CN106450242A - Compound active substance of lithium-ion battery, preparation method thereof, electrode slurry and anode or cathode of lithium-ion battery and lithium-ion battery - Google Patents

Compound active substance of lithium-ion battery, preparation method thereof, electrode slurry and anode or cathode of lithium-ion battery and lithium-ion battery Download PDF

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Publication number
CN106450242A
CN106450242A CN201611155023.5A CN201611155023A CN106450242A CN 106450242 A CN106450242 A CN 106450242A CN 201611155023 A CN201611155023 A CN 201611155023A CN 106450242 A CN106450242 A CN 106450242A
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ion battery
lithium
lithium ion
active material
metallic element
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先雪峰
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Individual
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Priority to CN201611155023.5A priority Critical patent/CN106450242A/en
Priority to PCT/CN2016/113807 priority patent/WO2018107546A1/en
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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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • 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 relates to the technical field of lithium-ion batteries, and discloses a compound active substance of a lithium-ion battery, a preparation method thereof, electrode slurry and an anode or a cathode of the lithium-ion battery and the lithium-ion battery. The compound active substance of the lithium-ion battery is an active substance coated with an additive, wherein the additive is M(OH)a; M is at least one element of a group-IIA metallic element, a group-IB metallic element, a group-IIB metallic element, a group-IIIB metallic element, a group-IVB metallic element, a group-VB metallic element, a group-VIB metallic element, a group-VIIB metallic element, a group-VIII metallic element, a group-IIIA metallic element, a group-IVA metallic element, a group-VA metallic element, boron and silicon; and a is greater than 0. The compound active substance of the lithium-ion battery is used as a positive and negative active substance to prepare the anode and/or the cathode of the lithium-ion battery; the safety of the lithium-ion battery which is prepared and obtained in this way can be obviously improved.

Description

Lithium ion battery active material and preparation method thereof, lithium ion cell electrode slurry Material, negative or positive electrode and lithium ion battery
Technical field
The present invention relates to technical field of lithium ion, in particular it relates to a kind of lithium ion battery active material and Its preparation method, a kind of lithium ion battery electrode sizing agent, a kind of negative or positive electrode and a kind of lithium ion battery.
Background technology
Lithium ion battery is the green high-capacity battery of a new generation, with voltage high, energy density is big, life-span length, self discharge The many merits such as little, memory-less effect, operating temperature range width, in small-sized movable energy field (such as mobile phone, digital camera Deng), Large-scale Mobile energy field (such as plug-in hybrid electric vehicle, pure electric vehicle etc.) and (the such as energy storage of fixed sources of energy field Power station, UPS etc.), suffer from being widely applied prospect.
Lithium ion battery voltage height is also implied that under state-of-charge, and the positive and negative electrode of battery has larger electric potential difference, Mean that cathodic reduction is higher, positive pole oxidisability is higher, and heat stability is worse.Especially for using cobalt acid lithium, lithium nickel For the battery of the high-voltage anode materials such as cobalt alumina, lithium nickel cobalt manganese oxygen, overcharging, acupuncture, under the abuse condition such as extruding usually Serious potential safety hazard can be there is because thermal runaway causes on fire or even blast.
In addition, with traditional plumbic acid, the alkalescence for doing electrolyte solvent using non-combustible and with fire retardation water Battery is compared, and commercial li-ion battery generally does electrolyte solvent using flammable carbonate based organic solvent, or gel is birdsed of the same feather flock together Compound does electrolyte, under abuse conditions, can expand the consequence of security incident further.
The potential safety hazard of existing lithium ion battery hinders the large-scale application to lithium ion battery, therefore, research and development one The lithium ion battery that safety is greatly improved is planted, is had important practical significance.
Content of the invention
The invention aims to overcoming, lithium ion battery security in prior art is low, there is severe compromise Defect, provides a kind of lithium ion battery active material and preparation method thereof, a kind of lithium ion battery electrode sizing agent, Yi Zhongzheng Pole or negative pole and a kind of lithium ion battery.
To achieve these goals, in a first aspect, the invention provides a kind of lithium ion battery active material, described The active substance that lithium ion battery active material is coated for additive, the additive is M (OH)a, wherein, M is Group IIA Metallic element, IB race metallic element, Group IIB metal element, IIIB race metallic element, Group IVB metallic element, metal unit of VB race Element, group vib metallic element, VIIB race metallic element, group VIII metal element, Group IIIA metallic element, IVA race metallic element, At least one element in VA race metallic element, boron and silicon, a ＞ 0.
Second aspect, the invention provides a kind of preparation method of lithium ion battery active material, the method includes： The hydroxide precipitation of element M is prepared, in the presence of dispersants, the hydroxide precipitation of the element M is mixed with active substance Close, then gained mixture is carried out heat treatment.
The third aspect, the invention provides a kind of lithium ion battery electrode sizing agent, the electrode slurry includes lithium-ion electric Pond active substance, binding agent, conductive agent, solvent and optional thickening agent, wherein, the lithium ion battery active substance is this Bright described lithium ion battery active material.
Fourth aspect, the invention provides a kind of lithium ion cell positive or negative pole, the lithium ion cell positive or negative Pole includes collector and the electrode dressing on collector, and the electrode dressing contains lithium ion battery active substance, bonding Agent, conductive agent and optional thickening agent, wherein, the lithium ion battery active substance is multiple for lithium ion battery of the present invention Close active substance.
5th aspect, the invention provides a kind of lithium ion battery, the lithium ion battery includes battery container and position Battery core component and electrolyte inside the battery container, the battery core component includes positive pole, negative pole and barrier film, and described just extremely Lithium ion cell positive of the present invention, and/or the negative pole be lithium ion battery negative of the present invention.
The present inventor is creative under study for action to be found, by the lithium ion battery active material of the present invention ( The Surface coating of active substance additive of the present invention, prepares lithium ion battery active material) as positive and negative Pole active substance prepares lithium ion cell positive and/or negative pole, can significantly improve the lithium ion battery that thus prepares Safety.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that described herein concrete Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
Herein the end points of disclosed scope and any value are not limited to the accurate scope or value, these scopes or Value should be understood to comprising the value for being close to these scopes or value.For numerical range, between the endpoint value of each scope, respectively Between the endpoint value of individual scope and single point value, and individually can be obtained with combination with one another between point value one or more New numerical range, these numerical rangies should be considered herein concrete open.
In a first aspect, the invention provides a kind of lithium ion battery active material, the lithium ion battery is compound to live Property the active substance that coats for additive of material, the additive bea, wherein, M is Group IIA metal element, IB race gold Category element, Group IIB metal element, IIIB race metallic element, Group IVB metallic element, VB race metallic element, group vib metallic element, VIIB race metallic element, group VIII metal element, Group IIIA metallic element, IVA race metallic element, VA race metallic element, boron and At least one element in silicon, a ＞ 0.
Wherein, it will be understood by those skilled in the art that M (OH)aIn, the selection of a meets the chemistry meter of respective substance Amount compares principle.
In the lithium ion battery active material of the present invention, under preferable case, in additive, the Group IIA metal unit Element is Be and/or Mg, and it is Zn that IB race metallic element is Cu, the Group IIB metal element, and IIIB race metallic element is At least one in Y, Sc, La, Ce, Nd, Sm, Gd and Er, the Group IVB metallic element is Ti and/or Zr, VB race metal Element is V and/or Nb, and it is Mn that the group vib metallic element is Cr and/or Mo, VIIB race metallic element, the VIII Metallic element is at least one in Fe, Co and Ni, and it is Sn that the Group IIIA metallic element is Al, IVA race metallic element, VA race metallic element is Bi and/or Sb.
In the lithium ion battery active material of the present invention, it was found by the inventors of the present invention that in lithium ion battery activity Material surface coats specific additive, can obtain the more preferable lithium ion battery active substance of safety, therefore, in order to enter one Step improves the safety of the lithium ion battery for preparing, and under preferable case, additive is aluminium hydroxide, orthosilicic acid and hydroxide At least one in titanium.
In the lithium ion battery active material of the present invention, improve and energy density for lithium ion battery security Consider, under preferable case, on the basis of the weight of lithium ion battery active material, the content of additive is 0.05- 30 weight %, more preferably 2-15.3 weight %, are still more preferably 5.7-9.9 weight %.
In the lithium ion battery active material of the present invention, for active substance, there is no particular limitation, can be this The conventional use of various active substances in field, under preferable case, active substance is positive active material or negative electrode active material, institute State positive active material for cobalt acid lithium, lithium nickel oxygen, lithium-nickel-cobalt-oxygen, lithium nickel cobalt alumina, lithium nickel cobalt manganese oxygen, Li-Ni-Mn-O, LiMn2O4, Lithium vanadate, LiFePO4, lithium manganese phosphate, iron manganese phosphate for lithium, iron manganese phosphate nickel lithium, iron manganese phosphate cobalt lithium, iron manganese phosphate nickel cobalt lithium, At least one in phosphoric acid vanadium lithium and ferric metasilicate lithium, the negative electrode active material is graphite, lithium titanate, silicon, hard carbon, stannum and oxidation At least one in stannum.
Second aspect, the invention provides the preparation method of above-mentioned lithium ion battery active material, the method bag Include：The hydroxide precipitation of element M is prepared, in the presence of dispersants, by the hydroxide precipitation of the element M and active substance Then gained mixture is carried out heat treatment by mixing.
In the preparation method of the present invention, the selection of element M is can be found in aforementioned corresponding interior with the element M in above-mentioned additive Hold, it is no longer repeated for here.
In the preparation method of the present invention, the preparation method for the hydroxide precipitation of aforementioned different element M does not have spy Other restriction, can be various methods commonly used in the art, and this is well known to those skilled in the art, and will not be described here.
In the preparation method of the present invention, it will be understood by those skilled in the art that in the hydroxide precipitation by element M Before mixing with active substance, first the impurity for remaining in the hydroxide precipitation of the element M for preparing is removed, for removing There is no particular limitation for the method for wherein impurity, can be various methods commonly used in the art, for example, can be washed with deionized water Wash to remove impurity therein.
In the preparation method of the present invention, for the species of dispersant, there is no particular limitation, can be to prepare element M Used by the process of hydroxide precipitation solvent, under preferable case, dispersant is isopropanol, deionized water, ethanol, butanol and third At least one in ketone, more preferably isopropanol or deionized water.
In the preparation method of the present invention, under preferable case, the hydroxide of element M is precipitated the side for being mixed with active substance Formula is strong stirring, and the condition of stirring is preferably included：Rotating speed is 100-400rpm, and the time is 1-10h.
In the preparation method of the present invention, for the mode of heat treatment, there is no particular limitation, can be commonly used in the art Various modes, under preferable case, the mode of heat treatment is spray drying, microwave drying, fluid bed drying or oven drying, in order to Efficiency is improved, is more preferably spray-dried.The condition of heat treatment can include：Temperature is 65-200 DEG C, and the time is 1s- 12h.Wherein, the condition of spray drying includes：Temperature is 65-200 DEG C, and the time is 1-100s, preferably 1-10s.For concrete Temperature and time, can be selected according to different heat treatment modes, this is well known to those skilled in the art, and here is not Repeat again.
According to the aforesaid preparation method of the present invention, can prepare Surface coating has the active substance of aforementioned additive, Lithium ion battery active material is obtained, by the hydroxide precipitation of control element M and the consumption of active substance, permissible Prepare the lithium ion battery active material of special additive content, under preferable case, the hydroxide of control element M Precipitation and the consumption of active substance so that on the basis of the weight of lithium ion battery active material, the content of additive is 0.05-30 weight %, more preferably 2-15.3 weight %, are still more preferably 5.7-9.9 weight %.
The third aspect, the invention provides a kind of lithium ion battery electrode sizing agent, the electrode slurry includes lithium-ion electric Pond active substance, binding agent, conductive agent, solvent and optional thickening agent, wherein, the lithium ion battery active substance is this Bright described lithium ion battery active material.
Wherein, it will be understood by those skilled in the art that lithium ion battery electrode sizing agent of the present invention can be Lithium ion battery anode glue size, or lithium ion battery cathode slurry.In lithium ion battery anode glue size or lithium-ion electric In the cathode size of pond, the species for active substance, binding agent, conductive agent, solvent and thickening agent is selected and consumption is not special Restriction, can be respectively this area respective components routine species select and consumption, for battery energy density and battery The consideration of combination property, under preferable case, on the basis of the weight of the lithium ion battery active material, binding agent is with dry The content of base meter is 0.5-5 weight %, and the content of conductive agent is 0.5-5 weight %, and the content of solvent is 55-200 weight %, increases Thick dose of content is 0-2.5 weight %.Wherein, thickening agent is not typically used in battery anode slurry in lithium, and in lithium ion Used in battery cathode slurry, on the basis of the weight of the lithium ion battery active material, content is 0.5-2.5 weight Amount %.
Wherein, in lithium ion battery anode glue size, for the positive active material in lithium ion battery active material There is no particular limitation, can be various positive active materials as previously described, and it is no longer repeated for here.
Wherein, in lithium ion battery cathode slurry, for the negative electrode active material in lithium ion battery active material There is no particular limitation, can be various negative electrode active materials as previously described, and it is no longer repeated for here.
In lithium ion battery anode glue size and lithium ion battery cathode slurry, for binding agent, there is no particular limitation, can Think various binding agents commonly used in the art, under preferable case, binding agent is polyacrylamide, polyvinylidene fluoride, poly- In tetrafluoroethene, butadiene-styrene rubber, cellulose-based polymer, polyvinyl alcohol, polyolefin, Viton and Polyurethane at least one Kind, cellulose-based polymer can be selected from methylcellulose, ethyl cellulose, hydroxypropyl methyl cellulose and hydroxypropyl ethyl fibre One or more in dimension element.When foregoing adhesives are polymer, the number-average molecular weight of each polymer is generally 30-150 ten thousand.
In lithium ion battery anode glue size and lithium ion battery cathode slurry, for conductive agent, there is no particular limitation, can Think various conductive agents commonly used in the art, under preferable case, conductive agent is Ketjen black, acetylene black, Graphene, carbon nanometer At least one in pipe, carbon fiber (VGCF), micro crystal graphite and conductive carbon black (Super-P).
Wherein, for solvent, there is no particular limitation, can be various solvents commonly used in the art, preferable case Under, solvent is N-Methyl pyrrolidone (NMP), deionized water, tetrahydrofuran, dimethyl sulfoxide, in ethanol and isopropanol extremely Few one kind.Wherein, it is further preferred that in lithium ion battery anode glue size, solvent is N-Methyl pyrrolidone；In lithium ion In battery cathode slurry, solvent is deionized water and/or N-Methyl pyrrolidone.
Wherein, it is applied to thickening agent in lithium ion battery cathode slurry more, whether adds in lithium ion battery anode glue size Plus thickening agent can be selected according to practical situations, it is selected specifically to as it is known to those skilled in the art that preferable case Under, thickening agent is at least one in sodium carboxymethyl cellulose (CMC), polyvinylpyrrolidone, Polyethylene Glycol and polyvinyl alcohol.
Wherein, for the preparation method of lithium ion battery electrode sizing agent of the present invention, there is no particular limitation, can be this The conventional various methods in field, as long as can be by the slurry mix homogeneously containing aforementioned component, for example, containing lithium-ion electric Pond active material, binding agent, conductive agent, the slurry of solvent and optional thickening agent can pass through first by binding agent and solvent Mixing, obtains mixed liquor, then carries out lithium ion battery active material, conductive agent and optional thickening agent and mixed liquor Mixing, or can pass through, by thickening agent or binding agent and solvent mixing, to obtain mixed liquor, then live compound for lithium ion battery Property material, conductive agent and binding agent or thickening agent are mixed with mixed liquor.
Fourth aspect, the invention provides a kind of lithium ion cell positive or negative pole, the lithium ion cell positive or negative Pole includes collector and the electrode dressing on collector, and the electrode dressing contains lithium ion battery active substance, bonding Agent, conductive agent and optional thickening agent, wherein, the lithium ion battery active substance is multiple for lithium ion battery of the present invention Close active substance.
In the lithium ion cell positive of the present invention or negative pole, for active substance, binding agent, conductive agent, thickening agent tool Body is selected, and may refer to corresponding description above, and it is no longer repeated for here.
In the lithium ion cell positive of the present invention or negative pole, in order to improve the peace of the lithium ion battery for preparing further Full property is while take into account battery energy density and battery combination property, on the basis of the dry weight of electrode dressing, the content of additive is 0.05-25 weight %, more preferably 2-14 weight %, more preferably 5-9 weight %.Those skilled in the art should understand that , the weight of the material that the dry weight of electrode dressing is obtained after referring to coat all slurries drying on a current collector.
Wherein, for the method for preparing lithium ion cell positive or negative pole, there is no particular limitation, can be that this area is normal Various methods, for example, can include：Lithium ion battery electrode sizing agent of the present invention is coated on a current collector, is dried Dry.
Wherein, in lithium ion cell positive, for collector, there is no particular limitation, can be commonly used in the art various Plus plate current-collecting body, such as plus plate current-collecting body can be aluminium foil.
Wherein, in lithium ion battery negative, for collector, there is no particular limitation, can be commonly used in the art various Negative current collector, such as negative current collector can be Copper Foil.
Wherein, for the method for coating, there is no particular limitation, can be various methods commonly used in the art, and this is ability Known to field technique people, will not be described here.
Wherein, for the method that dries, there is no particular limitation, can be various methods commonly used in the art, preferable case Under, the condition of drying includes：Temperature is 80-180 DEG C.
5th aspect, the invention provides a kind of lithium ion battery, the lithium ion battery includes battery container and position Battery core component and electrolyte inside the battery container, the battery core component includes positive pole, negative pole and barrier film, and described just extremely Lithium ion cell positive of the present invention, and/or the negative pole be lithium ion battery negative of the present invention.
In the lithium ion battery of the present invention, it will be understood by those skilled in the art that at least in positive pole and negative pole Individual electrode is the negative or positive electrode for being prepared by lithium ion battery active material of the present invention, i.e. just extremely originally The described lithium ion cell positive of invention, or negative pole be lithium ion battery negative of the present invention, or, positive pole and negative pole While respectively lithium ion cell positive of the present invention and negative pole.
In the lithium ion battery of the present invention, it can be commonly used in the art to form the barrier film of lithium ion battery and electrolyte Barrier film and nonaqueous electrolytic solution.
Wherein, barrier film is arranged between positive pole and negative pole, and it has electrical insulation capability and liquid retainability energy, and makes battery core Component and nonaqueous electrolytic solution are contained in battery case together.Barrier film can be various barrier films commonly used in the art, such as polyphosphazene polymer Compound microporous membrane, including the MULTILAYER COMPOSITE microporous membrane of polypropylene microporous membrane and polypropylene and polyethylene.The position of barrier film, Property and species are well known to those skilled in the art, and will not be described here.
Wherein, nonaqueous electrolytic solution is the mixed solution of electrolyte lithium salt and nonaqueous solvent, and it is not particularly limited, permissible Nonaqueous electrolytic solution using this area routine.Such as electrolyte lithium salt is selected from lithium hexafluoro phosphate (LiPF6), lithium perchlorate, tetrafluoro One or more in Lithium biborate, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and fluorohydrocarbon base Sulfonic Lithium.Chain selected by nonaqueous solvent Shape acid esters and ring-type acid esters mixed solution, wherein chain acid esters can be dimethyl carbonate (DMC), diethyl carbonate (DEC), carbon Sour methyl ethyl ester (EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC) and other fluorine-containing, sulfur-bearings or containing unsaturated bond At least one in chain organosilane ester, ring-type acid esters can be ethylene carbonate (EC), Allyl carbonate (PC), carbonic acid Asia second In alkene ester (VC), gamma-butyrolacton (γ-BL), sultone and other fluorine-containing, sulfur-bearings or the ring-type organosilane ester containing unsaturated bond At least one.The injection rate of electrolyte is generally 5-8 gram/ampere-hour, and the concentration of electrolyte is generally 0.8-1.2 mol/L.
In the lithium ion battery of the present invention, for battery container, there is no particular limitation, can be commonly used in the art each Battery container is planted, this is well known to those skilled in the art, and will not be described here.
In the lithium ion battery of the present invention, the common method of the method for this area of battery is prepared, in general, by positive pole A battery core component is constituted with negative pole with barrier film, the battery core component for obtaining and nonaqueous electrolytic solution are sealed in battery case, you can Obtain lithium ion battery.Concrete grammar is well known to those skilled in the art, and will not be described here.
Embodiment
Hereinafter will be described the present invention by embodiment, but and be not so limited the present invention, such as no especially say Bright, material used all can be by commercially available, and method used is the conventional method of this area.
Lithium nickel cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2Purchased from Shanghai Shanshan Science and Technology Co., Ltd.
Cobalt acid lithium LiCoO2Purchased from Tianjin Bamo Technology Co.
Lithium nickel cobalt alumina LiNi0.8Co0.15Al0.05O2Purchased from Japanese Toda Kogyo Corp..
Pvdf binding agent HSV900 is purchased from French Arkema.
PTFE emulsion binding agent D210 solid content is 60%, purchased from Daikin Industries,Ltd..
Conductive agent Super-P is purchased from Te Migao company of Switzerland.
Native graphite is purchased from Shenzhen Bei Te REFRESH PLUS energy and material limited company.
Thickening agent CMC is purchased from Japanese Di-ichi Kogyo Seiyaku Co., Ltd..
Butadiene-styrene rubber emulsion binder solid content is 50%, purchased from Zeon Corp.
Embodiment 1
A. the preparation of the active material of Surface coating aluminium hydroxide additive
Nine water aluminum nitrate of 3750g is dissolved in 10000g deionized water, prepared aluminum nitrate solution, under agitation, The ammonia that mass fraction is 25% is gradually added in aluminum nitrate solution, until pH value of reaction system is 7.3, during control ammonification water Between be 2 hours, reaction terminate after obtain aluminum hydroxide precipitation.The precipitate with deionized water is washed to remove nitric acid therein Ammonium, and replace water with isopropanol, using as the 9220g chemical formula of active component be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen Positive electrode is added in precipitation, addition 12000g isopropanol, and strong stirring 2 hours under 300rpm are spray-dried, obtain hydroxide Aluminum (Al (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (on the basis of the weight of active material, The content of additive is 7.8 weight %).
B. the making of cell
(1) prepared by battery positive pole piece
By above-mentioned for the 23875g positive pole active material for preparing, 500g binding agent HSV900,625g conductive agent Super-P mixes, and concrete grammar is：First with 25000g NMP as solvent, binding agent HSV900 is dissolved, and is distinguished under agitation Positive pole active material, conductive agent Super-P are mixed with the solution of above-mentioned binding agent, stirring afterwards forms uniform positive pole Slurry；
The anode sizing agent is coated uniformly on the aluminium foil that thickness is 25 μm, coating width is that 160mm, the two-sided face of dressing is close Spend for 331.4g/m2(in terms of weight of the two-sided surface density of dressing after drying, similarly hereinafter, and on the basis of the dry weight of electrode dressing, add Plus the content of agent is about 7.5 weight %), then dry at 110 DEG C, obtain anode pole piece.
(2) prepared by negative pole piece of battery
By 12220g natural graphite negative electrode material, 175g thickening agent CMC, 215g conductive agent Super-P and 780g butylbenzene rubber Latex glue caking agent mixes, and concrete grammar is：First with 12500g deionized water as solvent, thickening agent CMC is dissolved, and in stirring Lower respectively butadiene-styrene rubber emulsion binder, conductive agent Super-P, natural graphite negative electrode material and the solution of above-mentioned thickening agent are mixed Close, stirring afterwards forms uniform cathode size；
The cathode size is coated uniformly on the Copper Foil that thickness is 18 μm, coating width is that 164mm, the two-sided face of dressing is close Spend for 165g/m2(in terms of the weight after drying, similarly hereinafter), then dry at 100 DEG C, obtain cathode pole piece.
(3) assembling of cell
Anode pole piece is cut into the size of 120mm × 160mm as positive pole, by cathode pole piece be cut into 125mm × The size of 164mm is assembled into battery core component as negative pole with polypropylene screen as barrier film, is put in Soft Roll aluminum plastic film battery container, And both positive and negative polarity lug is welded together with aluminum plastic film respectively, during ensure the insulation of lug and battery container, through adjusting, In positive electrode, the weight of active component lithium nickel cobalt manganese oxygen is about 191g, and the weight of negative electrode active material native graphite is about 104g, the nominal capacity of battery is 30Ah.Subsequently by LiPF6EC/DMC=1 is dissolved in by the concentration of 1 mol/L:1 (volume Than) mixed solvent in form nonaqueous electrolytic solution, under nitrogen atmosphere protection, this electrolyte of 160g is injected above-mentioned battery and partly becomes In product, and by battery seal.The battery is aged 48 hours under conditions of 45 DEG C, is charged to the electric current of 0.6A afterwards The gas for producing in battery is finally taken out under nitrogen atmosphere protection by 4.00V, then secondary ageing 48 hours under conditions of 45 DEG C Go out and by battery secondary sealing, obtain lithium ion battery A1.
Embodiment 2
Method according to embodiment 1 prepares lithium ion battery A2, except for the difference that, with orthosilicic acid (Si (OH)4) cladding LiNi0.80Co0.15Al0.05O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole be combined Active substance, wherein, orthosilicic acid (Si (OH)4) cladding LiNi0.80Co0.15Al0.05O2Positive pole active material by as lower section Prepared by method：
2120g metasilicate pentahydrate sodium is added stirring and dissolving in 20000g deionized water, obtains solution of sodium metasilicate through.? To in solution of sodium metasilicate through, the dust technology of 15 weight % under 280rpm strong stirring, is rapidly joined, until pH value of reaction system is 7.3, reaction obtains orthosilicic acid (silicon hydroxide) precipitation after terminating.The precipitate with deionized water is washed to remove nitric acid therein Sodium, and replace water with isopropanol, using as the 11348g chemical formula of active component be LiNi0.80Co0.15Al0.05O2Lithium nickel cobalt Alumina positive electrode is added in precipitation, adds 14000g isopropanol, is continued strong stirring 2 hours under 310rpm, is spray-dried, obtains To orthosilicic acid (Si (OH)4) cladding LiNi0.80Co0.15Al0.05O2The positive pole active material (weight with active material On the basis of, the content of additive is 7.8 weight %).
Embodiment 3
Method according to embodiment 1 prepares lithium ion battery A3, except for the difference that, with titanium hydroxide (Ti (OH)4) cladding cobalt The positive pole active material of sour lithium replaces aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material, its In, titanium hydroxide (Ti (OH)4) cladding cobalt acid lithium positive pole active material matter be prepared as follows：
Will 1600g sodium hydroxide add 20000g deionized water in dissolve, obtain sodium hydroxide solution, 0 DEG C of water-bath, Under conditions of 240rpm strong stirring, 1900g titanium tetrachloride liquid is slowly added in sodium hydroxide solution, control adds four chlorinations The titanium time is 3 hours, and reaction obtains titanium hydroxide precipitation after terminating.The precipitate with deionized water is washed to remove chlorine therein Change sodium, and add isopropanol displacement water, using as active component 13712g chemical formula be LiCoO2Lithium cobaltate cathode material Add in precipitation, 16000g isopropanol is added, continue strong stirring 2 hours under 360rpm, be spray-dried, obtain titanium hydroxide (Ti(OH)4) cladding cobalt acid lithium positive pole active material (on the basis of the weight of active material, the content of additive For 7.8 weight %).
Embodiment 4
Method according to embodiment 1 prepares lithium ion battery A4, except for the difference that, (1) LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt The unused additive of manganese oxygen positive electrode carries out Surface coating, and battery positive pole piece prepares surface coated using not carrying out LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode, and when prepared by battery positive pole piece, the two-sided surface density of dressing is 305.5g/m2；(2) method that prepared by negative pole piece of battery is as follows：
Nine water aluminum nitrate of 3750g is dissolved in 10000g deionized water, prepared aluminum nitrate solution, under agitation, The ammonia that mass fraction is 25% is gradually added in aluminum nitrate solution, until pH value of reaction system is 7.3, during control ammonification water Between be 2 hours, reaction terminate after obtain aluminum hydroxide precipitation.The precipitate with deionized water is washed to remove nitric acid therein Ammonium, replaces water with isopropanol, will add in precipitation as the 9220g natural graphite negative electrode material of active component, adds 12000g Isopropanol, continues strong stirring 2 hours under 330rpm, is spray-dried, obtains aluminium hydroxide (Al (OH)3) coated natural graphite Negative pole active material (on the basis of the weight of active material, the content of additive is 7.8 weight %).
By 12220g aluminium hydroxide (Al (OH)3) the negative pole active material of coated natural graphite, 175g thickening agent CMC, 215g conductive agent Super-P and 780g butadiene-styrene rubber emulsion binder mix, and concrete grammar is：First with 12500g deionization Water is solvent, and thickening agent CMC is dissolved, and under agitation respectively by butadiene-styrene rubber emulsion binder, conductive agent Super-P, negative Pole active material is mixed with the solution of above-mentioned thickening agent, and stirring afterwards forms uniform cathode size；
The cathode size is coated uniformly on the Copper Foil that thickness is 18 μm, coating width is that 164mm, the two-sided face of dressing is close Spend for 179g/m2, then dry at 100 DEG C, obtain cathode pole piece.
Embodiment 5
Method according to embodiment 1 prepares lithium ion battery A5, except for the difference that, (1) Surface coating aluminium hydroxide additive Positive pole active material be prepared as follows：
Nine water aluminum nitrate of 3750g is dissolved in 10000g deionized water, prepared aluminum nitrate solution, under agitation, The ammonia that mass fraction is 25% is gradually added in aluminum nitrate solution, until pH value of reaction system is 7.3, during control ammonification water Between be 2 hours, reaction terminate after obtain aluminum hydroxide precipitation.The precipitate with deionized water is washed to remove nitric acid therein Ammonium, replaces water with isopropanol, using as active component 12904g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen Positive electrode is added in precipitation, addition 15000g isopropanol, and 320rpm strong stirring 2 hours is spray-dried, obtains aluminium hydroxide (Al(OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (on the basis of the weight of active material, add Plus the content of agent is 5.7 weight %).
(2), when prepared by battery positive pole piece, the two-sided surface density of anode dressing is adjusted to 324g/m2(positive-active in battery The weight of composition lithium nickel cobalt manganese oxygen is same as Example 1).
Embodiment 6
Method according to embodiment 1 prepares lithium ion battery A6, except for the difference that, (1) Surface coating aluminium hydroxide additive Positive pole active material be prepared as follows：
Nine water aluminum nitrate of 3750g is dissolved in 10000g deionized water, prepared aluminum nitrate solution, under agitation, The ammonia that mass fraction is 25% is gradually added in aluminum nitrate solution, until pH value of reaction system is 7.3, during control ammonification water Between be 2 hours, reaction terminate after obtain aluminum hydroxide precipitation.The precipitate with deionized water is washed to remove nitric acid therein Ammonium, replaces water with isopropanol, using as active component 7099g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen just Pole material is added in precipitation, addition 9000g isopropanol, and 230rpm strong stirring 2 hours is spray-dried, obtains aluminium hydroxide (Al (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (on the basis of the weight of active material, additive Content be 9.9 weight %).
(2), when prepared by battery positive pole piece, the two-sided surface density of anode dressing is adjusted to 339.1g/m2(in battery, positive pole is lived The weight of property composition lithium nickel cobalt manganese oxygen is same as Example 1).
Embodiment 7
Method according to embodiment 1 prepares lithium ion battery A7, except for the difference that, (1) Surface coating aluminium hydroxide additive Positive pole active material be prepared as follows：
Nine water aluminum nitrate of 3750g is dissolved in 10000g deionized water, prepared aluminum nitrate solution, under agitation, The ammonia that mass fraction is 25% is gradually added in aluminum nitrate solution, until pH value of reaction system is 7.3, during control ammonification water Between be 2 hours, reaction terminate after obtain aluminum hydroxide precipitation.The precipitate with deionized water is washed to remove nitric acid therein Ammonium, replaces water with isopropanol, using as active component 38220g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen Positive electrode is added in precipitation, adds 40000g isopropanol, continues 270rpm strong stirring 2 hours, is spray-dried, is obtained hydrogen-oxygen Change aluminum (Al (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (with the weight of active material as base Standard, the content of additive is 2 weight %).
(2), when prepared by battery positive pole piece, the two-sided surface density of anode dressing is adjusted to 311.8g/m2(in battery, positive pole is lived The weight of property composition lithium nickel cobalt manganese oxygen is same as Example 1).
Embodiment 8
Method according to embodiment 1 prepares lithium ion battery A8, except for the difference that, (1) Surface coating aluminium hydroxide additive Positive pole active material be prepared as follows：
Nine water aluminum nitrate of 3750g is dissolved in 10000g deionized water, prepared aluminum nitrate solution, under agitation, The ammonia that mass fraction is 25% is gradually added in aluminum nitrate solution, until pH value of reaction system is 7.3, during control ammonification water Between be 2 hours, reaction terminate after obtain aluminum hydroxide precipitation.The precipitate with deionized water is washed to remove nitric acid therein Ammonium, replaces water with isopropanol, using as active component 85887g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen Positive electrode is added in precipitation, adds 88000g isopropanol, continues 350rpm strong stirring 2 hours, is spray-dried, is obtained hydrogen-oxygen Change aluminum (Al (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (with the weight of active material as base Standard, the content of additive is 0.9 weight %).
(2), when prepared by battery positive pole piece, the two-sided surface density of anode dressing is adjusted to 308.3g/m2(in battery, positive pole is lived The weight of property composition lithium nickel cobalt manganese oxygen is same as Example 1).
Embodiment 9
Method according to embodiment 1 prepares lithium ion battery A9, except for the difference that, (1) Surface coating aluminium hydroxide additive Positive pole active material be prepared as follows：
Nine water aluminum nitrate of 3750g is dissolved in 10000g deionized water, prepared aluminum nitrate solution, under agitation, The ammonia that mass fraction is 25% is gradually added in aluminum nitrate solution, until pH value of reaction system is 7.3, during control ammonification water Between be 2 hours, reaction terminate after obtain aluminum hydroxide precipitation.The precipitate with deionized water is washed to remove nitric acid therein Ammonium, replaces water with isopropanol, using as active component 4599g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen just Pole material is added in precipitation, adds 7000g isopropanol, continues 270rpm strong stirring 2 hours, is spray-dried, is obtained hydroxide Aluminum (Al (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (on the basis of the weight of active material, The content of additive is 14.5 weight %).
(2), when prepared by battery positive pole piece, the two-sided surface density of anode dressing is adjusted to 357.4g/m2(in battery, positive pole is lived The weight of property composition lithium nickel cobalt manganese oxygen is same as Example 1).
Embodiment 10
Method according to embodiment 1 prepares lithium ion battery A10, except for the difference that, with Yttrium trihydroxide (Y (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, Yttrium trihydroxide (Y (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material make as follows Standby：
Six water Yttrium trinitrate of 3830g is dissolved in 10000g deionized water, prepared yttrium nitrate solution, under agitation, The ammonia that mass fraction is 25% is gradually added in yttrium nitrate solution, until pH value of reaction system is 7.3, during control ammonification water Between be 2 hours, reaction terminate after obtain Yttrium trihydroxide precipitation.The precipitate with deionized water is washed to remove nitric acid therein Ammonium, using as active component 16537g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode add precipitation In, 19000g water being added, continues 360rpm strong stirring 2 hours, dry Yttrium trihydroxide (Y is obtained finally by being spray-dried (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (on the basis of the weight of active material, additive Content be 7.8 weight %).
Embodiment 11
Method according to embodiment 1 prepares lithium ion battery A11, except for the difference that, with Scium trihydroxide. (Sc (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, Scium trihydroxide. (Sc (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
Six water Scium nitrate(Sc(NO3)3) of 3390g is dissolved in 10000g deionized water, prepared Scium nitrate(Sc(NO3)3) solution, under agitation, The ammonia that mass fraction is 25% is gradually added in Scium nitrate(Sc(NO3)3) solution, until pH value of reaction system is 7.3, during control ammonification water Between be 2 hours, reaction terminate after obtain Scium trihydroxide. precipitation.The precipitate with deionized water is washed to remove nitric acid therein Ammonium, using as active component 11348g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode add precipitation In, 14000g water being added, continues 290rpm strong stirring 2 hours, dry Scium trihydroxide. (Sc is obtained finally by being spray-dried (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (on the basis of the weight of active material, additive Content be 7.8 weight %).
Embodiment 12
Method according to embodiment 1 prepares lithium ion battery A12, except for the difference that, with zirconium hydroxide (Zr (OH)4) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, zirconium hydroxide (Zr (OH)4) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
Will 1600g sodium hydroxide add 20000g deionized water in dissolve, obtain sodium hydroxide solution, 0 DEG C of water-bath, Under conditions of 220rpm strong stirring, 2330g Zirconium tetrachloride. powder is slowly added in sodium hydroxide solution, control adds four chlorinations The zirconium powder time is 2 hours, and reaction obtains precipitated zirconium hydroxide after terminating.The precipitate with deionized water is washed to remove wherein Sodium Chloride, and add isopropanol displacement water, using as active component 18795g chemical formula be LiNi0.5Co0.2Mn0.3O2's Lithium nickel cobalt manganese oxygen positive electrode is added in precipitation, adds 21000g isopropanol, continues 350rpm strong stirring 2 hours, is finally led to Cross and be spray-dried the zirconium hydroxide (Zr (OH) for obtaining drying4) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (with On the basis of the weight of active material, the content of additive is 7.8 weight %).
Embodiment 13
Method according to embodiment 1 prepares lithium ion battery A13, except for the difference that, with vanadium hydroxide (V (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, vanadium hydroxide (V (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material make as follows Standby：
1200g sodium hydroxide is added in 20000g deionized water and is dissolved, sodium hydroxide solution is obtained, in 0 DEG C of water-bath, nitrogen Under conditions of gas shielded and 260rpm strong stirring, 1570g vanadium trichloride powder is slowly added in sodium hydroxide solution, control System plus vanadium trichloride powder time are 2 hours, and reaction obtains vanadium hydroxide precipitation after terminating.Under nitrogen protection, this is precipitated It is washed with deionized so that Sodium Chloride therein is removed, and isopropanol displacement water is added, using the 12045gization as active component Formula is LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode be added thereto, add 14000g isopropanol, continue Strong stirring 2 hours under 270rpm, obtain dry vanadium hydroxide (V (OH) finally by being spray-dried3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (on the basis of the weight of active material, the content of additive is 7.8 weight %).
Embodiment 14
Method according to embodiment 1 prepares lithium ion battery A14, except for the difference that, with lanthanum hydroxide (La (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, lanthanum hydroxide (La (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
4330g lanthanum nitrate hexahydrate is dissolved in 20000g deionized water, prepared lanthanum nitrate hexahydrate, under agitation, The ammonia that mass fraction is 25% is gradually added in lanthanum nitrate hexahydrate, until pH value of reaction system is 7.3, during control ammonification water Between be 2 hours, reaction terminate after obtain lanthanum hydroxide precipitation.The precipitate with deionized water is washed to remove nitric acid therein Ammonium, using as active component 22447g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode add which In, 25000g deionized water being added, continues 300rpm strong stirring 2 hours, dry hydrogen-oxygen is obtained finally by being spray-dried Change lanthanum (La (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (with the weight of active material as base Standard, the content of additive is 7.8 weight %).
Embodiment 15
Method according to embodiment 1 prepares lithium ion battery A15, except for the difference that, with cerium hydroxide (Ce (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, cerium hydroxide (Ce (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
Six water cerous nitrate of 4340g is dissolved in 15000g deionized water, prepared cerous nitrate solution, under agitation, The ammonia that mass fraction is 25% is gradually added in cerous nitrate solution, until pH value of reaction system is 7.3, during control ammonification water Between be 2 hours, reaction terminate after obtain cerium hydroxide precipitation.The precipitate with deionized water is washed to remove nitric acid therein Ammonium, using as active component 22589g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode add which In, 25000g deionized water being added, continues 330rpm strong stirring 2 hours, dry hydrogen-oxygen is obtained finally by being spray-dried Change cerium (Ce (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (with the weight of active material as base Standard, the content of additive is 7.8 weight %).
Embodiment 16
Method according to embodiment 1 prepares lithium ion battery A16, except for the difference that, with Neodymium hydroxide (Nd (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, Neodymium hydroxide (Nd (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
Six water neodymium nitrate of 4380g is dissolved in 15000g deionized water, prepared neodymium nitrate solution, under agitation, The ammonia that mass fraction is 25% is gradually added in neodymium nitrate solution, until pH value of reaction system is 7.3, during control ammonification water Between be 2 hours, reaction terminate after obtain Neodymium hydroxide precipitation.The precipitate with deionized water is washed to remove nitric acid therein Ammonium, using as active component 23074g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode add which In, 25000g deionized water being added, continues 330rpm strong stirring 2 hours, dry hydrogen-oxygen is obtained finally by being spray-dried Change neodymium (Nd (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (with the weight of active material as base Standard, the content of additive is 7.8 weight %).
Embodiment 17
Method according to embodiment 1 prepares lithium ion battery A17, except for the difference that, with Samarium trihydroxide. (Sm (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, Samarium trihydroxide. (Sm (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
Six water samaric nitrate of 4440g is dissolved in 15000g deionized water, prepared samarium nitrate solution, under agitation, The ammonia that mass fraction is 25% is gradually added in samarium nitrate solution, until pH value of reaction system is 7.3, during control ammonification water Between be 2 hours, reaction terminate after obtain Samarium trihydroxide. precipitation.The precipitate with deionized water is washed to remove nitric acid therein Ammonium, using as active component 23807g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode add which In, 26000g deionized water being added, continues 340rpm strong stirring 2 hours, dry hydrogen-oxygen is obtained finally by being spray-dried Change samarium (Sm (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (with the weight of active material as base Standard, the content of additive is 7.8 weight %).
Embodiment 18
Method according to embodiment 1 prepares lithium ion battery A18, except for the difference that, with Gadolinium trihydroxide (Gd (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, Gadolinium trihydroxide (Gd (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
Six water Gadolinium trinitrate of 4510g is dissolved in 15000g deionized water, prepared Gadolinium trinitrate solution, under agitation, The ammonia that mass fraction is 25% is gradually added in Gadolinium trinitrate solution, until pH value of reaction system is 7.3, during control ammonification water Between be 2 hours, reaction terminate after obtain Gadolinium trihydroxide precipitation.The precipitate with deionized water is washed to remove nitric acid therein Ammonium, using as active component 24622g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode add which In, 27000g deionized water being added, continues 290rpm strong stirring 2 hours, dry hydrogen-oxygen is obtained finally by being spray-dried Change gadolinium (Gd (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (with the weight of active material as base Standard, the content of additive is 7.8 weight %).
Embodiment 19
Method according to embodiment 1 prepares lithium ion battery A19, except for the difference that, with erbium hydroxide (Er (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, erbium hydroxide (Er (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
Five water Erbium trinitrate of 4433g is dissolved in 15000g deionized water, prepared Nitrate Solution, under agitation, The ammonia that mass fraction is 25% is gradually added in Nitrate Solution, until pH value of reaction system is 7.3, during control ammonification water Between be 2 hours, reaction terminate after obtain erbium hydroxide precipitation.The precipitate with deionized water is washed to remove nitric acid therein Ammonium, using as active component 25804g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode add which In, 28000g deionized water being added, continues 280rpm strong stirring 2 hours, dry hydrogen-oxygen is obtained finally by being spray-dried Change erbium (Er (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (with the weight of active material as base Standard, the content of additive is 7.8 weight %).
Embodiment 20
Method according to embodiment 1 prepares lithium ion battery A20, except for the difference that, with niobium hydroxide (Nb (OH)5) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, niobium hydroxide (Nb (OH)5) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
It is 40% that 929g metal niobium is dissolved in by the concentrated nitric acid that 3200g mass fraction is 65% and 5000g mass fraction Fluohydric acid. composition mixed solution in, prepared niobium liquid, under agitation, be gradually added mass fraction in niobium liquid for 25% Ammonia, until pH value of reaction system be 7.3, control the ammonification water time be 2 hours, reaction terminate after obtain niobium hydroxide forerunner Body.The presoma is washed with deionized to remove ammonium nitrate therein and ammonium fluoride, subsequently using as active component 21034g chemical formula is LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode be added thereto, add 24000g deionization Water, 380rpm strong stirring 2 hours, dry niobium hydroxide (Nb (OH) is obtained finally by being spray-dried5) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (on the basis of the weight of active material, the content of additive is 7.8 weight %).
Embodiment 21
Method according to embodiment 1 prepares lithium ion battery A21, except for the difference that, with chromic oxide gel (Cr (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, chromic oxide gel (Cr (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
Nine water chromic nitrate of 4000g is dissolved in 15000g deionized water, prepared chromium nitrate solution, under agitation, The ammonia that mass fraction is 25% is gradually added in chromium nitrate solution, until pH value of reaction system is 7.3, during control ammonification water Between be 2 hours, reaction terminate after obtain chromium hydroxide precipitation.The precipitate with deionized water is washed to remove nitric acid therein Ammonium, using as active component 12175g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode add which In, 14000g deionized water being added, continues 250rpm strong stirring 2 hours, dry hydrogen-oxygen is obtained finally by being spray-dried Change chromium (Cr (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (with the weight of active material as base Standard, the content of additive is 7.8 weight %).
Embodiment 22
Method according to embodiment 1 prepares lithium ion battery A22, except for the difference that, with molybdenum hydroxide (Mo (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, molybdenum hydroxide (Mo (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
Under agitation, tri- water molybdenum trichloride of 2560g is dissolved in 25000g dehydrated alcohol, settled solution is obtained, Under agitation, the ammonia that 2150g mass fraction is 25% is gradually added in the settled solution, and the control ammonification water time is 2 hours, reaction obtained molybdenum hydroxide precipitation after terminating.By the precipitate with deionized water washing to remove ammonium chloride therein, and Water is replaced with isopropanol, subsequently using as active component 17369g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen Positive electrode is added thereto, and adds 20000g isopropanol, continues 270rpm strong stirring 2 hours, finally by being spray-dried To dry molybdenum hydroxide (Mo (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (with active material Weight on the basis of, the content of additive is 7.8 weight %).
Embodiment 23
Method according to embodiment 1 prepares lithium ion battery A23, except for the difference that, with hydroxide manganese (Mn (OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, hydroxide manganese (Mn (OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material by as lower section Prepared by method：
The 50 weight % Mn nitrate aqueous solutions of 3580g are diluted with 15000g deionized water, prepared Mn nitrate solution, Under conditions of stirring and nitrogen protection, the ammonia that mass fraction is 25% is gradually added in Mn nitrate solution, until anti- System pH is answered for 7.3, the control ammonification water time is 2 hours, reaction obtains hydroxide manganese precipitation after terminating.Protect in nitrogen Under, by the precipitate with deionized water washing so that ammonium nitrate therein is removed, and water being replaced with isopropanol, subsequently will become as activity The 10513g chemical formula for dividing is LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode be added thereto, add 13000g isopropyl Alcohol, continues 240rpm strong stirring 2 hours, obtains dry hydroxide manganese (Mn (OH) finally by being spray-dried2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (on the basis of the weight of active material, the content of additive is 7.8 weight %).
Embodiment 24
Method according to embodiment 1 prepares lithium ion battery A24, except for the difference that, with hydrated ferric oxide. (Fe (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace hydroxyl hydrogen alumina-coated LiNi0.5Co0.2Mn0.3O2Positive pole multiple Close active substance, wherein, hydrated ferric oxide. (Fe (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material by as follows Prepared by method：
By nine water ferric nitrate 15000g deionized water dissolving of 4040g, prepared iron nitrate solution, in 260rpm strong stirring Under conditions of, the ammonia that mass fraction is 25% is rapidly joined in iron nitrate solution, until pH value of reaction system is 11, reaction It is precipitated after end.By the precipitate with deionized water quick wash so that ammonium nitrate therein and ammonia is removed, and use isopropanol Displacement water, using as active component 12630g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode add Wherein, 15000g isopropanol being added, continue 250rpm strong stirring 2 hours, hydrated ferric oxide. (Fe is obtained by being spray-dried (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (on the basis of the weight of active material, additive Content be 7.8 weight %).
Embodiment 25
Method according to embodiment 1 prepares lithium ion battery A25, except for the difference that, with hydroxide cobalt (Co (OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, hydroxide cobalt (Co (OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material by as lower section Prepared by method：
By the six water colbaltous nitrate 15000g deionized water dissolving of 2910g, prepared colbaltous nitrate solution, in stirring and nitrogen Under conditions of gas shielded, the ammonia that mass fraction is 25% is gradually added in colbaltous nitrate solution, until pH value of reaction system For 7.3, it is 2 hours to control the ammonification water time, and reaction obtains hydroxide cobalt precipitation after terminating.Under conditions of nitrogen protection, By the precipitate with deionized water washing so that ammonium nitrate therein is removed, and water is replaced with isopropanol, subsequently will be used as active component 10984g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode be added thereto, add 13000g isopropyl Alcohol, continues 290rpm strong stirring 2 hours, obtains dry hydroxide cobalt (Co (OH) finally by being spray-dried2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (on the basis of the weight of active material, the content of additive is 7.8 weight %).
Embodiment 26
Method according to embodiment 1 prepares lithium ion battery A26, except for the difference that, with hickelous nydroxide (Ni (OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, hickelous nydroxide (Ni (OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material by as lower section Prepared by method：
By the six liquid glauber salt acid Asia nickel 15000g deionized water dissolving of 2910g, prepared nitric acid Asia nickel solution, in stirring and nitrogen Under conditions of gas shielded, it is gradually added, in the nickel solution of nitric acid Asia, the ammonia that mass fraction is 25%, until pH value of reaction system For 7.3, it is 2 hours to control the ammonification water time, and reaction obtains hickelous nydroxide precipitation after terminating.Under conditions of nitrogen protection, By the precipitate with deionized water washing so that ammonium nitrate therein is removed, and water is replaced with isopropanol, subsequently will be used as active component 10956g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode be added thereto, add 13000g isopropyl Alcohol, continues 300rpm strong stirring 2 hours, obtains dry hickelous nydroxide (Ni (OH) finally by being spray-dried2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (on the basis of the weight of active material, the content of additive is 7.8 weight %).
Embodiment 27
Method according to embodiment 1 prepares lithium ion battery A27, except for the difference that, with stannic hydroxide (Sn (OH)4) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, stannic hydroxide (Sn (OH)4) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
3510g stannic chloride pentahydrate is dissolved in 20000g dehydrated alcohol, settled solution is obtained, under agitation, The ammonia that 2860g mass fraction is 25% is gradually added in the settled solution, the control ammonification water time is 2 hours, reaction knot Stannic hydroxide precipitation is obtained after bundle.By the precipitate with deionized water washing to remove ammonium chloride therein, and replaced with isopropanol Water, subsequently using as active component 22070g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode add Wherein, 24000g isopropanol being added, continue 320rpm strong stirring 2 hours, dry hydrogen-oxygen is obtained finally by being spray-dried Change stannum (Sn (OH)4) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (with the weight of active material as base Standard, the content of additive is 7.8 weight %).
Embodiment 28
Method according to embodiment 1 prepares lithium ion battery A28, except for the difference that, with Bismuth hydrate. (Bi (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, Bismuth hydrate. (Bi (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
Five water bismuth nitrate of 4850g is added and is dissolved in the 20000g diluted nitric acid aqueous solution that mass fraction is 2%, prepared nitric acid Bismuth solution, under the conditions of 330rpm strong stirring, bismuth nitrate solution is rapidly joined the ammonia that 2600g mass fraction is 25% In, reaction obtains Bismuth hydrate. precipitation after terminating.The precipitate with deionized water is washed to remove ammonium nitrate therein and ammonia, Subsequently using as the 30733g chemical formula of active component be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode add which In, 33000g deionized water is added, continues 330rpm strong stirring 2 hours, and by being spray-dried the hydroxide for obtaining drying Bismuth (Bi (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (on the basis of the weight of active material, The content of additive is 7.8 weight %).
Embodiment 29
Method according to embodiment 1 prepares lithium ion battery A29, except for the difference that, with antimony hydroxide (Sb (OH)3) cover LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, antimony hydroxide (Sb (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
Under agitation, 2280g Butter of antimony. is dissolved in 25000g dehydrated alcohol, settled solution is obtained, stirring Under the conditions of mixing, the ammonia that 2150g mass fraction is 25% is gradually added in the settled solution, the control ammonification water time is little for 2 When, reaction obtains antimony hydroxide precipitation after terminating.By precipitate with deionized water washing to remove ammonium chloride therein, and with different Propanol replace water, using as active component 20420g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode Being added thereto, 23000g isopropanol is added, continue 340rpm strong stirring 2 hours, drying is obtained finally by being spray-dried Antimony hydroxide (Sb (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (weight with active material is Benchmark, the content of additive is 7.8 weight %).
Embodiment 30
Method according to embodiment 1 prepares lithium ion battery A30, except for the difference that, with boric acid (B (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, boric acid (B (OH)3) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material be prepared as follows：
618g boric acid is added in 15000g deionized water and is dissolved, prepared boric acid solution, using the 7305g as active component Chemical formula is LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode be added thereto, add 10000g deionized water, 300rpm strong stirring 2 hours, the solution is spray-dried the boric acid (B (OH) for obtaining drying3) cladding LiNi0.5Co0.2Mn0.3O2 Positive pole active material (on the basis of the weight of active material, the content of additive is 7.8 weight %).
Embodiment 31
Method according to embodiment 1 prepares lithium ion battery A31, except for the difference that, with beryllium hydroxide (Be (OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, beryllium hydroxide (Be (OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
By 1870g nitrate trihydrate beryllium 10000g deionized water dissolving, prepared beryllium nitrate solution, under agitation, to The ammonia that mass fraction is 25% is gradually added in beryllium nitrate solution, until pH value of reaction system is 7.3, controls the ammonification water time For 2 hours, reaction obtained beryllium hydroxide presoma after terminating.The presoma is washed with deionized to remove nitric acid therein Ammonium, using as active component 5083g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode be added thereto, 7000g deionized water is added, continues 340rpm strong stirring 2 hours, the solution is spray-dried the beryllium hydroxide for obtaining drying (Be(OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (on the basis of the weight of active material, add Plus the content of agent is 7.8 weight %).
Embodiment 32
Method according to embodiment 1 prepares lithium ion battery A32, except for the difference that, with magnesium hydroxide (Mg (OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, magnesium hydroxide (Mg (OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
By 2560g magnesium nitrate hexahydrate 10000g deionized water dissolving, prepared magnesium nitrate solution, under agitation, to The ammonia that mass fraction is 25% is gradually added in magnesium nitrate solution, until pH value of reaction system is 7.3, controls the ammonification water time For 2 hours, reaction obtained magnesium hydrate precipitate after terminating.The presoma is washed with deionized to remove nitric acid therein Ammonium, using as active component 6891g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode be added thereto, 9000g deionized water is added, continues 270rpm strong stirring 2 hours, the solution is spray-dried the magnesium hydroxide for obtaining drying (Mg(OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (on the basis of the weight of active material, add Plus the content of agent is 7.8 weight %).
Embodiment 33
Method according to embodiment 1 prepares lithium ion battery A33, except for the difference that, with Copper hydrate (Cu (OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, Copper hydrate (Cu (OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
By 2420g nitrate trihydrate copper 10000g deionized water dissolving, prepared copper nitrate solution, under agitation, to The ammonia that mass fraction is 25% is gradually added in copper nitrate solution, until pH value of reaction system is 7.3, controls the ammonification water time For 2 hours, reaction obtained Copper hydrate precipitation after terminating.The precipitate with deionized water is washed to remove ammonium nitrate therein, Using as active component 11530g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode be added thereto, plus Enter 14000g deionized water, continue 290rpm strong stirring 2 hours, the solution is spray-dried the Copper hydrate for obtaining drying (Cu(OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (on the basis of the weight of active material, add Plus the content of agent is 7.8 weight %).
Embodiment 34
Method according to embodiment 1 prepares lithium ion battery A34, except for the difference that, with zinc hydroxide (Zn (OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material replace aluminium hydroxide cladding LiNi0.5Co0.2Mn0.3O2Positive pole compound live Property material, wherein, zinc hydroxide (Zn (OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material as follows Prepare：
By 2970g zinc nitrate hexahydrate 10000g deionized water dissolving, prepared zinc nitrate solution, under agitation, to The ammonia that mass fraction is 25% is gradually added in zinc nitrate solution, until pH value of reaction system is 7.3, controls the ammonification water time For 2 hours, reaction obtained zinc hydroxide precipitation after terminating.The precipitate with deionized water is washed to remove ammonium nitrate therein, Using as active component 11747g chemical formula be LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode be added thereto, plus Enter 14000g deionized water, continue 360rpm strong stirring 2 hours, the solution is spray-dried the zinc hydroxide for obtaining drying (Zn(OH)2) cladding LiNi0.5Co0.2Mn0.3O2Positive pole active material (on the basis of the weight of active material, add Plus the content of agent is about 7.8 weight %).
Comparative example 1
Method according to embodiment 1 prepares lithium ion battery D1, except for the difference that, (1) LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt The unused additive of manganese oxygen positive electrode carries out Surface coating, and battery positive pole piece is surface coated using not carrying out when preparing LiNi0.5Co0.2Mn0.3O2Lithium nickel cobalt manganese oxygen positive electrode；
(2), when prepared by battery positive pole piece, the two-sided surface density of anode dressing is adjusted to 305.5g/m2(in battery, positive pole is lived The weight of property composition lithium nickel cobalt manganese oxygen is same as Example 1).
Comparative example 2
Method according to embodiment 2 prepares lithium ion battery D2, except for the difference that, (1) LiNi0.8Co0.15Al0.05O2Lithium nickel cobalt The unused additive of alumina positive electrode carries out Surface coating, and battery positive pole piece is surface coated using not carrying out when preparing LiNi0.8Co0.15Al0.05O2Lithium nickel cobalt alumina positive electrode；
(2), when prepared by battery positive pole piece, the two-sided surface density of anode dressing is adjusted to 305.5g/m2(in battery, positive pole is lived The weight of property composition lithium nickel cobalt alumina is same as Example 2).
Comparative example 3
Method according to embodiment 3 prepares lithium ion battery D3, except for the difference that, (1) cobalt acid lithium LiCoO2Positive electrode is not Carry out Surface coating with additive, battery positive pole piece is prepared using not carrying out surface coated cobalt acid lithium LiCoO2Positive pole material Material；
(2), when prepared by battery positive pole piece, the two-sided surface density of anode dressing is adjusted to 305.5g/m2(in battery, positive pole is lived The weight of property composition cobalt acid lithium is same as Example 3).
Test example
The abuse test of cell
1st, test is overcharged
By cell (including lithium ion battery A1-A34 obtained in embodiment 1-34 and lithium obtained in comparative example 1-3 Ion battery D1-D3) 8.5V is charged to the electric current of 30A, and under the voltage of 8.5V, constant voltage is kept for 1 hour, is observed and is recorded During phenomenon.Respectively take 30 cells and do parallel testing.The results are shown in Table 1.
2nd, 30% extruding test
By cell (including lithium ion battery A1-A34 obtained in embodiment 1-34 and lithium obtained in comparative example 1-3 Ion battery D1-D3) 4.25V is charged to the electric current of 30A, and constant-voltage charge is less than up to electric current under the voltage of 4.25V 1.5A.Battery is extruded with the end face of the semicylinder that two pieces of radiuses are 75mm from perpendicular to battery pole piece direction, extrusion speed is 5mm/s, until cell deformation amount reaches 30%, stops one hour after the completion of extruding, the phenomenon in observation recording process.Respectively take 30 cells do parallel testing.The results are shown in Table 2.
3rd, 50% extruding test
By cell (including lithium ion battery A1-A34 obtained in embodiment 1-34 and lithium obtained in comparative example 1-3 Ion battery D1-D3) 4.25V is charged to the electric current of 30A, and constant-voltage charge is less than up to electric current under the voltage of 4.25V 1.5A.Battery is extruded with the end face of the semicylinder that two pieces of radiuses are 75mm from perpendicular to battery pole piece direction, extrusion speed is 5mm/s, until cell deformation amount reaches 50%, stops one hour after the completion of extruding, the phenomenon in observation recording process.Respectively take 30 cells do parallel testing.The results are shown in Table 3.
4th, lancing test
By cell (including lithium ion battery A1-A34 obtained in embodiment 1-34 and lithium obtained in comparative example 1-3 Ion battery D1-D3) 4.25V is charged to the electric current of 30A, and constant-voltage charge is less than up to electric current under the voltage of 4.25V 1.5A.With a diameter of 6 millimeters of nails along perpendicular to the direction in battery length and width face, battery is at the uniform velocity passed through with the speed of 25mm/s, And stop one hour, the phenomenon in observation recording process.Respectively take 30 cells and do parallel testing.The results are shown in Table 4.
Table 1
Table 2
Table 3
Table 4
The data of each embodiment and comparative example in table 1-4 being compared and being understood, the present invention is introduced when negative or positive electrode is prepared Lithium ion battery active material, the safety of the lithium ion battery for thus preparing can be significantly improved.
Results contrast of the embodiment in table 1-4 1 with embodiment 7-9 is understood, is introduced with lithium when negative or positive electrode is prepared On the basis of the weight of ion battery active material, additive level is combined for the lithium ion battery of 5.7-9.9 weight % and lives Property material, can improve the safety of the lithium ion battery for thus preparing further, and work as additive amount and increase further Added-time can also improve safety of the lithium ion battery for preparing under extremely harsh condition further.
Results contrast of embodiment 1-4 in table 1-4 with embodiment 10-34 is understood, the additive is aluminium hydroxide, original During at least one in silicic acid and titanium hydroxide, the safety of the lithium ion battery for preparing can be improved further.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can The compound mode of energy is no longer separately illustrated.
Additionally, combination in any can also be carried out between a variety of embodiments of the present invention, as long as which is without prejudice to this The thought of invention, which should equally be considered as content disclosed in this invention.

Claims (10)

1. a kind of lithium ion battery active material, it is characterised in that the lithium ion battery active material is for adding The active substance of agent cladding, the additive is M (OH)a, wherein, M is Group IIA metal element, IB race metallic element, Group IIB Metallic element, IIIB race metallic element, Group IVB metallic element, VB race metallic element, group vib metallic element, metal unit of VIIB race In element, group VIII metal element, Group IIIA metallic element, IVA race metallic element, VA race metallic element, boron and silicon at least one Plant element, a ＞ 0.
2. lithium ion battery active material according to claim 1, wherein, in the additive, the Group IIA gold Category element is Be and/or Mg, and it is Zn that IB race metallic element is Cu, the Group IIB metal element, metal unit of the IIIB race Element is at least one in Y, Sc, La, Ce, Nd, Sm, Gd and Er, and the Group IVB metallic element is Ti and/or Zr, the VB race Metallic element is V and/or Nb, and it is Mn that the group vib metallic element is Cr and/or Mo, VIIB race metallic element, described Group VIII metal element is at least one in Fe, Co and Ni, and the Group IIIA metallic element is metal unit of Al, the IVA race Element is Sn, and VA race metallic element is Bi and/or Sb；
Preferably, the additive is at least one in aluminium hydroxide, orthosilicic acid and titanium hydroxide.
3. lithium ion battery active material according to claim 1 and 2, wherein, compound with the lithium ion battery On the basis of the weight of active substance, the content of the additive is 0.05-30 weight %, and preferably 2-15.3 weight %, enters one Step is preferably 5.7-9.9 weight %.
4. the lithium ion battery active material according to any one in claim 1-3, wherein, the active substance For positive active material or negative electrode active material, described positive active material is cobalt acid lithium, lithium nickel oxygen, lithium-nickel-cobalt-oxygen, lithium nickel cobalt Alumina, lithium nickel cobalt manganese oxygen, Li-Ni-Mn-O, LiMn2O4, lithium vanadate, LiFePO4, lithium manganese phosphate, iron manganese phosphate for lithium, iron manganese phosphate At least one in nickel lithium, iron manganese phosphate cobalt lithium, iron manganese phosphate nickel cobalt lithium, phosphoric acid vanadium lithium and ferric metasilicate lithium, the negative electrode active Material is at least one in graphite, lithium titanate, silicon, hard carbon, stannum and stannum oxide.
5. the preparation method of the lithium ion battery active material in claim 1-4 described in any one, it is characterised in that The method includes：Prepare the hydroxide precipitation of element M, in the presence of dispersants, by the hydroxide of element M precipitation with Active substance mixes, and then gained mixture is carried out heat treatment.
6. method according to claim 5, wherein, the dispersant be At least one in ketone.
7. method according to claim 5, wherein, the mode of the heat treatment is spray drying, microwave drying, fluid bed Dry or oven drying, be preferably spray-dried.
8. a kind of lithium ion battery electrode sizing agent, it is characterised in that the electrode slurry includes lithium ion battery active substance, viscous Knot agent, conductive agent, solvent and optional thickening agent, wherein, the lithium ion battery active substance is any in claim 1-4 Lithium ion battery active material described in one；
Preferably, on the basis of the weight of the lithium ion battery active material, content of the binding agent in terms of butt For 0.5-5 weight %, the content of the conductive agent is 0.5-5 weight %, and the content of the solvent is 55-200 weight %, described The content of thickening agent is 0-2.5 weight %.
9. a kind of lithium ion cell positive or negative pole, it is characterised in that the lithium ion cell positive or negative pole include collector And the electrode dressing on collector, the electrode dressing contain lithium ion battery active substance, binding agent, conductive agent and appoint The thickening agent of choosing, wherein, the lithium ion battery active substance is the lithium ion battery in claim 1-4 described in any one Active material.
10. a kind of lithium ion battery, it is characterised in that the lithium ion battery includes battery container and is located in battery container The battery core component in portion and electrolyte, the battery core component includes positive pole, negative pole and barrier film, and just extremely claim 9 institute The lithium ion cell positive that states, and/or the negative pole be claim 9 described in lithium ion battery negative.
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* Cited by examiner, † Cited by third party
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101154726A (en) * 2006-09-29 2008-04-02 比亚迪股份有限公司 Anode active substance and its preparing method and anode and battery
CN101308925A (en) * 2008-07-04 2008-11-19 深圳市贝特瑞新能源材料股份有限公司 Composite coated positive pole material of lithium ionic cell and preparing method thereof
CN101728521A (en) * 2009-11-28 2010-06-09 内蒙古科技大学 Preparation method of Co-covered nickel hydroxide anode material with surface covered by rare earth compound
CN101728529A (en) * 2008-10-10 2010-06-09 深圳市天骄科技开发有限公司 Lithium ion battery anode material and manufacturing method thereof
CN101944599A (en) * 2010-09-15 2011-01-12 宁波科博特钴镍有限公司 Preparation method of cobalt-based material
CN105118972A (en) * 2015-07-06 2015-12-02 浙江大学 Metal hydroxide coated carbon and sulfur lithium-sulfur battery positive electrode material, and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101154726A (en) * 2006-09-29 2008-04-02 比亚迪股份有限公司 Anode active substance and its preparing method and anode and battery
CN101308925A (en) * 2008-07-04 2008-11-19 深圳市贝特瑞新能源材料股份有限公司 Composite coated positive pole material of lithium ionic cell and preparing method thereof
CN101728529A (en) * 2008-10-10 2010-06-09 深圳市天骄科技开发有限公司 Lithium ion battery anode material and manufacturing method thereof
CN101728521A (en) * 2009-11-28 2010-06-09 内蒙古科技大学 Preparation method of Co-covered nickel hydroxide anode material with surface covered by rare earth compound
CN101944599A (en) * 2010-09-15 2011-01-12 宁波科博特钴镍有限公司 Preparation method of cobalt-based material
CN105118972A (en) * 2015-07-06 2015-12-02 浙江大学 Metal hydroxide coated carbon and sulfur lithium-sulfur battery positive electrode material, and preparation method and application thereof

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107039650A (en) * 2017-06-09 2017-08-11 北京当升材料科技股份有限公司 A kind of manganese coating modification lithium battery tertiary cathode material and preparation method thereof
CN107799741A (en) * 2017-09-28 2018-03-13 华南理工大学 A kind of preparation method of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide
CN108039449B (en) * 2017-12-07 2020-02-11 福建荣华科技有限公司 Preparation method of lithium ion battery and lithium ion battery
CN108039449A (en) * 2017-12-07 2018-05-15 福建荣华科技有限公司 The preparation method and lithium ion battery of lithium ion battery
CN108390065A (en) * 2018-01-25 2018-08-10 湖北师范大学 A method of in li-ion electrode materials surface coating cerium oxide
CN108682842A (en) * 2018-03-23 2018-10-19 格林美（无锡）能源材料有限公司 A kind of Y doping CaMnO3Tertiary cathode material of cladding and preparation method thereof
CN108682842B (en) * 2018-03-23 2021-03-30 格林美（无锡）能源材料有限公司 Y-doped CaMnO3Coated ternary positive electrode material and preparation method thereof
CN110061225A (en) * 2019-05-06 2019-07-26 湖南金富力新能源股份有限公司 A kind of monocrystalline high capacity nickel-cobalt lithium manganate cathode material and preparation method thereof
CN110311104A (en) * 2019-06-20 2019-10-08 桑顿新能源科技(长沙)有限公司 A kind of slurry and preparation method, cathode pole piece, lithium ion battery
CN110311105A (en) * 2019-06-20 2019-10-08 桑顿新能源科技(长沙)有限公司 A kind of cathode pole piece slurry and preparation method, cathode pole piece, lithium ion battery
CN111403700A (en) * 2020-03-06 2020-07-10 武汉理工大学 Chromium hydroxide-coated chromium chromate lithium primary battery positive electrode material and preparation method thereof
CN111403700B (en) * 2020-03-06 2021-07-20 武汉理工大学 Chromium hydroxide-coated chromium chromate lithium primary battery positive electrode material and preparation method thereof
CN111477859A (en) * 2020-05-09 2020-07-31 宁波锋成纳米科技有限公司 Composite positive electrode material, preparation method thereof and water-based secondary battery
CN112216825A (en) * 2020-08-31 2021-01-12 合肥国轩高科动力能源有限公司 Preparation method of nitrogen-doped lithium vanadate/lithium iron phosphate composite material
CN112216825B (en) * 2020-08-31 2022-04-12 合肥国轩高科动力能源有限公司 Preparation method of nitrogen-doped lithium vanadate/lithium iron phosphate composite material
CN112079400A (en) * 2020-09-09 2020-12-15 合肥国轩高科动力能源有限公司 Low-pH-value lithium ion battery high-nickel ternary material and preparation method and application thereof
CN115072805A (en) * 2022-07-21 2022-09-20 多氟多新材料股份有限公司 Sodium-ion battery positive electrode material precursor, preparation method thereof and preparation method of sodium-ion battery positive electrode material
CN115072805B (en) * 2022-07-21 2024-03-12 多氟多新材料股份有限公司 Precursor of sodium ion battery positive electrode material, preparation method of precursor and preparation method of sodium ion battery positive electrode material

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