CN106784850A - The application of additive, electrode slurry, additive slurry, lithium ion cell positive or negative pole and preparation method thereof and lithium ion battery - Google Patents

The application of additive, electrode slurry, additive slurry, lithium ion cell positive or negative pole and preparation method thereof and lithium ion battery Download PDF

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Publication number
CN106784850A
CN106784850A CN201710080769.2A CN201710080769A CN106784850A CN 106784850 A CN106784850 A CN 106784850A CN 201710080769 A CN201710080769 A CN 201710080769A CN 106784850 A CN106784850 A CN 106784850A
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metallic element
additive
lithium
group
races
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先雪峰
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Priority to CN201710080769.2A priority Critical patent/CN106784850A/en
Priority to PCT/CN2017/074513 priority patent/WO2018148978A1/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
    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • 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
    • H01M4/139—Processes of manufacture
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention relates to technical field of lithium ion, a kind of application of additive, electrode slurry, additive slurry, lithium ion cell positive or negative pole and preparation method thereof and lithium ion battery are disclosed.Wherein, application of the additive in lithium ion cell positive and/or negative pole is prepared is specifically disclosed, the additive is M (OH)a(PO4)b(CO3)c(OCOCH3)d·eH2O, wherein, M is at least one element in Group IIA metal element, IB races metallic element, Group IIB metal element, IIIB races metallic element, Group IVB metallic element, VB races metallic element, group vib metallic element, VIIB races metallic element, group VIII metal element, Group IIIA metallic element, IVA races metallic element and VA races metallic element, a>0, b >=0, c >=0, d >=0, and be 0, e >=0 when b, c, d difference.Additive of the present invention is used to prepare lithium ion cell positive and/or negative pole, the security of the lithium ion battery for thus preparing can be significantly improved.

Description

The application of additive, electrode slurry, additive slurry, lithium ion cell positive or negative Pole and preparation method thereof and lithium ion battery
Technical field
The present invention relates to technical field of lithium ion, in particular it relates to a kind of additive is preparing lithium ion battery just Application, a kind of lithium ion battery electrode sizing agent in pole and/or negative pole, a kind of additive slurry, a kind of lithium ion cell positive Or negative pole and preparation method thereof and a kind of lithium ion battery.
Background technology
Lithium ion battery is the green high-capacity battery of a new generation, with voltage is high, energy density big, long lifespan, self discharge The many merits such as small, memory-less effect, operating temperature range be wide, 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 (such as energy storage of fixed sources of energy field Power station, UPS etc.), suffer from being widely applied prospect.
Lithium ion battery voltage is high to be also implied that under state-of-charge, and the positive and negative electrode of battery has larger electrical potential difference, Mean that cathodic reduction is stronger, positive pole oxidisability is stronger, and heat endurance 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, alkalescence that electrolyte solvent is done 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 further expand the consequence of security incident.
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 security is greatly improved is planted, is had important practical significance.
The content of the invention
The invention aims to overcome, lithium ion battery security in the prior art is low, there is severe compromise Defect, there is provided application, a kind of lithium ion cell electrode slurry of a kind of additive in lithium ion cell positive and/or negative pole is prepared Material, a kind of additive slurry, a kind of lithium ion cell positive or negative pole and preparation method thereof and a kind of lithium ion battery.
To achieve these goals, in a first aspect, preparing lithium ion cell positive the invention provides a kind of additive And/or the application in negative pole, the additive is M (OH)a(PO4)b(CO3)c(OCOCH3)d·eH2O, wherein, M is Group IIA gold Category element, IB races metallic element, Group IIB metal element, IIIB races metallic element, Group IVB metallic element, VB races metallic element, Group vib metallic element, VIIB races metallic element, group VIII metal element, Group IIIA metallic element, IVA races metallic element and VA At least one element in race's metallic element, a>0, b >=0, c >=0, d >=0, and be 0, e >=0 when b, c, d difference.
Second aspect, the invention provides a kind of lithium ion battery electrode sizing agent, the electrode slurry include active material, Binding agent, conductive agent, additive, solvent and optional thickener, on the basis of the weight of the active material, the additive Content be 0.05-31 weight %；The additive is M (OH)a(PO4)b(CO3)c(OCOCH3)d·eH2O, wherein, M is IIA Race's metallic element, IB races metallic element, Group IIB metal element, IIIB races metallic element, Group IVB metallic element, metal unit of VB races Element, group vib metallic element, VIIB races metallic element, group VIII metal element, Group IIIA metallic element, IVA races metallic element and At least one element in VA races metallic element, a>0, b >=0, c >=0, d >=0, and be 0, e >=0 when b, c, d difference.
The third aspect, the invention provides a kind of additive slurry, the additive slurry include binding agent, additive, Solvent and optional conductive agent, on the basis of the weight of the additive, the content that the binding agent is counted with butt is as 0.5-13 Weight %, the content of the solvent is 85-430 weight %, and the content of the conductive agent is 0-11 weight %；The additive is M(OH)a(PO4)b(CO3)c(OCOCH3)d·eH2O, wherein, M is Group IIA metal element, IB races metallic element, Group IIB metal unit Element, IIIB races metallic element, Group IVB metallic element, VB races metallic element, group vib metallic element, VIIB races metallic element, At least one element in group VIII metal element, Group IIIA metallic element, IVA races metallic element and VA races metallic element, a> 0, b >=0, c >=0, d >=0, and be 0, e >=0 when b, c, d difference.
Fourth aspect, the invention provides a kind of lithium ion cell positive or negative pole, the lithium ion cell positive or negative Pole include collector and the electrode dressing on collector, the electrode dressing contain active material, binding agent, conductive agent, Additive and optional thickener, the additive are M (OH)a(PO4)b(CO3)c(OCOCH3)d·eH2O, wherein, M is Group IIA Metallic element, IB races metallic element, Group IIB metal element, IIIB races metallic element, Group IVB metallic element, metal unit of VB races Element, group vib metallic element, VIIB races metallic element, group VIII metal element, Group IIIA metallic element, IVA races metallic element and At least one element in VA races metallic element, a>0, b >=0, c >=0, d >=0, and be 0, e >=0 when b, c, d difference.
5th aspect, the invention provides a kind of method for preparing lithium ion cell positive or negative pole, methods described includes： By lithium ion battery electrode sizing agent of the present invention coating on a current collector, drying；Or
(1) by additive slurry of the present invention coating on a current collector, drying, obtains the afflux of additive coating Body；
(2) prepare active material slurry, the active material slurry include active material, binding agent, conductive agent, solvent and , then be coated in the active material slurry on the collector of the additive coating that step (1) is obtained by optional thickener, dries It is dry；Or
(1) prepare active material slurry, the active material slurry include active material, binding agent, conductive agent, solvent and Optional thickener, then by active material slurry coating on a current collector, drying obtains electrode plates；
(2) additive slurry of the present invention is coated on the electrode plates that step (1) is obtained, is dried.
6th aspect, the invention provides lithium ion cell positive or negative pole that the above-mentioned method of the present invention is prepared.
7th 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 battery container, the battery core component include positive pole, negative pole and barrier film, and it is described just extremely Lithium ion cell positive of the present invention, and/or the negative pole is lithium ion battery negative of the present invention.
The present inventor is creative under study for action to be found, additive of the present invention is used to prepare lithium-ion electric Pond positive pole and/or negative pole, can significantly improve the security of the lithium ion battery for thus preparing, and almost to lithium-ion electric The electric conductivity and cycle performance in pond etc. have no adverse effects.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, these scopes or Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively One or more can be obtained with combination with one another between the endpoint value of individual scope and single point value, and individually between point value New number range, these number ranges should be considered as specific open herein.
In a first aspect, the application the invention provides a kind of additive in lithium ion cell positive and/or negative pole is prepared, The additive is M (OH)a(PO4)b(CO3)c(OCOCH3)d·eH2O, wherein, M is Group IIA metal element, metal unit of IB races Element, Group IIB metal element, IIIB races metallic element, Group IVB metallic element, VB races metallic element, group vib metallic element, VIIB In race's metallic element, group VIII metal element, Group IIIA metallic element, IVA races metallic element and VA races metallic element at least A kind of element, a>0, b >=0, c >=0, d >=0, and be 0, e >=0 when b, c, d difference.
Wherein, it will be understood by those skilled in the art that in the present invention, additive is basic salt, its normalization formula It is M (OH)a(PO4)b(CO3)c(OCOCH3)d·eH2O, and at M (OH)a(PO4)b(CO3)c(OCOCH3)d·eH2In O, a, b, c, The selection of d meets the stoichiometric proportion principle of respective substance.
In application of the invention, under preferable case, in additive, the Group IIA metal element be Mg, Ca and Sr in extremely Few one kind, IB races metallic element is Cu, and the Group IIB metal element is Zn, IIIB races metallic element be Y, Sc, At least one in La, Ce, Nd, Sm, Gd and Er, the Group IVB metallic element is Ti and/or Zr, VB races metallic element It is V and/or Nb, the group vib metallic element is Cr and/or Mo, VIIB races metallic element is Mn, the group VIII metal Element is at least one in Fe, Co and Ni, and the Group IIIA metallic element is Al, and IVA races metallic element is Sn, described VA races metallic element is Bi and/or Sb.
In application of the invention, additive can also may be used for that can be crystalline state one or more in foregoing various basic salt Being amorphous state.In order to further improve the security of the lithium ion battery for preparing, it is preferable that the additive is alkali formula At least one in magnesium carbonate, basic copper acetate and basic nickel carbonate；It is further preferred that the additive is Mg (OH)0.40 (CO3)0.80·H2O、Cu(OH)1.50(OCOCH3)0.50·0.50H2O and Ni (OH)4/3(CO3)1/3·4/3H2In O at least one Kind.
In application of the invention, in the method for lithium ion cell positive and/or negative pole is prepared, for aforementioned additive There is no particular limitation for concrete application mode or incorporation way, as long as preparing the process of lithium ion cell positive and/or negative pole In apply additive of the present invention and belong to the respective additive in lithium ion cell positive and/or negative pole is prepared Using.Wherein, under preferable case, in negative or positive electrode, on the basis of the dry weight of electrode dressing, the content of additive is 0.05-23 weight %, in view of battery energy density and battery combination property consider that more preferably 3-16 weight % is more excellent Elect 5.5-10 weight % as.It will be understood by those skilled in the art that the dry weight of electrode dressing refers to coat on a current collector The drying of all slurries after the weight of material that obtains.
In application of the invention, individual particle or Water-borne paint for additive are not specially required, but from being easy to For scattered angle, additive is preferably dimensioned to be less than 300 microns, more preferably less than 30 microns.
In the present invention, for foregoing different additive, i.e., the preparation method of the basic salt of different element M is without special Restriction, can be various methods commonly used in the art, this is well known to those skilled in the art, and will not be repeated here.
Second aspect, the invention provides a kind of lithium ion battery electrode sizing agent, the electrode slurry include active material, Binding agent, conductive agent, additive, solvent and optional thickener, on the basis of the weight of the active material, the additive Content be 0.05-31 weight %；The additive is M (OH)a(PO4)b(CO3)c(OCOCH3)d·eH2O, wherein, M is IIA Race's metallic element, IB races metallic element, Group IIB metal element, IIIB races metallic element, Group IVB metallic element, metal unit of VB races Element, group vib metallic element, VIIB races metallic element, group VIII metal element, Group IIIA metallic element, IVA races metallic element and At least one element in VA races metallic element, a>0, b >=0, c >=0, d >=0, and be 0, e >=0 when b, c, d difference.
Preferably, on the basis of the weight of the active material, the content of the additive is 2-20 weight %, further Preferably 7-13 weight %.
In lithium ion battery electrode sizing agent of the invention, under preferable case, in additive, the Group IIA metal element is At least one in Mg, Ca and Sr, IB races metallic element is Cu, and the Group IIB metal element is Zn, the IIIB races gold Category 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, described VB races metallic element is V and/or Nb, and the group vib metallic element is Cr and/or Mo, and VIIB races metallic element is Mn, institute It is at least one in Fe, Co and Ni to state group VIII metal element, and the Group IIIA metallic element is Al, IVA races metal Element is Sn, and VA races metallic element is Bi and/or Sb.
In lithium ion battery electrode sizing agent of the invention, in order to further improve the safety of the lithium ion battery for preparing Property, it is preferable that the additive is at least one in basic magnesium carbonate, basic copper acetate and basic nickel carbonate；It is further excellent Selection of land, the additive is Mg (OH)0.40(CO3)0.80·H2O、Cu(OH)1.50(OCOCH3)0.50·0.50H2O and Ni (OH)4/3 (CO3)1/3·4/3H2At least one in O.
It is no for the individual particle or Water-borne paint of additive special in lithium ion battery electrode sizing agent of the invention It is required that, but from being easy to for scattered angle, additive is preferably dimensioned to be less than 300 microns, more preferably less than 30 microns.
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, for the species selection of active material, binding agent, conductive agent, solvent and thickener and consumption without special Restriction, conventional species selection and the consumption of this area respective components can be respectively, for battery energy density and battery The consideration of combination property, under preferable case, on the basis of the weight of the active material, content of the binding agent in terms of butt It is 0.5-5 weight %, the content of the conductive agent is 0.5-5 weight %, and the content of the solvent is 50-230 weight %, described The content of thickener is 0-3 weight %.Thickener is not used typically in lithium ion battery anode glue size, and in lithium ion battery Used in cathode size, on the basis of the weight of active material, content is 0.5-3 weight %.
In lithium ion battery anode glue size, do not selected particularly for positive active material, can be this area routine The various positive active materials for using, under preferable case, 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.
In lithium ion battery cathode slurry, do not selected particularly for negative electrode active material, can be this area routine The various negative electrode active materials for using, under preferable case, negative electrode active material is graphite, lithium titanate, silicon, hard carbon, tin and oxidation At least one in tin.
In lithium ion battery anode glue size and lithium ion battery cathode slurry, do not selected particularly for binding agent, can Think various binding agents commonly used in the art, under preferable case, binding agent is polyacrylamide, polyvinylidene fluoride, gathers In tetrafluoroethene, butadiene-styrene rubber, cellulose-based polymer, polyvinyl alcohol, polyolefin, Viton and Polyurethane at least one Kind, cellulose-based polymer can be fine selected from methylcellulose, ethyl cellulose, hydroxypropyl methyl cellulose and hydroxypropyl ethyl Dimension element in one or more.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, do not selected particularly for conductive agent, 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).
Do not selected particularly for solvent, can be various solvents commonly used in the art, under preferable case, solvent It is at least one in 1-METHYLPYRROLIDONE (NMP), deionized water, tetrahydrofuran, dimethyl sulfoxide (DMSO), ethanol and isopropanol. Wherein, it is further preferred that in lithium ion battery anode glue size, solvent is 1-METHYLPYRROLIDONE；It is negative in lithium ion battery In the slurry of pole, solvent is deionized water and/or 1-METHYLPYRROLIDONE.
Wherein, being applied in lithium ion battery cathode slurry thickener more, whether added in lithium ion battery anode glue size Plus thickener 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, thickener is at least one in sodium carboxymethylcellulose (CMC), polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol.
Wherein, for the preparation method of lithium ion battery electrode sizing agent of the invention, there is no particular limitation, can be this The conventional various methods in field, as long as can be well mixed by the slurry containing aforementioned component, for example, containing active matter The slurry of matter, binding agent, conductive agent, additive, solvent and optional thickener can by the way that first binding agent and solvent are mixed, Mixed liquor is obtained, is then mixed active material, conductive agent, additive and optional thickener with mixed liquor, Huo Zheke Mix with by by thickener or binding agent and solvent, obtain mixed liquor, then by active material, conductive agent, additive and viscous Knot agent or thickener are mixed with mixed liquor.
The third aspect, the invention provides a kind of additive slurry, the additive slurry include binding agent, additive, Solvent and optional conductive agent, on the basis of the weight of the additive, the content that the binding agent is counted with butt is as 0.5-13 Weight %, the content of the solvent is 85-430 weight %, and the content of the conductive agent is 0-11 weight %；The additive is M(OH)a(PO4)b(CO3)c(OCOCH3)d·eH2O, wherein, M is Group IIA metal element, IB races metallic element, Group IIB metal unit Element, IIIB races metallic element, Group IVB metallic element, VB races metallic element, group vib metallic element, VIIB races metallic element, At least one element in group VIII metal element, Group IIIA metallic element, IVA races metallic element and VA races metallic element, a> 0, b >=0, c >=0, d >=0, and be 0, e >=0 when b, c, d difference.
In additive slurry of the invention, under preferable case, in additive, the Group IIA metal element is Mg, Ca and Sr In at least one, IB races metallic element is Cu, and the Group IIB metal element is Zn, and IIIB races 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 races metal Element is V and/or Nb, and the group vib metallic element is Cr and/or Mo, and VIIB races metallic element is Mn, the VIII Metallic element is at least one in Fe, Co and Ni, and the Group IIIA metallic element is Al, and IVA races metallic element is Sn, VA races metallic element is Bi and/or Sb.
In additive slurry of the invention, in order to further improve the security of the lithium ion battery for preparing, preferably Ground, the additive is at least one in basic magnesium carbonate, basic copper acetate and basic nickel carbonate；It is further preferred that The additive is Mg (OH)0.40(CO3)0.80·H2O、Cu(OH)1.50(OCOCH3)0.50·0.50H2O and Ni (OH)4/3 (CO3)1/3·4/3H2At least one in O.
In additive slurry of the invention, individual particle or Water-borne paint for additive are not specially required, but From being easy to for scattered angle, additive is preferably dimensioned to be less than 300 microns, more preferably less than 30 microns.
In additive slurry, for binding agent, solvent and optional conductive agent species selection there is no particular limitation, The conventional species selection of this area respective components can be respectively, under preferable case, binding agent is polyacrylamide, poly- inclined two In PVF, polytetrafluoroethylene (PTFE), butadiene-styrene rubber, cellulose-based polymer, polyvinyl alcohol, polyolefin, Viton and Polyurethane At least one, cellulose-based polymer can be selected from methylcellulose, ethyl cellulose, hydroxypropyl methyl cellulose and hydroxypropyl One or more in base ethyl cellulose.When foregoing adhesives are polymer, the number-average molecular weight of each polymer is generally 30- 1500000.
In additive slurry, under preferable case, solvent is 1-METHYLPYRROLIDONE, deionized water, tetrahydrofuran, dimethyl At least one in sulfoxide, ethanol and isopropanol.Wherein, it is further preferred that solvent be 1-METHYLPYRROLIDONE and/or go from Sub- water.
In additive slurry, conductive agent is added to can be used to improve the electric conductivity of coating, under preferable case, conductive agent is section Qin is black, at least one in acetylene black, Graphene, CNT, carbon fiber, micro crystal graphite and conductive carbon black.
Wherein, for the preparation method of additive slurry of the invention, there is no particular limitation, can be commonly used in the art Various methods, as long as can be well mixed by the slurry containing aforementioned component, for example, containing binding agent, additive, molten The slurry of agent and optional conductive agent can obtain mixed liquor by first mixing binding agent and solvent, then by additive, appoint The conductive agent of choosing is 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 include collector and the electrode dressing on collector, the electrode dressing contain active material, binding agent, conductive agent, Additive and optional thickener, the additive are M (OH)a(PO4)b(CO3)c(OCOCH3)d·eH2O, wherein, M is Group IIA Metallic element, IB races metallic element, Group IIB metal element, IIIB races metallic element, Group IVB metallic element, metal unit of VB races Element, group vib metallic element, VIIB races metallic element, group VIII metal element, Group IIIA metallic element, IVA races metallic element and At least one element in VA races metallic element, a>0, b >=0, c >=0, d >=0, and be 0, e >=0 when b, c, d difference.
In lithium ion cell positive of the invention or negative pole, under preferable case, in additive, the Group IIA metal element It is at least one in Mg, Ca and Sr, IB races metallic element is Cu, and the Group IIB metal element is Zn, the IIIB races Metallic 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, institute VB races metallic element is stated for V and/or Nb, the group vib metallic element is Cr and/or Mo, VIIB races metallic element is Mn, The group VIII metal element is at least one in Fe, Co and Ni, and the Group IIIA metallic element is Al, the IVA races gold Category element is Sn, and VA races metallic element is Bi and/or Sb.
In lithium ion cell positive of the invention or negative pole, in order to further improve the peace of the lithium ion battery for preparing Quan Xing, it is preferable that the additive is at least one in basic magnesium carbonate, basic copper acetate and basic nickel carbonate；More enter one Preferably, the additive is Mg (OH) to step0.40(CO3)0.80·H2O、Cu(OH)1.50(OCOCH3)0.50·0.50H2O and Ni (OH)4/3(CO3)1/3·4/3H2At least one in O.
In lithium ion cell positive of the invention or negative pole, do not selected particularly for active material, can be ability The conventional use of various active materials in domain, under preferable case, the active material be positive active material or negative electrode active material, The 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, mangaic acid Lithium, 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 At least one in lithium, phosphoric acid vanadium lithium and ferric metasilicate lithium, the negative electrode active material be graphite, lithium titanate, silicon, hard carbon, tin and At least one in tin oxide.
In lithium ion cell positive of the invention or negative pole, do not selected particularly for binding agent, can be this area Conventional use of various binding agents, under preferable case, binding agent is polyacrylamide, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), fourth At least one in benzene rubber, cellulose-based polymer, polyvinyl alcohol, polyolefin, Viton and Polyurethane.
In lithium ion cell positive of the invention or negative pole, do not selected particularly for conductive agent, can be this area Conventional use of various conductive agents, under preferable case, conductive agent be Ketjen black, acetylene black, Graphene, CNT, carbon fiber, At least one in micro crystal graphite and conductive carbon black.
In lithium ion cell positive of the invention or negative pole, as it was previously stated, typically containing thickening in lithium ion battery negative Agent, under preferable case, thickener be sodium carboxymethylcellulose, polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol in extremely Few one kind.
In lithium ion cell positive of the invention or negative pole, in order to further improve the peace of the lithium ion battery for preparing Full property takes into account battery energy density and battery combination property simultaneously, it is preferable that on the basis of the dry weight of electrode dressing, the addition The content of agent is 0.05-23 weight %, more preferably 3-16 weight %, is still more preferably 5.5-10 weight %.
5th aspect, the invention provides a kind of method for preparing lithium ion cell positive or negative pole, methods described includes： By lithium ion battery electrode sizing agent of the present invention coating on a current collector, drying；Or
(1) by additive slurry of the present invention coating on a current collector, drying, obtains the afflux of additive coating Body；
(2) prepare active material slurry, the active material slurry include active material, binding agent, conductive agent, solvent and , then be coated in the active material slurry on the collector of the additive coating that step (1) is obtained by optional thickener, dries It is dry；Or
(1) prepare active material slurry, the active material slurry include active material, binding agent, conductive agent, solvent and Optional thickener, then by active material slurry coating on a current collector, drying obtains electrode plates；
(2) additive slurry of the present invention is coated on the electrode plates that step (1) is obtained, is dried.
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, in each step coat method there is no particular limitation, can be various methods commonly used in the art, This is that known to people in the art, will not be repeated here.
Wherein, under preferable case, for the active material slurry of lithium ion cell positive in, the slurry include positive pole live Property material, binding agent, conductive agent and solvent, on the basis of the weight of the active material, the binding agent containing in terms of butt It is 0.5-5 weight % to measure, and the content of the conductive agent is 0.5-5 weight %, and the content of the solvent is 50-230 weight %.
Under preferable case, for the active material slurry of lithium ion battery negative in, the slurry include negative electrode active material Matter, binding agent, conductive agent, solvent and thickener, on the basis of the weight of the active material, the binding agent is in terms of butt Content is 0.5-5 weight %, and the content of the conductive agent is 0.5-5 weight %, and the amount of thickener is 0.5-3 weight %, The content of the solvent is 50-230 weight %.
Wherein, the tool of foregoing various positive active materials, negative electrode active material, binding agent, conductive agent, solvent and thickener Body species is selected, and can be found in corresponding contents above, be will not be repeated here.And it will be understood by those skilled in the art that When preparing lithium ion cell positive or negative pole, each self-corresponding collector and active material slurry are used.
Wherein, for dry method 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.
6th aspect, the invention provides lithium ion cell positive or negative pole that methods described is prepared.
7th 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 battery container, the battery core component include positive pole, negative pole and barrier film, and it is described just extremely Lithium ion cell positive of the present invention, and/or the negative pole is lithium ion battery negative of the present invention.
In lithium ion battery of the invention, it will be understood by those skilled in the art that in positive pole and negative pole at least one Individual electrode is to be added with the negative or positive electrode prepared after additive of the present invention, i.e. lithium just extremely of the present invention Ion battery positive pole, or negative pole is lithium ion battery negative of the present invention, or, positive pole and negative pole are respectively this simultaneously Invention described lithium ion cell positive and negative pole.
In lithium ion battery of the invention, the barrier film and electrolyte for forming lithium ion battery can be commonly used in the art 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 polypropylene microporous membrane and polypropylene and polyethylene MULTILAYER COMPOSITE microporous membrane.The position of barrier film, Property and species are well known to those skilled in the art, and will not be repeated here.
Wherein, nonaqueous electrolytic solution is the mixed solution of electrolyte lithium salt and nonaqueous solvents, and it is not particularly limited, can be with Use the conventional nonaqueous electrolytic solution in this area.Such as electrolyte lithium salt is selected from lithium hexafluoro phosphate (LiPF6), lithium perchlorate, tetrafluoro One or more in lithium borate, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and fluorohydrocarbon base Sulfonic Lithium.Nonaqueous solvents selects chain 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), propene 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 grams/ampere-hour, and the concentration of electrolyte is generally 0.8-1.2 mol/Ls.
In lithium ion battery of the 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 repeated here.
In lithium ion battery of the invention, the method for preparing battery is the common method of this area, in general, by positive pole A battery core component is constituted with negative pole and barrier film, the battery core component and nonaqueous electrolytic solution that will be obtained are sealed in battery case, you can Obtain lithium ion battery.Specific method is well known to those skilled in the art, and will not be repeated here.
Embodiment
Below will by embodiment, the present invention will be described in detail, but and be not so limited the present invention, such as without especially saying Bright, material used can be the conventional method of this area by commercially available, used method, and room temperature is 25 DEG C.
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 agents HSV900 is purchased from French Arkema.
PTFE emulsion binding agent D210 solid contents are 60%, purchased from Daikin Industries,Ltd..
Conductive agent Super-P is purchased from Te Migao companies of Switzerland.
Native graphite is purchased from Shenzhen Bei Terui new energy materialses limited company.
Thickener CMC is purchased from Japanese Di-ichi Kogyo Seiyaku Co., Ltd..
Butadiene-styrene rubber emulsion binder solid content is 50%, purchased from Zeon Corp.
(normalization formula is Mg (OH) to basic magnesium carbonate0.40(CO3)0.80·H2O preparation method) includes：By 2560g six Water magnesium nitrate 10000g deionized water dissolvings, are obtained magnesium nitrate solution, by 160g NaOH, 848g sodium carbonate 20000g Deionized water dissolving, obtains NaOH, sodium carbonate mixture.At room temperature, under conditions of 280rpm strong stirrings, by nitre Sour magnesium solution mixes with NaOH, sodium carbonate mixture, controls incorporation time for 2 hours, obtains suspension, passes through Filter, is precipitated.The precipitation is washed with deionized to remove impurity therein, then by spray drying at 105 DEG C (normalization formula is Mg (OH) to obtain alkali formula magnesium phosphate0.40(CO3)0.80·H2O) powder, measures wherein particle diameter D50 for 340nm.
(normalization formula is Cu (OH) to basic copper acetate1.50(OCOCH3)0.50·0.50H2O preparation method) includes：Will The water acetic acid copper 20000g deionized water dissolvings of 2000g mono-, are obtained acetic acid copper solution, by 600g NaOH with 20000g go from Sub- water dissolves, obtain sodium hydroxide solution.At room temperature, under conditions of 230rpm strong stirrings, by acetic acid copper solution and hydrogen-oxygen Change sodium solution mixing, control incorporation time for 2 hours, obtain suspension, the suspension is heated to boiling, and kept for 2 hours, By filtering, it is precipitated.The precipitation is washed with deionized to remove impurity therein, then by spray at 105 DEG C Mist is dried to obtain basic copper acetate, and (normalization formula is Cu (OH)1.50(OCOCH3)0.50·0.50H2O) powder, measures wherein grain Footpath D50 is 220nm.
(normalization formula is Ni (OH) to basic nickel carbonate4/3(CO3)1/3·4/3H2O preparation method) includes：By 2910g Six water nitric acid Asia nickel 20000g deionized water dissolvings, are obtained nitric acid Asia nickel solution.534g NaOH, 354g sodium carbonate are used 20000g deionized water dissolvings, obtain NaOH, sodium carbonate mixture.Under nitrogen protection, at room temperature, 310rpm is strong Under conditions of power stirring, nitric acid Asia nickel solution is mixed with NaOH, sodium carbonate mixture, control incorporation time for 2 is small When, suspension is obtained, by filtering, it is precipitated.Under nitrogen protection, the precipitation is washed with deionized to remove wherein Impurity, then at 110 DEG C by spray drying obtain basic nickel carbonate (normalization formula be Ni (OH)4/3(CO3)1/3· 4/3H2O) powder, measures wherein particle diameter D50 for 280nm.
(normalization formula is Ca (PO to alkali calcium phosphate4)0.60(OH)0.20) preparation method include：By the anhydrous nitre of 1640g Sour calcium 20000g deionized water dissolvings, are obtained calcium nitrate solution, and 984g tertiary sodium phosphates 20000g deionized water dissolvings are obtained To trisodium phosphate solution.At room temperature, under conditions of 340rpm strong stirrings, calcium nitrate solution is mixed with trisodium phosphate solution Close, and it is 10.0 to control the pH value of mixed system with the sodium hydroxide solution of 2 moles of every liter of concentration, controls incorporation time for 2 is small When, suspension is obtained, by filtering, it is precipitated.The precipitation is washed with deionized to remove impurity therein, Ran Hou At 105 DEG C by spray drying obtain alkali calcium phosphate (normalization formula be Ca (PO4)0.60(OH)0.20) powder, measure wherein Particle diameter D50 is 170nm.
(normalization formula is Sr (PO to alkali formula strontium phosphate4)0.60(OH)0.20) preparation method include：By the anhydrous nitre of 2117g Sour strontium 20000g deionized water dissolvings, are obtained strontium nitrate solution, and 984g tertiary sodium phosphates 20000g deionized water dissolvings are obtained To trisodium phosphate solution.At room temperature, under conditions of 280rpm strong stirrings, strontium nitrate solution is mixed with trisodium phosphate solution Close, and it is 10.0 to control the pH value of mixed system with the sodium hydroxide solution of 2 moles of every liter of concentration, controls incorporation time for 2 is small When, suspension is obtained, by filtering, it is precipitated.The precipitation is washed with deionized to remove impurity therein, Ran Hou At 105 DEG C by spray drying obtain alkali formula strontium phosphate (normalization formula be Sr (PO4)0.60(OH)0.20) powder, measure wherein Particle diameter D50 is 130nm.
(normalization formula is Zn (OH) to basic zinc carbonate4/3(CO3)1/3·1/3H2O preparation method) includes：By 2970g Zinc nitrate hexahydrate 10000g deionized water dissolvings, are obtained zinc nitrate solution, and 636g sodium carbonate is water-soluble with 20000g deionizations Solution, obtains sodium carbonate liquor.At 45 DEG C, under conditions of 260rpm strong stirrings, by zinc nitrate solution and sodium carbonate liquor simultaneously Stream, controls the time for adding of zinc nitrate solution for 2 hours, and control to react by controlling the rate of addition of sodium carbonate liquor PH value is 7.0 in journey, after zinc nitrate solution is dripped, obtains suspension, by filtering, is precipitated.The precipitation is spent Then ion water washing obtains basic zinc carbonate (normalization formula at 105 DEG C to remove impurity therein by spray drying It is Zn (OH)4/3(CO3)1/3·1/3H2O) powder, measures wherein particle diameter D50 for 300nm.
(normalization formula is Y (OH) (CO to basic yttrium carbonate3)) preparation method include：The water yttrium nitrates of 3830g six are used 10000g deionized water dissolvings, are obtained yttrium nitrate solution, by 400g NaOH, 1060g sodium carbonate 20000g deionized waters Dissolving, obtains NaOH, sodium carbonate mixture.At room temperature, under conditions of 300rpm strong stirrings, by yttrium nitrate solution Mix with NaOH, sodium carbonate mixture, control incorporation time for 2 hours, obtain suspension, by filtering, sunk Form sediment.The precipitation is washed with deionized to remove impurity therein, alkali formula carbon is then obtained by spray drying at 110 DEG C (normalization formula is Y (OH) (CO to sour yttrium3)) powder, wherein particle diameter D50 is measured for 280nm.
(normalization formula is Sc (OH) (CO to basic carbonate scandium3)) preparation method include：The water scandium nitrates of 3390g six are used 10000g deionized water dissolvings, are obtained scandium nitrate solution, by 400g NaOH, 1060g sodium carbonate 20000g deionized waters Dissolving, obtains NaOH, sodium carbonate mixture.At room temperature, under conditions of 270rpm strong stirrings, by scandium nitrate solution Mix with NaOH, sodium carbonate mixture, control incorporation time for 2 hours, obtain suspension, by filtering, sunk Form sediment.The precipitation is washed with deionized to remove impurity therein, alkali formula carbon is then obtained by spray drying at 110 DEG C (normalization formula is Sc (OH) (CO to sour scandium3)) powder, wherein particle diameter D50 is measured for 260nm.
(normalization formula is La (OH) (CO to basic carbonate lanthanum3)) preparation method include：4330g lanthanum nitrate hexahydrates are used 10000g deionized water dissolvings, are obtained lanthanum nitrate hexahydrate, by 400g NaOH, 1060g sodium carbonate 20000g deionized waters Dissolving, obtains NaOH, sodium carbonate mixture.At room temperature, under conditions of 250rpm strong stirrings, by lanthanum nitrate hexahydrate Mix with NaOH, sodium carbonate mixture, control incorporation time for 2 hours, obtain suspension, by filtering, sunk Form sediment.The precipitation is washed with deionized to remove impurity therein, alkali formula carbon is then obtained by spray drying at 110 DEG C (normalization formula is La (OH) (CO to sour lanthanum3)) powder, wherein particle diameter D50 is measured for 240nm.
(normalization formula is Ce (OH) (CO to basic carbonate cerium3)) preparation method include：The water cerous nitrates of 4340g six are used 10000g deionized water dissolvings, are obtained cerous nitrate solution, by 400g NaOH, 1060g sodium carbonate 20000g deionized waters Dissolving, obtains NaOH, sodium carbonate mixture.At room temperature, under conditions of 220rpm strong stirrings, by cerous nitrate solution Mix with NaOH, sodium carbonate mixture, control incorporation time for 2 hours, obtain suspension, by filtering, sunk Form sediment.The precipitation is washed with deionized to remove impurity therein, alkali formula carbon is then obtained by spray drying at 110 DEG C (normalization formula is Ce (OH) (CO to sour cerium3)) powder, wherein particle diameter D50 is measured for 230nm.
(normalization formula is Nd (OH) (CO to neodymium hydroxyl-carbonate3)) preparation method include：The water neodymium nitrates of 4380g six are used 10000g deionized water dissolvings, are obtained neodymium nitrate solution, by 400g NaOH, 1060g sodium carbonate 20000g deionized waters Dissolving, obtains NaOH, sodium carbonate mixture.At room temperature, under conditions of 240rpm strong stirrings, by neodymium nitrate solution Mix with NaOH, sodium carbonate mixture, control incorporation time for 2 hours, obtain suspension, by filtering, sunk Form sediment.The precipitation is washed with deionized to remove impurity therein, alkali formula carbon is then obtained by spray drying at 110 DEG C (normalization formula is Nd (OH) (CO to sour neodymium3)) powder, wherein particle diameter D50 is measured for 200nm.
(normalization formula is Sm (OH) (CO to basic carbonate samarium3)) preparation method include：The water samaric nitrates of 4440g six are used 10000g deionized water dissolvings, are obtained samarium nitrate solution, by 400g NaOH, 1060g sodium carbonate 20000g deionized waters Dissolving, obtains NaOH, sodium carbonate mixture.At room temperature, under conditions of 370rpm strong stirrings, by samarium nitrate solution Mix with NaOH, sodium carbonate mixture, control incorporation time for 2 hours, obtain suspension, by filtering, sunk Form sediment.The precipitation is washed with deionized to remove impurity therein, alkali formula carbon is then obtained by spray drying at 110 DEG C (normalization formula is Sm (OH) (CO to sour samarium3)) powder, wherein particle diameter D50 is measured for 300nm.
(normalization formula is Gd (OH) (CO to basic carbonate gadolinium3)) preparation method include：The water gadolinium nitrates of 4510g six are used 10000g deionized water dissolvings, are obtained gadolinium nitrate solution, by 400g NaOH, 1060g sodium carbonate 20000g deionized waters Dissolving, obtains NaOH, sodium carbonate mixture.At room temperature, under conditions of 390rpm strong stirrings, by gadolinium nitrate solution Mix with NaOH, sodium carbonate mixture, control incorporation time for 2 hours, obtain suspension, by filtering, sunk Form sediment.The precipitation is washed with deionized to remove impurity therein, alkali formula carbon is then obtained by spray drying at 110 DEG C (normalization formula is Gd (OH) (CO to sour gadolinium3)) powder, wherein particle diameter D50 is measured for 240nm.
(normalization formula is Er (OH) (CO to basic carbonate erbium3)) preparation method include：The water erbium nitrates of 4430g five are used 10000g deionized water dissolvings, are obtained Nitrate Solution, by 400g NaOH, 1060g sodium carbonate 20000g deionized waters Dissolving, obtains NaOH, sodium carbonate mixture.At room temperature, under conditions of 300rpm strong stirrings, by Nitrate Solution Mix with NaOH, sodium carbonate mixture, control incorporation time for 2 hours, obtain suspension, by filtering, sunk Form sediment.The precipitation is washed with deionized to remove impurity therein, alkali formula carbon is then obtained by spray drying at 110 DEG C (normalization formula is Er (OH) (CO to sour erbium3)) powder, wherein particle diameter D50 is measured for 270nm.
(normalization formula is Ti (OH) to alkali formula titanium phosphate1.66(PO4)0.78) preparation method include：By 880g hydroxides Sodium, 1640g tertiary sodium phosphates 20000g deionized water dissolvings, obtain NaOH, tertiary sodium phosphate mixed solution.At room temperature, Under conditions of 280rpm strong stirrings, 1897g titanium tetrachloride liquids are slowly added to NaOH, tertiary sodium phosphate mixed solution In, control feed time for 2 hours, suspension is obtained, by filtering, it is precipitated.By the precipitation be washed with deionized with Remove impurity therein, then at 110 DEG C by spray drying obtain alkali formula titanium phosphate (normalization formula be Ti (OH)1.66 (PO4)0.78) powder, wherein particle diameter D50 is measured for 140nm.
(normalization formula is Zr (OH) to alkali formula phosphoric acid zirconium carbonate1.45(PO4)0.60(CO3)0.375) preparation method include：Will 800g NaOH, 1312g tertiary sodium phosphates, 636g sodium carbonate 20000g deionized water dissolvings, obtain NaOH, tricresyl phosphate The mixed solution of sodium, sodium carbonate.At room temperature, under conditions of 330rpm strong stirrings, 2330g zirconium chloride powder is slowly added Enter into above-mentioned mixed solution, control feed time for 2 hours, obtain suspension, by filtering, be precipitated.This is precipitated It is washed with deionized to remove impurity therein, then obtaining alkali formula phosphoric acid zirconium carbonate by spray drying at 110 DEG C (returns One changes formula for Zr (OH)1.45(PO4)0.60(CO3)0.375) powder, wherein particle diameter D50 is measured for 260nm.
(normalization formula is V (OH) to alkali formula vanadium phosphate1.62(PO4)0.46) preparation method include：By 1640g tricresyl phosphates Sodium, 1440g NaOH 20000g deionized water dissolvings, obtain tertiary sodium phosphate, NaOH mixed solution.In nitrogen protection Under, at room temperature, under conditions of 360rpm strong stirrings, by 1570g vanadium trichloride powder be slowly added to 15 liters 2 moles every liter it is dense Dissolved in the aqueous hydrochloric acid solution of degree, obtain vanadium trichloride solution.Vanadium trichloride solution is slowly added to above-mentioned tertiary sodium phosphate, hydrogen In sodium oxide molybdena mixed solution, control feed time for 2 hours, obtain suspension, by filtering, be precipitated.In nitrogen protection Under, the precipitation is washed with deionized to remove impurity therein, alkali formula phosphorus is then obtained by spray drying at 110 DEG C (normalization formula is V (OH) to sour vanadium1.62(PO4)0.46) powder, wherein particle diameter D50 is measured for 430nm.
(normalization formula is Nb (OH) to alkali formula niobium phosphate1.22(PO4)1.26) preparation method include：By 18040g tricresyl phosphates Sodium, 6720g NaOH 300000g deionized water dissolvings, obtain tertiary sodium phosphate, NaOH mixed solution.By 929g gold Category niobium is dissolved in by mixing that the concentrated nitric acid that 3200g mass fractions are 65% and the hydrofluoric acid that 5000g mass fractions are 40% are constituted Close in solution, niobium liquid is obtained.At room temperature, under conditions of 390rpm strong stirrings, niobium liquid is slowly added to above-mentioned tricresyl phosphate In sodium, NaOH mixed solution, control feed time for 2 hours, obtain suspension, by filtering, be precipitated.This is sunk Shallow lake is washed with deionized to remove impurity therein, then obtains alkali formula niobium phosphate (normalizing by spray drying at 110 DEG C Change formula is Nb (OH)1.22(PO4)1.26) powder, wherein particle diameter D50 is measured for 460nm.
(normalization formula is Cr (OH) to alkali formula chromium phosphate0.90(PO4)0.70) preparation method include：By 1148g tricresyl phosphates Sodium 20000g deionized water dissolvings, obtain trisodium phosphate solution.The water chromic nitrates of 4000g nine are dissolved in 15000g deionized waters In, chromium nitrate solution is obtained.At room temperature, under conditions of 350rpm strong stirrings, by chromium nitrate solution and trisodium phosphate solution Mixing, and it is 10.0 to control the pH value of mixed system with the ammonia spirit that mass fraction is 25%, controls incorporation time for 2 is small When, suspension is obtained, by filtering, it is precipitated.The precipitation is washed with deionized to remove impurity therein, Ran Hou At 110 DEG C by spray drying obtain alkali formula chromium phosphate (normalization formula be Cr (OH)0.90(PO4)0.70) powder, measure wherein Particle diameter D50 is 320nm.
(normalization formula is Mo (OH) to alkali formula molybdenum phosphate0.75(PO4)0.75) preparation method include：By 1230g tricresyl phosphates Sodium 20000g deionized water dissolvings, obtain trisodium phosphate solution.The water molybdenum trichlorides of 2560g tri- are dissolved in 15000g deionizations In water, molybdenum trichloride solution is obtained.At room temperature, under conditions of 270rpm strong stirrings, by molybdenum trichloride solution and tricresyl phosphate Sodium solution mixes, and it is 10.0 to control the pH value of mixed system with the ammonia spirit that mass fraction is 25%, controls incorporation time It is 2 hours, obtains suspension, by filtering, is precipitated.The precipitation is washed with deionized to remove impurity therein, Then at 110 DEG C by spray drying obtain alkali formula molybdenum phosphate (normalization formula be Mo (OH)0.75(PO4)0.75) powder, survey It is 220nm to obtain wherein particle diameter D50.
(normalization formula is Mn (OH) (CO to basic carbonate manganese3)0.50) preparation method include：By the 50 weight % of 3580g The Mn nitrate aqueous solution is diluted with 20000g deionized waters, and Mn nitrate solution is obtained.By 400g NaOH, 530g sodium carbonate 20000g deionized water dissolvings are used, NaOH, sodium carbonate mixture is obtained.Under nitrogen protection, at room temperature, 220rpm Under conditions of strong stirring, Mn nitrate solution is mixed with NaOH, sodium carbonate mixture, it is 2 to control incorporation time Hour, suspension is obtained, by filtering, it is precipitated.Under nitrogen protection, the precipitation is washed with deionized to remove it In impurity, then at 110 DEG C by spray drying obtain basic carbonate manganese (normalization formula be Mn (OH) (CO3)0.50) powder End, measures wherein particle diameter D50 for 360nm.
(normalization formula is Fe (OH) to alkali formula ferric phosphate0.60(PO4)0.80·0.40H2O preparation method) includes：Will 984g tertiary sodium phosphates 20000g deionized water dissolvings, obtain trisodium phosphate solution.The water ferric nitrates of 4040g nine are gone with 15000g Ion water dissolves, are obtained iron nitrate solution.At room temperature, under conditions of 270rpm strong stirrings, by iron nitrate solution and phosphoric acid Three sodium solutions mix, and it is 10.0 to control the pH value of mixed system with the sodium hydroxide solution of 2 moles of every liter of concentration, control mixing Time is 2 hours, obtains suspension, and suspension is transferred into hydrothermal reaction kettle, and 200 DEG C are kept for 8 hours, by filtering, are obtained Precipitation.The precipitation is washed with deionized to remove impurity therein, alkali formula is then obtained by spray drying at 110 DEG C (normalization formula is Fe (OH) to ferric phosphate0.60(PO4)0.80·0.40H2O) powder, measures wherein particle diameter D50 for 250nm.
(normalization formula is Co (OH) to basic cobaltous carbonate1.20(CO3)0.40·0.20H2O preparation method) includes：Will The water colbaltous nitrate 15000g deionized water dissolvings of 2910g six, are obtained colbaltous nitrate solution.By 480g NaOH, 424g carbon Sour sodium 10000g deionized water dissolvings, obtain NaOH, sodium carbonate mixture.Under nitrogen protection, at room temperature, Under conditions of 290rpm strong stirrings, colbaltous nitrate solution is mixed with NaOH, sodium carbonate mixture, during control mixing Between be 2 hours, obtain suspension, by filtering, be precipitated.Under nitrogen protection, by the precipitation be washed with deionized with Remove impurity therein, then at 110 DEG C by spray drying obtain basic cobaltous carbonate (normalization formula be Co (OH)1.20 (CO3)0.40·0.20H2O) powder, measures wherein particle diameter D50 for 320nm.
(normalization formula is Al (OH) (OCOCH to eston3)2) preparation method include：820g sodium metaaluminates are used 20000g deionized water dissolvings, are obtained sodium aluminate solution.By 1320g glacial acetic acid 10000g deionized water dissolvings, vinegar is obtained Acid solution.At room temperature, under conditions of 340rpm strong stirrings, acetum is mixed with sodium aluminate solution, control mixing Time is 2 hours, obtains suspension, and the suspension is heated into boiling, and is kept for 2 hours, by filtering, is precipitated.Will The precipitation is washed with deionized to remove impurity therein, then obtains eston by spray drying at 105 DEG C (normalization formula is Al (OH) (OCOCH3)2) powder, wherein particle diameter D50 is measured for 190nm.
(normalization formula is Sn (OH) (CO to basic carbonate tin3)0.50) preparation method include：By the water dichlorides of 2257g bis- Tin is dissolved in 20000g absolute ethyl alcohols, obtains clarifying stannous chloride solution.520g NaOH, 689g sodium carbonate are used 20000g deionized water dissolvings, obtain NaOH, tertiary sodium phosphate mixed solution.At room temperature, the bar of 310rpm strong stirrings Under part, during stannous chloride solution is added into NaOH, tertiary sodium phosphate mixed solution, control incorporation time for 2 hours, hanged Supernatant liquid, by filtering, is precipitated.The precipitation is washed with deionized to remove impurity therein, then led at 110 DEG C Cross spray drying obtain basic carbonate tin (normalization formula be Sn (OH) (CO3)0.50) powder, measuring wherein particle diameter D50 is 130nm。
(normalization formula is Bi (PO to alkali formula bismuth phosphate4)0.84(OH)0.48) preparation method include：By the water nitre of 4850g five Sour bismuth dissolves in adding the 20000g diluted nitric acid aqueous solutions that mass fraction is 2%, and bismuth nitrate solution is obtained.By 520g hydroxides Sodium, 1722g tertiary sodium phosphates 20000g deionized water dissolvings, obtain NaOH, tertiary sodium phosphate mixed solution.At room temperature, Under conditions of 310rpm strong stirrings, during bismuth nitrate solution is added into NaOH, tertiary sodium phosphate mixed solution, during control mixing Between be 2 hours, obtain suspension, by filtering, be precipitated.The precipitation is washed with deionized therein miscellaneous to remove Matter, then at 105 DEG C by spray drying obtain alkali formula bismuth phosphate (normalization formula be Bi (PO4)0.84(OH)0.48) powder, Wherein particle diameter D50 is measured for 190nm.
(normalization formula is Sb (OH) to basic carbonate antimony1.40(CO3)0.80) preparation method include：Under agitation, 2280g trichloride antimonies are dissolved in 25000g absolute ethyl alcohols, trichloride antimony solution is obtained.By 1060g sodium carbonate, 680g mass Fraction is 25% ammoniacal liquor 20000g deionized water dissolvings, obtains sodium carbonate, ammoniacal liquor mixed solution.At room temperature, 390rpm Under conditions of strong stirring, by trichloride antimony solution addition sodium carbonate, ammoniacal liquor mixed solution, feed time is controlled for 2 hours, Suspension is obtained, by filtering, is precipitated.The precipitation is washed with deionized to remove impurity therein, then 110 At DEG C by spray drying obtain basic carbonate antimony (normalization formula be Sb (OH)1.40(CO3)0.80) powder, measure wherein particle diameter D50 is 210nm.
Embodiment 1
(1) prepared by battery positive pole piece
By 21500g lithium nickel cobalt manganese oxygens LiNi0.5Co0.2Mn0.3O2Positive electrode, 600g binding agents HSV900,900g are conductive (normalization formula is Mg (OH) to agent Super-P and 1946g basic magnesium carbonate0.40(CO3)0.80·H2O) powder additive mixing, Specific method is：First with 25000g NMP as solvent, by binding agent HSV900 dissolvings, and under agitation respectively by lithium nickel cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2(normalization formula is Mg (OH) for positive electrode, conductive agent Super-P, basic magnesium carbonate0.40 (CO3)0.80·H2O) powder additive mixes with the solution of above-mentioned binding agent, and stirring afterwards forms uniform anode sizing agent；
The anode sizing agent is coated uniformly on the aluminium foil that thickness is 25 μm, coating width is 160mm, the two-sided face of dressing is close It is 338.6g/m to spend2(the two-sided surface density of dressing similarly hereinafter, and on the basis of the dry weight of electrode dressing, adds in terms of the weight after drying Plus the content of agent is 7.8 weight %), then dried at 110 DEG C, obtain anode pole piece.
(2) prepared by negative pole piece of battery
By 12285g natural graphite negative electrode materials, 155g thickener CMC, 170g conductive agent Super-P and 780g butylbenzene rubbers Latex glue caking agent mixes, and specific method is：First with 12500g deionized waters as solvent, by thickener CMC dissolvings, and in stirring It is lower respectively to mix butadiene-styrene rubber emulsion binder, conductive agent Super-P, natural graphite negative electrode material and the solution of above-mentioned thickener 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 164mm, the two-sided face of dressing is close It is 164.1g/m to spend2(in terms of the weight after drying, similarly hereinafter), then dried 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, with polypropylene screen as barrier film, is assembled into battery core component as negative pole, is put into 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, by adjusting, Positive electrode active material lithium-nickel-cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2Weight be about 191g, the weight of negative electrode active material native graphite Amount is about 104g, and the nominal capacity of battery is 30Ah.Then by LiPF6EC/DMC=1 is dissolved in by the concentration of 1 mol/L:1 Nonaqueous electrolytic solution is formed in the mixed solvent of (volume ratio), this electrolyte injects above-mentioned battery by 160g under nitrogen atmosphere protection In semi-finished 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 4.00V, then secondary ageing 48 hours under conditions of 45 DEG C, the gas that will finally be produced in battery under nitrogen atmosphere protection are taken out Go out and by battery secondary sealing, obtain lithium ion battery A1.
Embodiment 2
Method according to embodiment 1 prepares lithium ion battery A2, unlike, in step (1), the system of battery positive pole piece Preparation Method is as follows：
By 21500g lithium nickel cobalt aluminas LiNi0.8Co0.15Al0.05O2Positive electrode, 1072g PTFE emulsion binding agents D210, 857g conductive agents acetylene black mixes, and specific method is：First with 25000g water as solvent, by PTFE emulsion binding agent D210 dispersions, Emulsion is obtained, and under agitation respectively by lithium nickel cobalt alumina LiNi0.8Co0.15Al0.05O2Positive electrode, conductive agent acetylene black with it is upper The emulsion mixing of binding agent is stated, stirring afterwards forms uniform slurry；
The slurry is coated uniformly on the aluminium foil that thickness is 25 μm, coating width is 160mm, the two-sided surface density of dressing is 312.2g/m2(in terms of the weight after drying), then dries at 100 DEG C, obtains anode pole piece；
By 1000g basic copper acetates, (normalization formula is Cu (OH)1.50(OCOCH3)0.50·0.50H2O) powder addition Agent, 70g PTFE emulsion binding agents D210 mix, and specific method is：First with 2500g water as solvent, by PTFE emulsion binding agent D210 disperses, and obtains emulsion, and under agitation mix powder additive with the emulsion of above-mentioned binding agent, and stirring afterwards is formed Even additive slurry；
The additive slurry is coated uniformly on above-mentioned anode pole piece surface, coating width is 162mm, to cover activity Material, the two-sided surface density of dressing is 27.6g/m2(on the basis of the dry weight of electrode dressing, the weight % of content 7.8 of additive), Then dried at 100 DEG C, obtain to surface and be coated with the anode pole piece of additive.
Embodiment 3
Method according to embodiment 1 prepares lithium ion battery A3, unlike, in step (1), the system of battery positive pole piece Preparation Method is as follows：
By 1000g basic nickel carbonates, (normalization formula is Ni (OH)4/3(CO3)1/3·4/3H2O) powder additive, 45g lead Electric agent Super-P, 45g binding agent HSV900 mixes, and specific method is：First with 2500g NMP as solvent, by binding agent HSV900 Dissolving, and powder additive, conductive agent Super-P mix with the solution of above-mentioned binding agent under agitation, stirring formation afterwards Uniform additive slurry；
The additive slurry is coated uniformly on the aluminium foil that thickness is 25 μm, coating width is 162mm, the two-sided face of dressing Density is 29.0g/m2(in terms of the weight after drying), then dries at 120 DEG C, obtains the aluminium foil of additive coating；
By 21500g cobalt acid lithiums LiCoO2Positive electrode, the mixing of 600g binding agent HSV900,900g conductive agents CNT, Specific method is：First with 25000g NMP as solvent, by binding agent HSV900 dissolvings, and under agitation respectively by cobalt acid lithium LiCoO2Positive electrode, conductive agent CNT mix with the solution of above-mentioned binding agent, and stirring afterwards forms uniform active matter Chylema material；
The active material slurry is coated uniformly on the aluminium foil surface of additive coating, coating width is 160mm, and dressing is double Face surface density is 312.2g/m2(on the basis of the dry weight of electrode dressing, the content of additive is 7.8 weight %), then 120 Dried at DEG C, obtain the anode pole piece that aluminium foil is coated by additive.
Embodiment 4
(1) prepared by battery positive pole piece
By 21500g lithium nickel cobalt manganese oxygens LiNi0.5Co0.2Mn0.3O2Positive electrode, 600g binding agents HSV900,900g are conductive Agent Super-P mixes, and specific method is：First with 25000g NMP as solvent, by binding agent HSV900 dissolvings, and divide under agitation Not by lithium nickel cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, conductive agent Super-P mix with the solution of above-mentioned binding agent, it Stirring afterwards forms uniform anode sizing agent；
The anode sizing agent is coated uniformly on the aluminium foil that thickness is 25 μm, coating width is 160mm, the two-sided face of dressing is close It is 312.2g/m to spend2(in terms of the weight after drying), then dries at 110 DEG C, obtains anode pole piece.
(2) prepared by negative pole piece of battery
By 11327g natural graphite negative electrode materials, 143g thickener CMC, 157g conductive agent Super-P, 719g butadiene-styrene rubber (normalization formula is Mg (OH) for emulsion binder and 1014g basic magnesium carbonates0.40(CO3)0.80·H2O) powder additive mixing, Specific method is：First with 13500g deionized waters as solvent, by thickener CMC dissolvings, and under agitation respectively by butadiene-styrene rubber Emulsion binder, conductive agent Super-P, natural graphite negative electrode material, powder additive mix with the solution of above-mentioned thickener, it Stirring afterwards forms uniform cathode size；
The cathode size is coated uniformly on the Copper Foil that thickness is 18 μm, coating width is 164mm, the two-sided face of dressing is close It is 178.0g/m to spend2(on the basis of the dry weight of electrode dressing, the content of additive is 7.8 weight %), then dries at 100 DEG C It is dry, 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, with polypropylene screen as barrier film, is assembled into battery core component as negative pole, is put into 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, by adjusting, Positive electrode active material lithium-nickel-cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2Weight be about 191g, the weight of negative electrode active material native graphite Amount is about 104g, and the nominal capacity of battery is 30Ah.Then by LiPF6EC/DMC=1 is dissolved in by the concentration of 1 mol/L:1 Nonaqueous electrolytic solution is formed in the mixed solvent of (volume ratio), this electrolyte injects above-mentioned battery by 160g under nitrogen atmosphere protection In semi-finished 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 4.00V, then secondary ageing 48 hours under conditions of 45 DEG C, the gas that will finally be produced in battery under nitrogen atmosphere protection are taken out Go out and by battery secondary sealing, obtain lithium ion battery A4.
Embodiment 5
Method according to embodiment 1 prepares lithium ion battery A5, unlike, in step (1), by 21500g lithium nickel cobalt manganeses Oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, 600g binding agent HSV900,900g conductive agent Super-P and 1494g basic carbonates (normalization formula is Mg (OH) to magnesium0.40(CO3)0.80·H2O) powder additive mixes, and specific method is：First with 25000g NMP It is solvent, by binding agent HSV900 dissolvings, and under agitation respectively by lithium nickel cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, Conductive agent Super-P, powder additive mix with the solution of above-mentioned binding agent, and stirring afterwards forms uniform anode sizing agent；
The anode sizing agent is coated uniformly on the aluminium foil that thickness is 25 μm, coating width is 160mm, the two-sided face of dressing is close It is 332.4g/m to spend2(on the basis of the dry weight of electrode dressing, the content of additive is 6.1 weight %), then dries at 110 DEG C It is dry, obtain anode pole piece.
Embodiment 6
Method according to embodiment 1 prepares lithium ion battery A6, unlike, in step (1), by 21500g lithium nickel cobalt manganeses Oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, 600g binding agent HSV900,900g conductive agent Super-P and 2414g basic carbonates (normalization formula is Mg (OH) to magnesium0.40(CO3)0.80·H2O) powder additive mixes, and specific method is：First with 25000g NMP It is solvent, by binding agent HSV900 dissolvings, and under agitation respectively by lithium nickel cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, Conductive agent Super-P, powder additive mix with the solution of above-mentioned binding agent, and stirring afterwards forms uniform anode sizing agent；
The anode sizing agent is coated uniformly on the aluminium foil that thickness is 25 μm, coating width is 160mm, the two-sided face of dressing is close It is 344.9g/m to spend2(on the basis of the dry weight of electrode dressing, the content of additive is 9.5 weight %), then dries at 110 DEG C It is dry, obtain anode pole piece.
Embodiment 7
Method according to embodiment 2 prepares lithium ion battery A7, unlike, in step (1), the preparation of additive slurry Method is：First with 1500g water as solvent, by 50g PTFE emulsion binding agents D210 dispersions, emulsion is obtained, and under agitation will (normalization formula is Cu (OH) to 1000g basic copper acetates1.50(OCOCH3)0.50·0.50H2O) the breast of powder and above-mentioned binding agent Liquid mixes, and stirring afterwards forms uniform additive slurry.
The additive slurry is coated uniformly on above-mentioned anode pole piece surface, coating width is 162mm, to cover activity Material, the two-sided surface density of dressing is 20.9g/m2(on the basis of the dry weight of electrode dressing, the content of additive is 6.1 weights Amount %), then dried at 100 DEG C, obtain to surface and be coated with the anode pole piece of additive.
Embodiment 8
Method according to embodiment 2 prepares lithium ion battery A8, unlike, in step (1), the preparation of additive slurry Method is：First with 3500g water as solvent, by 130gPTFE emulsion binders D210 dispersions, emulsion is obtained, and under agitation will (normalization formula is Cu (OH) to 1000g basic copper acetates1.50(OCOCH3)0.50·0.50H2O) the breast of powder and above-mentioned binding agent Liquid mixes, and stirring afterwards forms uniform additive slurry.
The additive slurry is coated uniformly on above-mentioned anode pole piece surface, coating width is 162mm, to cover activity Material, the two-sided surface density of dressing is 35.6g/m2(on the basis of the dry weight of electrode dressing, the content of additive is 9.5 weights Amount %), then dried at 100 DEG C, obtain to surface and be coated with the anode pole piece of additive.
Embodiment 9
Method according to embodiment 1 prepares lithium ion battery A9, unlike, in step (1), by 21500g lithium nickel cobalt manganeses Oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, 600g binding agent HSV900,900g conductive agent Super-P and 760g basic magnesium carbonates (normalization formula is Mg (OH)0.40(CO3)0.80·H2O) powder additive mixes, and specific method is：It is with 25000g NMP first Solvent, by binding agent HSV900 dissolvings, and under agitation respectively by lithium nickel cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, lead Electric agent Super-P, additive mix with the solution of above-mentioned binding agent, and stirring afterwards forms uniform anode sizing agent；
The anode sizing agent is coated uniformly on the aluminium foil that thickness is 25 μm, coating width is 160mm, the two-sided face of dressing is close It is 322.5g/m to spend2(on the basis of the dry weight of electrode dressing, the content of additive is 3.2 amount %), then dries at 110 DEG C It is dry, obtain anode pole piece.
Embodiment 10
Method according to embodiment 1 prepares lithium ion battery A10, unlike, in step (1), by 21500g lithium nickel cobalts Manganese oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, 600g binding agent HSV900,900g conductive agent Super-P and 209g basic carbonates (normalization formula is Mg (OH) to magnesium0.40(CO3)0.80·H2O) powder additive mixes, and specific method is：First with 25000g NMP It is solvent, by binding agent HSV900 dissolvings, and under agitation respectively by lithium nickel cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, Conductive agent Super-P, additive mix with the solution of above-mentioned binding agent, and stirring afterwards forms uniform anode sizing agent；
The anode sizing agent is coated uniformly on the aluminium foil that thickness is 25 μm, coating width is 160mm, the two-sided face of dressing is close It is 315.0g/m to spend2(on the basis of the dry weight of electrode dressing, the content of additive is 0.9 amount %), then dries at 110 DEG C It is dry, obtain anode pole piece.
Embodiment 11
Method according to embodiment 1 prepares lithium ion battery A11, unlike, in step (1), by 21500g lithium nickel cobalts Manganese oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, 600g binding agent HSV900,900g conductive agent Super-P and 3744g alkali formula carbon (normalization formula is Mg (OH) to sour magnesium0.40(CO3)0.80·H2O) powder additive mixes, and specific method is：First with 25000g NMP is solvent, by binding agent HSV900 dissolvings, and under agitation respectively by lithium nickel cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2Positive pole material Material, conductive agent Super-P, additive mix with the solution of above-mentioned binding agent, and stirring afterwards forms uniform anode sizing agent；
The anode sizing agent is coated uniformly on the aluminium foil that thickness is 25 μm, coating width is 160mm, the two-sided face of dressing is close It is 388.4g/m to spend2(on the basis of the dry weight of electrode dressing, the content of additive is 14.0 amount %), then dries at 110 DEG C It is dry, obtain anode pole piece.
Embodiment 12
Method according to embodiment 1 prepares lithium ion battery A12, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with alkali calcium phosphate (normalization formula be Ca (PO4)0.60 (OH)0.20) powder.
Embodiment 13
Method according to embodiment 1 prepares lithium ion battery A13, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with alkali formula strontium phosphate (normalization formula be Sr (PO4)0.60 (OH)0.20)。
Embodiment 14
Method according to embodiment 1 prepares lithium ion battery A14, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with basic zinc carbonate (normalization formula be Zn (OH)4/3 (CO3)1/3·1/3H2O)。
Embodiment 15
Method according to embodiment 1 prepares lithium ion battery A15, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with basic yttrium carbonate (normalization formula be Y (OH) (CO3))。
Embodiment 16
Method according to embodiment 1 prepares lithium ion battery A16, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with basic carbonate scandium (normalization formula be Sc (OH) (CO3)) Powder.
Embodiment 17
Method according to embodiment 1 prepares lithium ion battery A17, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with basic carbonate lanthanum (normalization formula be La (OH) (CO3)) Powder.
Embodiment 18
Method according to embodiment 1 prepares lithium ion battery A18, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with basic carbonate cerium (normalization formula be Ce (OH) (CO3))。
Embodiment 19
Method according to embodiment 1 prepares lithium ion battery A19, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with neodymium hydroxyl-carbonate (normalization formula be Nd (OH) (CO3)) Powder.
Embodiment 20
Method according to embodiment 1 prepares lithium ion battery A20, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with basic carbonate samarium (normalization formula be Sm (OH) (CO3)) Powder.
Embodiment 21
Method according to embodiment 1 prepares lithium ion battery A21, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with basic carbonate gadolinium (normalization formula be Gd (OH) (CO3)) Powder.
Embodiment 22
Method according to embodiment 1 prepares lithium ion battery A22, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with basic carbonate erbium (normalization formula be Er (OH) (CO3)) Powder.
Embodiment 23
Method according to embodiment 1 prepares lithium ion battery A23, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with alkali formula titanium phosphate (normalization formula be Ti (OH)1.66 (PO4)0.78) powder.
Embodiment 24
Method according to embodiment 1 prepares lithium ion battery A24, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with alkali formula phosphoric acid zirconium carbonate (normalization formula be Zr (OH)1.45 (PO4)0.60(CO3)0.375) powder.
Embodiment 25
Method according to embodiment 1 prepares lithium ion battery A25, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with alkali formula vanadium phosphate (normalization formula be V (OH)1.62 (PO4)0.46) powder.
Embodiment 26
Method according to embodiment 1 prepares lithium ion battery A26, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with alkali formula niobium phosphate (normalization formula be Nb (OH)1.22 (PO4)1.26) powder.
Embodiment 27
Method according to embodiment 1 prepares lithium ion battery A27, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with alkali formula chromium phosphate (normalization formula be Cr (OH)0.90 (PO4)0.70) powder.
Embodiment 28
Method according to embodiment 1 prepares lithium ion battery A28, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with alkali formula molybdenum phosphate (normalization formula be Mo (OH)0.75 (PO4)0.75) powder.
Embodiment 29
Method according to embodiment 1 prepares lithium ion battery A29, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with basic carbonate manganese (normalization formula be Mn (OH) (CO3)0.50) powder.
Embodiment 30
Method according to embodiment 1 prepares lithium ion battery A30, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with alkali formula ferric phosphate (normalization formula be Fe (OH)0.60 (PO4)0.80·0.40H2O) powder.
Embodiment 31
Method according to embodiment 1 prepares lithium ion battery A31, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with basic cobaltous carbonate (normalization formula be Co (OH)1.20 (CO3)0.40·0.20H2O) powder.
Embodiment 32
Method according to embodiment 1 prepares lithium ion battery A32, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with eston (normalization formula be Al (OH) (OCOCH3)2) powder.
Embodiment 33
Method according to embodiment 1 prepares lithium ion battery A33, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with basic carbonate tin (normalization formula be Sn (OH) (CO3)0.50) powder.
Embodiment 34
Method according to embodiment 1 prepares lithium ion battery A34, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with alkali formula bismuth phosphate (normalization formula be Bi (PO4)0.84 (OH)0.48) powder.
Embodiment 35
Method according to embodiment 1 prepares lithium ion battery A35, unlike, in step (1), basic magnesium carbonate (is returned One changes formula for Mg (OH)0.40(CO3)0.80·H2O) powder replace with basic carbonate antimony (normalization formula be Sb (OH)1.40 (CO3)0.80) powder.
Comparative example 1
Method according to embodiment 1 prepares lithium ion battery D1, unlike, in step (1), it is not added with basic magnesium carbonate (normalization formula is Mg (OH)0.40(CO3)0.80·H2O) powder additive, obtains anode active material slurry, and the positive pole is lived Property compound paste is coated uniformly on the aluminium foil that thickness is 25 μm, and coating width is 160mm, and the two-sided surface density of dressing is 312.2g/m2(in terms of the weight after drying), then dries at 110 DEG C, obtains anode pole piece.
Comparative example 2
Method according to embodiment 2 prepares lithium ion battery D2, unlike, in step (1), obtain anode pole piece it Afterwards, basic copper acetate is not added when additive slurry is prepared, and (normalization formula is Cu (OH)1.50(OCOCH3)0.50· 0.50H2O) powder additive, specifically, first with 2500g water as solvent, PTFE emulsion binding agent D210 dispersions is bonded The emulsion of agent, above-mentioned anode pole piece surface is coated uniformly on by the emulsion, and coating width is 162mm, to cover active material, The two-sided surface density of dressing is 27.6g/m2(in terms of the weight after drying), then dries at 100 DEG C.
Comparative example 3
Method according to embodiment 3 prepares lithium ion battery D3, unlike, in step (1), preparing additive slurry When does not add basic nickel carbonate, and (normalization formula is Ni (OH)4/3(CO3)1/3·4/3H2O) powder additive, will 45g conductions Agent Super-P, 45g binding agent HSV900 mixes, specifically, first with 2500g NMP as solvent, by binding agent HSV900 dissolvings, The solution of binding agent is obtained, then mixes conductive agent Super-P with the solution of above-mentioned binding agent, stirring afterwards forms uniform Slurry；
Above-mentioned slurry is coated uniformly on the aluminium foil that thickness is 25 μm, coating width is 162mm, the dressing for obtaining is two-sided Surface density is 29.0g/m2(in terms of the weight after drying), then dries at 120 DEG C, obtains treated aluminium foil；
By 21500g cobalt acid lithiums LiCoO2Positive electrode, the mixing of 600g binding agent HSV900,900g conductive agents CNT, Specific method is：First with 25000g NMP as solvent, by binding agent HSV900 dissolvings, and under agitation respectively by cobalt acid lithium LiCoO2Positive electrode, conductive agent CNT mix with the solution of above-mentioned binding agent, and stirring afterwards forms uniform active matter Chylema material；
The active material slurry is coated uniformly on treated aluminium foil surface, coating width is 160mm, the two-sided face of dressing Density is 312.2g/m2(in terms of the weight after drying), then dries at 120 DEG C, obtains the treated anode pole piece of aluminium foil.
Test example
The abuse test of cell
1st, test is overcharged
By cell (including lithium ion battery A1-A35 obtained in embodiment 1-35 and lithium obtained in comparative example 1-3 Ion battery D1-D3) 8.5V is charged to the electric current of 30A, and constant pressure is kept for 1 hour under the voltage of 8.5V, 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-A35 obtained in embodiment 1-35 and lithium obtained in comparative example 1-3 Ion battery D1-D3) 4.25V is charged to the electric current of 30A, and under the voltage of 4.25V constant-voltage charge until electric current is less than 1.5A.Battery is extruded from perpendicular to battery pole piece direction with the end face of the semicylinder that two pieces of radiuses are 75mm, extrusion speed is 5mm/s, until cell deformation amount reaches 30%, stops one hour after the completion of extruding, observes and the phenomenon in 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-A35 obtained in embodiment 1-35 and lithium obtained in comparative example 1-3 Ion battery D1-D3) 4.25V is charged to the electric current of 30A, and under the voltage of 4.25V constant-voltage charge until electric current is less than 1.5A.Battery is extruded from perpendicular to battery pole piece direction with the end face of the semicylinder that two pieces of radiuses are 75mm, extrusion speed is 5mm/s, until cell deformation amount reaches 50%, stops one hour after the completion of extruding, observes and the phenomenon in 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-A35 obtained in embodiment 1-35 and lithium obtained in comparative example 1-3 Ion battery D1-D3) 4.25V is charged to the electric current of 30A, and under the voltage of 4.25V constant-voltage charge until electric current is less than 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, observe and the phenomenon in 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 are compared and is understood, the present invention is introduced when negative or positive electrode is prepared Additive, the security of the lithium ion battery for thus preparing can be significantly improved.
The results contrast of embodiment 1 in table 1-4 and embodiment 9-11 is understood, in negative or positive electrode, with electrode dressing Dry weight on the basis of, when the content of additive is 5.5-10 weight %, can further improve the lithium ion for thus preparing The security of battery, and the lithium ion battery for preparing can also be further improved when additive amount further increases and is existed Security under extremely harsh condition.
The results contrast of embodiment 1-4 in table 1-4 and embodiment 12-35 is understood, the additive is basic magnesium carbonate (normalization formula is Mg (OH)0.40(CO3)0.80·H2O), (normalization formula is Cu (OH) to basic copper acetate1.50 (OCOCH3)0.50·0.50H2O) and basic nickel carbonate (normalization formula be Ni (OH)4/3(CO3)1/3·4/3H2O in) at least When a kind of, the security of the lithium ion battery for preparing can be further improved.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this A little simple variants 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 it is various can The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims (10)

1. application of a kind of additive in lithium ion cell positive and/or negative pole is prepared, it is characterised in that the additive is M(OH)a(PO4)b(CO3)c(OCOCH3)d·eH2O, wherein, M is Group IIA metal element, IB races metallic element, Group IIB metal unit Element, IIIB races metallic element, Group IVB metallic element, VB races metallic element, group vib metallic element, VIIB races metallic element, At least one element in group VIII metal element, Group IIIA metallic element, IVA races metallic element and VA races metallic element, a> 0, b >=0, c >=0, d >=0, and be 0, e >=0 when b, c, d difference.
2. application according to claim 1, wherein, in the additive, the Group IIA metal element is Mg, Ca and Sr In at least one, IB races metallic element is Cu, and the Group IIB metal element is Zn, and IIIB races 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 races metal Element is V and/or Nb, and the group vib metallic element is Cr and/or Mo, and VIIB races metallic element is Mn, the VIII Metallic element is at least one in Fe, Co and Ni, and the Group IIIA metallic element is Al, and IVA races metallic element is Sn, VA races metallic element is Bi and/or Sb；
Preferably, the additive is at least one in basic magnesium carbonate, basic copper acetate and basic nickel carbonate；
It is further preferred that the additive is Mg (OH)0.40(CO3)0.80·H2O、Cu(OH)1.50(OCOCH3)0.50· 0.50H2O and Ni (OH)4/3(CO3)1/3·4/3H2At least one in O.
3. application according to claim 1 and 2, wherein, in negative or positive electrode, on the basis of the dry weight of electrode dressing, The content of the additive is 0.05-23 weight %, more preferably preferably 3-16 weight %, 5.5-10 weight %.
4. a kind of lithium ion battery electrode sizing agent, it is characterised in that the electrode slurry includes active material, binding agent, conduction Agent, additive, solvent and optional thickener, on the basis of the weight of the active material, the content of the additive is 0.05-31 weight %, preferably 2-20 weight %, more preferably 7-13 weight %；The additive is M (OH)a(PO4)b (CO3)c(OCOCH3)d·eH2O, wherein, M is Group IIA metal element, IB races metallic element, Group IIB metal element, IIIB races gold Category element, Group IVB metallic element, VB races metallic element, group vib metallic element, VIIB races metallic element, group VIII metal unit At least one element in element, Group IIIA metallic element, IVA races metallic element and VA races metallic element, a>0, b >=0, c >=0, d >=0, and be 0, e >=0 when b, c, d difference；
Preferably, on the basis of the weight of the active material, the binding agent with the content that butt is counted be 0.5-5 weight %, The content of the conductive agent is 0.5-5 weight %, and the content of the solvent is 50-230 weight %, and the content of the thickener is 0-3 weight %；
Preferably, in additive, the Group IIA metal element is at least one in Mg, Ca and Sr, IB races metallic element Be Cu, the Group IIB metal element be Zn, IIIB races metallic element be Y, Sc, La, Ce, Nd, Sm, Gd and Er in extremely Few one kind, the Group IVB metallic element is Ti and/or Zr, and VB races metallic element is V and/or Nb, the group vib metal Element be Cr and/or Mo, VIIB races metallic element be Mn, the group VIII metal element be Fe, Co and Ni at least One kind, the Group IIIA metallic element be Al, IVA races metallic element be Sn, VA races metallic element be Bi and/or Sb；It is further preferred that the additive is at least one in basic magnesium carbonate, basic copper acetate and basic nickel carbonate；More It is further preferred that the additive is Mg (OH)0.40(CO3)0.80·H2O、Cu(OH)1.50(OCOCH3)0.50·0.50H2O and Ni(OH)4/3(CO3)1/3·4/3H2At least one in O；
Preferably, the active material be positive active material or negative electrode active material, the positive active material be 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, manganese phosphate In lithium, iron manganese phosphate for lithium, iron manganese phosphate nickel lithium, iron manganese phosphate cobalt lithium, iron manganese phosphate nickel cobalt lithium, phosphoric acid vanadium lithium and ferric metasilicate lithium At least one, the negative electrode active material is at least one in graphite, lithium titanate, silicon, hard carbon, tin and tin oxide；
Preferably, the binding agent be polyacrylamide, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), butadiene-styrene rubber, cellulose base gather At least one in compound, polyvinyl alcohol, polyolefin, Viton and Polyurethane；
Preferably, the conductive agent is Ketjen black, acetylene black, Graphene, CNT, carbon fiber, micro crystal graphite and conductive carbon At least one in black；
Preferably, the solvent is 1-METHYLPYRROLIDONE, deionized water, tetrahydrofuran, dimethyl sulfoxide (DMSO), ethanol and isopropanol In at least one；
The thickener is at least one in sodium carboxymethylcellulose, polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol.
5. a kind of additive slurry, it is characterised in that the additive slurry includes binding agent, additive, solvent and optional Conductive agent, on the basis of the weight of the additive, the binding agent with the content that butt is counted be 0.5-13 weight %, it is described molten The content of agent is 85-430 weight %, and the content of the conductive agent is 0-11 weight %；The additive is M (OH)a(PO4)b (CO3)c(OCOCH3)d·eH2O, wherein, M is Group IIA metal element, IB races metallic element, Group IIB metal element, IIIB races gold Category element, Group IVB metallic element, VB races metallic element, group vib metallic element, VIIB races metallic element, group VIII metal unit At least one element in element, Group IIIA metallic element, IVA races metallic element and VA races metallic element, a>0, b >=0, c >=0, d >=0, and be 0, e >=0 when b, c, d difference；
Preferably, in additive, the Group IIA metal element is at least one in Mg, Ca and Sr, IB races metallic element Be Cu, the Group IIB metal element be Zn, IIIB races metallic element be Y, Sc, La, Ce, Nd, Sm, Gd and Er in extremely Few one kind, the Group IVB metallic element is Ti and/or Zr, and VB races metallic element is V and/or Nb, the group vib metal Element be Cr and/or Mo, VIIB races metallic element be Mn, the group VIII metal element be Fe, Co and Ni at least One kind, the Group IIIA metallic element be Al, IVA races metallic element be Sn, VA races metallic element be Bi and/or Sb；It is further preferred that the additive is at least one in basic magnesium carbonate, basic copper acetate and basic nickel carbonate；More It is further preferred that the additive is Mg (OH)0.40(CO3)0.80·H2O、Cu(OH)1.50(OCOCH3)0.50·0.50H2O and Ni(OH)4/3(CO3)1/3·4/3H2At least one in O；
Preferably, the binding agent be polyacrylamide, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), butadiene-styrene rubber, cellulose base gather At least one in compound, polyvinyl alcohol, polyolefin, Viton and Polyurethane；
Preferably, the solvent is 1-METHYLPYRROLIDONE, deionized water, tetrahydrofuran, dimethyl sulfoxide (DMSO), ethanol and isopropanol In at least one；
Preferably, the conductive agent is Ketjen black, acetylene black, Graphene, CNT, carbon fiber, micro crystal graphite and conductive carbon At least one in black.
6. 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 active material, binding agent, conductive agent, additive and optionally Thickener, the additive be M (OH)a(PO4)b(CO3)c(OCOCH3)d·eH2O, wherein, M is Group IIA metal element, IB Race's metallic element, Group IIB metal element, IIIB races metallic element, Group IVB metallic element, VB races metallic element, group vib metal Element, VIIB races metallic element, group VIII metal element, Group IIIA metallic element, IVA races metallic element and VA races metallic element In at least one element, a>0, b >=0, c >=0, d >=0, and be 0, e >=0 when b, c, d difference；
Preferably, in additive, the Group IIA metal element is at least one in Mg, Ca and Sr, IB races metallic element Be Cu, the Group IIB metal element be Zn, IIIB races metallic element be Y, Sc, La, Ce, Nd, Sm, Gd and Er in extremely Few one kind, the Group IVB metallic element is Ti and/or Zr, and VB races metallic element is V and/or Nb, the group vib metal Element be Cr and/or Mo, VIIB races metallic element be Mn, the group VIII metal element be Fe, Co and Ni at least One kind, the Group IIIA metallic element be Al, IVA races metallic element be Sn, VA races metallic element be Bi and/or Sb；It is further preferred that the additive is at least one in basic magnesium carbonate, basic copper acetate and basic nickel carbonate；More It is further preferred that the additive is Mg (OH)0.40(CO3)0.80·H2O、Cu(OH)1.50(OCOCH3)0.50·0.50H2O and Ni(OH)4/3(CO3)1/3·4/3H2At least one in O；
Preferably, the active material be positive active material or negative electrode active material, the positive active material be 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, manganese phosphate In lithium, iron manganese phosphate for lithium, iron manganese phosphate nickel lithium, iron manganese phosphate cobalt lithium, iron manganese phosphate nickel cobalt lithium, phosphoric acid vanadium lithium and ferric metasilicate lithium At least one, the negative electrode active material is at least one in graphite, lithium titanate, silicon, hard carbon, tin and tin oxide；
Preferably, the binding agent be polyacrylamide, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), butadiene-styrene rubber, cellulose base gather At least one in compound, polyvinyl alcohol, polyolefin, Viton and Polyurethane；
Preferably, the conductive agent is Ketjen black, acetylene black, Graphene, CNT, carbon fiber, micro crystal graphite and conductive carbon At least one in black；
Preferably, the thickener be sodium carboxymethylcellulose, polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol in extremely Few one kind.
7. lithium ion cell positive according to claim 6 or negative pole, wherein, on the basis of the dry weight of electrode dressing, institute The content for stating additive is 0.05-23 weight %, more preferably preferably 3-16 weight %, 5.5-10 weight %.
8. a kind of method for preparing lithium ion cell positive or negative pole, it is characterised in that methods described includes：By claim 4 Described lithium ion battery electrode sizing agent coating on a current collector, is dried；Or
(1) by the additive slurry coating described in claim 5 on a current collector, drying obtains the collector of additive coating；
(2) prepare active material slurry, the active material slurry include active material, binding agent, conductive agent, solvent and optionally Thickener, then the active material slurry is coated on the collector of the additive coating that step (1) obtains, drying； Or
(1) prepare active material slurry, the active material slurry include active material, binding agent, conductive agent, solvent and optionally Thickener, then by the active material slurry coating on a current collector, drying, obtain electrode plates；
(2) additive slurry described in claim 5 is coated on the electrode plates that step (1) is obtained, is dried.
9. the method described in claim 8 is prepared lithium ion cell positive or negative pole.
10. a kind of lithium ion battery, it is characterised in that the lithium ion battery includes battery container and in battery container The battery core component and electrolyte in portion, the battery core component include positive pole, negative pole and barrier film, and the just extremely claim 6,7 Or the lithium ion cell positive described in 9, and/or the negative pole is the lithium ion battery negative described in claim 6,7 or 9.
CN201710080769.2A 2017-02-15 2017-02-15 The application of additive, electrode slurry, additive slurry, lithium ion cell positive or negative pole and preparation method thereof and lithium ion battery Pending CN106784850A (en)

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