illustrate to serve the lifting nickelic positive electrode of lithium ion battery based on technological means provided by the present invention thermally-stabilised
Property, and significantly improve the high temperature cyclic performance of its lithium ion battery and the Expected Results of high-temperature storage performance.
Claims (10)
1. a kind of preparation method of nickelic positive electrode, comprises the following steps：
Nonmetal doping agent is added in the presoma of nickelic positive electrode, lithium source is added and is obtained with nonmetallic unit after sintering
The nickelic positive electrode of element doping.
2. the method for claim 1, it is characterised in that the nickelic positive electrode is Li (NixCoyMn1-x-y)O2, its
In 0.4≤x<1,0<y≤0.4；Or Li (NixCoyAl1-x-y)O2, wherein 0.7≤x<1,0<y<0.3.
3. method as claimed in claim 1 or 2, it is characterised in that comprise the following steps：
The presoma of nickelic positive electrode and nonmetal doping agent are scattered in into liquid phase medium, it is to be dried after, add lithium source, then
Sintering, obtains nickelic positive electrode；
Preferably, the presoma of nickelic positive electrode, nonmetal doping agent and lithium source are scattered in into liquid phase medium, it is to be dried
Afterwards, it is sintered, obtains nickelic positive electrode；
Preferably, the presoma of nickelic positive electrode, nonmetal doping agent and lithium source are sufficiently mixed, are then sintered, obtained
Nickelic positive electrode.
4. the method as described in one of claim 1-3, it is characterised in that the presoma of nickelic positive electrode is NixCoyMn1-x-y
Hydroxide, carbonate coprecipitation thing or oxalate coprecipitation thing in one kind or at least two combination, wherein 0.4≤x<
1,0<y≤0.4；
Preferably, the presoma of the nickelic positive electrode is NixCoyAl1-x-yHydroxide, carbonate coprecipitation thing or grass
One kind or at least two combination in hydrochlorate co-precipitate, wherein 0.7≤x<1,0<y<0.3；
Preferably, the presoma of the nickelic positive electrode is the presoma through preheating；
Preferably, the atmosphere of the preheating is air, and the temperature of preheating is 200～1000 DEG C, preheating when
Between be 1～30h.
5. the method as described in one of claim 1-4, it is characterised in that the nonmetal doping agent is siliceous, phosphorous or contain
One kind or at least two combinations in the compound of boron；
Preferably, siliceous, phosphorous, boracic the compound includes：Lithium metasilicate, lithium metasilicate, ammonium silicate, metasilicic acid ammonium, silicon
Acid esters, lithium phosphate, lithium hydrogen phosphate, lithium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphoric acid, pyrophosphoric acid, five oxidations
In two phosphorus, lithium pyroborate, lithium metaborate, pyroboric acid ammonium, ammonium metaborate, boric acid, metaboric acid, pyroboric acid or diboron trioxide one
Kind or at least two combination；
Preferably, the consumption of the nonmetal doping agent is the 0.1%～10% of forerunner's weight of nickelic positive electrode.
6. the method as described in one of claim 3-5, it is characterised in that the liquid phase medium is in water, alcohol or glycerine
It is a kind of or at least two combination；
Preferably, the consumption of the liquid phase medium is 1/10～20 times of forerunner's weight of nickelic positive electrode.
7. the method as described in one of claim 3-6, it is characterised in that the scattered mode is that magnetic agitation, machinery are stirred
Mix, the one kind in sonic oscillation, ball milling or three-dimensional hybrid；
Preferably, the drying is carried out in drying equipment, and baking temperature is 40～400 DEG C, and drying time is 1～48h.
8. the method as described in one of claim 3-7, it is characterised in that the lithium source is lithium acetate, lithium sulfate, hydroxide
One kind or at least two combination in lithium, lithium nitrate or lithium carbonate；
Preferably, the addition of the lithium source 0.9～1.2 times of addition stoichiometrically；
Preferably, the atmosphere of the sintering is the mixed gas of air, oxygen or nitrogen and oxygen；
Preferably, the temperature of the sintering is 400～1000 DEG C, and the time of sintering is 4～48h.
9. the nickelic positive pole material that a kind of preparation method of the nickelic positive electrode using as described in one of claim 1-8 is obtained
Material.
10. a kind of lithium ion battery, the lithium ion battery is using nickelic positive electrode as claimed in claim 9 as positive pole material
Material.
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