CN106601991A - Application of additive, electrode slurry, additive slurry, lithium ion battery positive electrode or negative electrode and preparation method therefor, and lithium ion battery - Google Patents

Application of additive, electrode slurry, additive slurry, lithium ion battery positive electrode or negative electrode and preparation method therefor, and lithium ion battery Download PDF

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Publication number
CN106601991A
CN106601991A CN201611260951.8A CN201611260951A CN106601991A CN 106601991 A CN106601991 A CN 106601991A CN 201611260951 A CN201611260951 A CN 201611260951A CN 106601991 A CN106601991 A CN 106601991A
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additive
metallic element
lithium
lithium ion
group
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先雪峰
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Priority to CN201611260951.8A priority Critical patent/CN106601991A/en
Priority to PCT/CN2017/070979 priority patent/WO2018120295A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • 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

Abstract

The invention relates to the technical field of a lithium ion battery, and discloses an application of an additive, electrode slurry, additive slurry, a lithium ion battery positive electrode or negative electrode and a preparation method therefor, and the lithium ion battery. The invention specifically discloses the application of the additive in preparation of the positive electrode and/or negative electrode of the lithium ion battery; the additive is M(PO<4>)<a>(HPO<4>)<b>.cH<2>O, wherein M is at least one kind of elements of IIA group metal element, IB group metal element, IIB group metal element, IIIB group metal element, IVB group metal element, VIB group metal element, VIIB group metal element, VIII group metal element and VA group metal element; a is greater than or equal to 0; b is greater than or equal to 0; and a and b cannot be equal to 0 concurrently, and c is greater than 0. When the additive disclosed by the invention is applied to preparation of the positive electrode and/or negative electrode of the lithium ion battery, the safety of the prepared lithium ion battery can be obviously 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 height, big energy density, life-span length, self discharge The many merits such as little, memory-less effect, operating temperature range width, in small-sized movable energy field (such as mobile phone, digital camera Deng), Large-scale Mobile energy field (such as plug-in hybrid electric vehicle, pure electric vehicle etc.) and (such as energy storage of fixed sources of energy field Power station, UPS etc.), suffer from being widely applied prospect.
Lithium ion battery voltage height also implies that under state-of-charge the positive and negative electrode of battery has larger electric potential difference, Mean that cathodic reduction is higher, positive pole oxidisability is higher, and heat stability is worse.Especially for using cobalt acid lithium, lithium nickel For the battery of the high-voltage anode materials such as cobalt alumina, lithium nickel cobalt manganese oxygen, overcharging, acupuncture, under the abuse condition such as extruding usually Serious potential safety hazard can be there is because thermal runaway causes on fire or even blast.
In addition, with traditional plumbic acid, 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 safety is greatly improved is planted, is had important practical significance.
The content of the invention
The invention aims to overcoming, lithium ion battery security in prior art is low, there is severe compromise A kind of defect, there is provided application, a kind of lithium ion cell electrode slurry 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, the invention provides a kind of additive is preparing lithium ion cell positive And/or the application in negative pole, the additive is M (PO4)a(HPO4)b·cH2O, wherein, M is Group IIA metal element, IB races gold Category element, Group IIB metal element, IIIB races metallic element, Group IVB metallic element, group vib metallic element, metal unit of VIIB races It is 0, c when at least one element in element, group VIII metal element and VA races metallic element, a >=0, b >=0, and a, b are different>0.
Second aspect, the invention provides a kind of lithium ion battery electrode sizing agent, the electrode slurry include active substance, Binding agent, conductive agent, additive, solvent and optional thickening agent, on the basis of the weight of the active substance, the additive Content be 0.05-30 weight %；The additive is M (PO4)a(HPO4)b·cH2O, wherein, M is Group IIA metal element, IB Race's metallic element, Group IIB metal element, IIIB races metallic element, Group IVB metallic element, group vib metallic element, VIIB races gold At least one element in category element, group VIII metal element and VA races metallic element, a >=0, b >=0, and a, b are 0 when different, c>0。
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 0.5-12 Weight %, the content of the solvent is 90-420 weight %, and the content of the conductive agent is 0-12 weight %；The additive is M(PO4)a(HPO4)b·cH2O, wherein, M is Group IIA metal element, IB races metallic element, Group IIB metal element, IIIB races gold Category element, Group IVB metallic element, group vib metallic element, VIIB races metallic element, group VIII metal element and metal unit of VA races It is 0, c when at least one element in element, a >=0, b >=0, and a, b are different>0.
Fourth aspect, the invention provides a kind of lithium ion cell positive or negative pole, the lithium ion cell positive or negative Pole includes collector and the electrode dressing on collector, the electrode dressing contain active substance, binding agent, conductive agent, Additive and optional thickening agent, the additive is M (PO4)a(HPO4)b·cH2O, wherein, M is Group IIA metal element, IB Race's metallic element, Group IIB metal element, IIIB races metallic element, Group IVB metallic element, group vib metallic element, VIIB races gold At least one element in category element, group VIII metal element and VA races metallic element, a >=0, b >=0, and a, b are 0 when different, c>0。
5th aspect, the invention provides a kind of method for preparing lithium ion cell positive or negative pole, methods described includes： Lithium ion battery electrode sizing agent of the present invention is coated on a current collector, drying；Or
(1) additive slurry of the present invention is coated on a current collector, drying obtains the afflux of additive coating Body；
(2) prepare active material slurry, the active material slurry include active substance, binding agent, conductive agent, solvent and Optional thickening agent, is then coated in the active material slurry on the collector of the additive coating that step (1) is obtained, and dries It is dry；Or
(1) prepare active material slurry, the active material slurry include active substance, binding agent, conductive agent, solvent and Optional thickening agent, then coats the active material slurry on a current collector, and 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 the lithium ion cell positive for preparing of the above-mentioned method of the present invention or negative pole.
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 safety 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.Wherein, must be containing could during water of crystallization in additive of the invention Improve the security performance of lithium ion battery, thus it is speculated that its reason is probably, under abuse conditions, contained additive is by inhaling in battery The heat that the mode of water of crystallization absorbs battery generation is released in thermal decomposition, it is to avoid the thermal runaway of battery, so as to improving battery Safety.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that described herein concrete Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
Herein the end points and any value of disclosed scope is not limited to the accurate scope or value, these scopes or Value should be understood to the value comprising close these scopes or value.For numerical range, between the endpoint value of each scope, respectively Between the endpoint value of individual scope and single point value, and individually one or more can be obtained with combination with one another between point value New numerical range, these numerical rangies should be considered concrete open herein.
In a first aspect, the invention provides a kind of application of additive in lithium ion cell positive and/or negative pole is prepared, The additive is M (PO4)a(HPO4)b·cH2O, wherein, M is Group IIA metal element, IB races metallic element, Group IIB metal unit Element, IIIB races metallic element, Group IVB metallic element, group vib metallic element, VIIB races metallic element, group VIII metal element and It is 0, c when at least one element in VA races metallic element, a >=0, b >=0, and a, b are different>0.
Wherein, it will be understood by those skilled in the art that M (PO4)a(HPO4)b·cH2In O, the selection of a, b meets phase Answer the stoichiometric proportion principle of material.
The present invention application in, under preferable case, in additive, the Group IIA metal element be Mg, IB races metal Element is Cu, and the Group IIB metal element is Zn, and IIIB races metallic element is in Y, Sc, La, Ce, Nd, Sm, Gd and Er At least one, the Group IVB metallic element be Ti and/or Zr, the group vib metallic element be Cr, VIIB races metal Element is Mn, and the group VIII metal element is at least one in Fe, Co and Ni, and VA races metallic element is Bi.
In the application of the present invention, additive can be one or more in aforementioned various phosphate, can be crystalline state, also may be used Being amorphous state.In order to further improve the safety of the lithium ion battery for preparing, it is preferable that the additive is hydration Chromic orthophosphate (CrPO4·7/2H2O), (normalization formula is Co (PO to eight hydration orthophosphoric acid Asia cobalts4)2/3·8/3H2O) and hydration (normalization formula is Mg (PO to magnesium phosphate4)0.6(HPO4)0.1·3/2H2O at least one in).
In the application of the present 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 in the process for preparing 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 0.05-22 weight %, in view of battery energy density and the consideration of battery combination property, more preferably 3-15 weight %, more excellent Elect 5.5-10.5 weight % as.It will be understood by those skilled in the art that the dry weight of electrode dressing is referred to and is coated in collector On the drying of all slurries after the weight of material that obtains.
In the application of the present invention, for the individual particle or Water-borne paint of 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 aforementioned different additive, i.e., the preparation method of the hydrated phosphate of different element M does not have It is special to limit, can be various methods commonly used in the art, this is well known to those skilled in the art, and will not be described here. Wherein, it will be understood by those skilled in the art that in preparation process, be dried at a temperature of no more than 150 DEG C or Person carries out hydrothermal treatment consists, the crystallization in the hydrated phosphate of element M using water at a temperature of no more than 200 DEG C as primary solvent Water will not be lost, i.e., still contain water of crystallization in the hydrated phosphate of element M；But heat treatment is carried out in the case where being not less than 400 DEG C, can be thorough The water of crystallization in the hydrated phosphate of element M is removed, that is, water of crystallization is not contained in the phosphate of the element M for obtaining.
Second aspect, the invention provides a kind of lithium ion battery electrode sizing agent, the electrode slurry include active substance, Binding agent, conductive agent, additive, solvent and optional thickening agent, on the basis of the weight of the active substance, the additive Content be 0.05-30 weight %；The additive is M (PO4)a(HPO4)b·cH2O, wherein, M is Group IIA metal element, IB Race's metallic element, Group IIB metal element, IIIB races metallic element, Group IVB metallic element, group vib metallic element, VIIB races gold At least one element in category element, group VIII metal element and VA races metallic element, a >=0, b >=0, and a, b are 0 when different, c>0。
Preferably, on the basis of the weight of the active substance, the content of the additive is 2-19 weight %, further Preferably 6-13 weight %.
In the lithium ion battery electrode sizing agent of the present invention, under preferable case, in additive, the Group IIA metal element is Mg, IB races metallic element be Cu, the Group IIB metal element be Zn, IIIB races metallic element be Y, Sc, La, Ce, At least one in Nd, Sm, Gd and Er, the Group IVB metallic element is Ti and/or Zr, and the group vib metallic element is Cr, VIIB races metallic element is Mn, and the group VIII metal element is at least one in Fe, Co and Ni, VA races metal Element is Bi.
In the lithium ion battery electrode sizing agent of the present invention, in order to further improve the safety of the lithium ion battery for preparing Property, it is preferable that the additive is hydration chromic orthophosphate (CrPO4·7/2H2O), eight hydration orthophosphoric acid Asia cobalt (normalization formula For Co (PO4)2/3·8/3H2O) and hydrated magnesium phosphate (normalization formula be Mg (PO4)0.6(HPO4)0.1·3/2H2O in) at least It is a kind of.
In the lithium ion battery electrode sizing agent of the present invention, for the individual particle or Water-borne paint of additive is without special Require, 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 of active substance, binding agent, conductive agent, solvent and thickening agent is selected and consumption is without special Restriction, the conventional species that can be respectively this area respective components is selected and consumption, for battery energy density and battery The consideration of combination property, under preferable case, on the basis of the weight of the active substance, content of the binding agent in terms of butt For 0.5-5.5 weight %, the content of the conductive agent is 0.5-5.5 weight %, and the content of the solvent is 50-220 weight %, The content of the thickening agent is 0-3 weight %.Thickening agent is not typically used in lithium ion battery anode glue size, and in lithium ion Used in battery cathode slurry, on the basis of the weight of active substance, content is 0.5-3 weight %.
Can be this area routine for positive active material is without special selection in lithium ion battery anode glue size 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.
Can be this area routine for negative electrode active material is without special selection in lithium ion battery cathode slurry The various negative electrode active materials for using, under preferable case, negative electrode active material is graphite, lithium titanate, silicon, hard carbon, stannum and oxidation At least one in stannum.
In lithium ion battery anode glue size and lithium ion battery cathode slurry, for binding agent is without special selection, 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 One or more in dimension element.When foregoing adhesives are polymer, the number-average molecular weight of each polymer is generally 30-150 ten thousand.
In lithium ion battery anode glue size and lithium ion battery cathode slurry, for conductive agent is without special selection, 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).
Can be various solvents commonly used in the art for solvent is without special selection, under preferable case, solvent For at least one in N-Methyl pyrrolidone (NMP), deionized water, tetrahydrofuran, dimethyl sulfoxide, ethanol and isopropanol. Wherein, it is further preferred that in lithium ion battery anode glue size, solvent is N-Methyl pyrrolidone；It is negative in lithium ion battery In the slurry of pole, solvent is deionized water and/or N-Methyl pyrrolidone.
Wherein, it is applied to thickening agent in lithium ion battery cathode slurry more, whether adds in lithium ion battery anode glue size Plus thickening agent can be selected according to practical situations, it is selected specifically to as it is known to those skilled in the art that preferable case Under, thickening agent is at least one in sodium carboxymethyl cellulose (CMC), polyvinylpyrrolidone, Polyethylene Glycol and polyvinyl alcohol.
Wherein, for the preparation method of lithium ion battery electrode sizing agent of the invention, there is no particular limitation, can be this The conventional various methods in field, as long as can be by the slurry mix homogeneously containing aforementioned component, for example, containing active matter The slurry of matter, binding agent, conductive agent, additive, solvent and optional thickening agent can pass through first to mix binding agent and solvent, Mixed liquor is obtained, is then mixed active substance, conductive agent, additive and optional thickening agent with mixed liquor, Huo Zheke With by by thickening agent or binding agent and solvent mixing, obtaining mixed liquor, then by active substance, conductive agent, additive and viscous Knot agent or thickening agent 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 0.5-12 Weight %, the content of the solvent is 90-420 weight %, and the content of the conductive agent is 0-12 weight %；The additive is M(PO4)a(HPO4)b·cH2O, wherein, M is Group IIA metal element, IB races metallic element, Group IIB metal element, IIIB races gold Category element, Group IVB metallic element, group vib metallic element, VIIB races metallic element, group VIII metal element and metal unit of VA races It is 0, c when at least one element in element, a >=0, b >=0, and a, b are different>0.
In the additive slurry of the present invention, under preferable case, in additive, the Group IIA metal element is Mg, the IB Race's metallic element is Cu, and the Group IIB metal element is Zn, and IIIB races metallic element is Y, Sc, La, Ce, Nd, Sm, Gd With at least one in Er, the Group IVB metallic element is Ti and/or Zr, and the group vib metallic element is Cr, the VIIB Race's metallic element is Mn, and the group VIII metal element is at least one in Fe, Co and Ni, and VA races metallic element is Bi。
In the additive slurry of the present invention, in order to further improve the safety of the lithium ion battery for preparing, preferably Ground, the additive is hydration chromic orthophosphate (CrPO4·7/2H2O), (normalization formula is Co to eight hydration orthophosphoric acid Asia cobalts (PO4)2/3·8/3H2O) and hydrated magnesium phosphate (normalization formula be Mg (PO4)0.6(HPO4)0.1·3/2H2O at least in) Kind.
In the additive slurry of the present invention, for the individual particle or Water-borne paint of 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 select there is no particular limitation, The conventional species that this area respective components can be respectively is selected, and under preferable case, binding agent is polyacrylamide, gathers inclined two In fluorothene, politef, 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 N-Methyl pyrrolidone, deionized water, tetrahydrofuran, dimethyl At least one in sulfoxide, ethanol and isopropanol.Wherein, it is further preferred that solvent be N-Methyl pyrrolidone 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 by the slurry mix homogeneously 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 includes collector and the electrode dressing on collector, the electrode dressing contain active substance, binding agent, conductive agent, Additive and optional thickening agent, the additive is M (PO4)a(HPO4)b·cH2O, wherein, M is Group IIA metal element, IB Race's metallic element, Group IIB metal element, IIIB races metallic element, Group IVB metallic element, group vib metallic element, VIIB races gold At least one element in category element, group VIII metal element and VA races metallic element, a >=0, b >=0, and a, b are 0 when different, c>0。
In the lithium ion cell positive or negative pole of the present invention, under preferable case, in additive, the Group IIA metal element For Mg, IB races metallic element is Cu, and the Group IIB metal element is Zn, IIIB races metallic element be Y, Sc, La, At least one in Ce, Nd, Sm, Gd and Er, the Group IVB metallic element is Ti and/or Zr, and the group vib metallic element is Cr, VIIB races metallic element is Mn, and the group VIII metal element is at least one in Fe, Co and Ni, the VA races Metallic element is Bi.
In the lithium ion cell positive or negative pole of the present invention, in order to further improve the peace of the lithium ion battery for preparing Quan Xing, it is preferable that the additive is hydration chromic orthophosphate (CrPO4·7/2H2O), eight hydration orthophosphoric acid Asia cobalts (lead to by normalization Formula is Co (PO4)2/3·8/3H2O) and hydrated magnesium phosphate (normalization formula be Mg (PO4)0.6(HPO4)0.1·3/2H2O in) extremely Few one kind.
Can be ability for active substance is without special selection in the lithium ion cell positive or negative pole of the present invention The conventional use of various active substances in domain, under preferable case, the active substance is 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, stannum and At least one in stannum oxide.
Can be this area for binding agent is without special selection in the lithium ion cell positive or negative pole of the present invention Conventional use of various binding agents, under preferable case, binding agent is polyacrylamide, polyvinylidene fluoride, politef, fourth At least one in benzene rubber, cellulose-based polymer, polyvinyl alcohol, polyolefin, Viton and Polyurethane.
Can be this area for conductive agent is without special selection in the lithium ion cell positive or negative pole of the present invention 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 the lithium ion cell positive or negative pole of the present invention, as it was previously stated, typically containing thickening in lithium ion battery negative Agent, under preferable case, thickening agent be sodium carboxymethyl cellulose, polyvinylpyrrolidone, Polyethylene Glycol and polyvinyl alcohol in extremely Few one kind.
In the lithium ion cell positive or negative pole of the present invention, 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 0.05-22 weight %, more preferably 3-15 weight %, is still more preferably 5.5-10.5 weight %.
5th aspect, the invention provides a kind of method for preparing lithium ion cell positive or negative pole, methods described includes： Lithium ion battery electrode sizing agent of the present invention is coated on a current collector, drying；Or
(1) additive slurry of the present invention is coated on a current collector, drying obtains the afflux of additive coating Body；
(2) prepare active material slurry, the active material slurry include active substance, binding agent, conductive agent, solvent and Optional thickening agent, is then coated in the active material slurry on the collector of the additive coating that step (1) is obtained, and dries It is dry；Or
(1) prepare active material slurry, the active material slurry include active substance, binding agent, conductive agent, solvent and Optional thickening agent, then coats the active material slurry on a current collector, and 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, for the method coated in each step, there is no particular limitation, can be various methods commonly used in the art, This is known to people in the art, to will not be described 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 substance, the binding agent containing in terms of butt Measure as 0.5-5.5 weight %, the content of the conductive agent is 0.5-5.5 weight %, and the content of the solvent is 50-220 weights Amount %.
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 thickening agent, on the basis of the weight of the active substance, the binding agent is in terms of butt Content is 0.5-5.5 weight %, and the content of the conductive agent is 0.5-5.5 weight %, and the amount of thickener is 0.5-3 weights Amount %, the content of the solvent is 50-220 weight %.
Wherein, the tool of aforementioned various positive active materials, negative electrode active material, binding agent, conductive agent, solvent and thickening agent Body species is selected, and can be found in corresponding contents above, be will not be described here.And it will be understood by those skilled in the art that When preparing lithium ion cell positive or negative pole, using each self-corresponding collector and active material slurry.
Wherein, for drying 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 the lithium ion cell positive for preparing of methods described or negative pole.
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 the lithium ion battery of the present invention, it will be understood by those skilled in the art that at least in positive pole and negative pole Individual electrode is 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 The described lithium ion cell positive of invention and negative pole.
In the lithium ion battery of the present 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 together in battery case.Barrier film can be various barrier films commonly used in the art, such as polyphosphazene polymer Compound microporous membrane, including the MULTILAYER COMPOSITE microporous membrane of polypropylene microporous membrane and polypropylene and polyethylene.The position of barrier film, Property and species are well known to those skilled in the art, and will not be described here.
Wherein, nonaqueous electrolytic solution is the mixed solution of electrolyte lithium salt and nonaqueous solvent, and it is not particularly limited, can be with Using 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 biborate, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and fluorohydrocarbon base Sulfonic Lithium.Nonaqueous solvent 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), Allyl carbonate (PC), carbonic acid Asia second In alkene ester (VC), gamma-butyrolacton (γ-BL), sultone and other fluorine-containing, sulfur-bearings or the ring-type organosilane ester containing unsaturated bond At least one.The injection rate of electrolyte is generally 5-8 gram/ampere-hour, and the concentration of electrolyte is generally 0.8-1.2 mol/Ls.
In the lithium ion battery of the present invention, for battery container, there is no particular limitation, can be commonly used in the art each Battery container is planted, this is well known to those skilled in the art, and will not be described here.
In the lithium ion battery of the present invention, the common method of the method for this area of battery is prepared, in general, by positive pole A battery core component is constituted with negative pole and barrier film, the battery core component for obtaining and nonaqueous electrolytic solution is sealed in battery case, you can Obtain lithium ion battery.Concrete grammar is well known to those skilled in the art, and will not be described here.
Embodiment
Hereinafter will be described the present invention by embodiment, but and be not so limited the present invention, such as without especially saying Bright, material used can pass through commercially available, and method used is the conventional method of this area.
Lithium nickel cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2Purchased from Shanghai Shanshan Science and Technology Co., Ltd.
Cobalt acid lithium LiCoO2Purchased from Tianjin Bamo Technology Co.
Lithium nickel cobalt alumina LiNi0.8Co0.15Al0.05O2Purchased from Japanese Toda Kogyo Corp..
Pvdf binding 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 Te REFRESH PLUS energy and materials limited company.
Thickening agent CMC is purchased from Japanese Di-ichi Kogyo Seiyaku Co., Ltd..
Butadiene-styrene rubber emulsion binder solid content is 50%, purchased from Zeon Corp.
The preparation method of hydration chromic orthophosphate includes：By the water chromic nitrate 20000g deionized water dissolving of 4000g nine, it is obtained Chromium nitrate solution, by 1640g trisodium Phosphate Anhydrous 16000g deionized water dissolving, obtains trisodium phosphate solution.In stirring Under the conditions of, by the mixing of above two solution, and it is 5 to adjust mixed system pH value with the strong phosphoric acid that mass fraction is 85%, control Incorporation time is 2 hours, obtains suspension.Then the suspension is transferred to into hydrothermal reaction kettle, under conditions of stirring, 180 DEG C heat treatment 10 hours, is precipitated.The precipitate with deionized water is washed to remove sodium ion therein and phosphate radical, then Hydration chromic orthophosphate (CrPO is obtained by spray drying at 110 DEG C4·7/2H2O) powder, measuring wherein particle diameter D50 is 340nm。
The preparation method of eight hydration orthophosphoric acid Asia cobalts includes：The water colbaltous nitrates of 2910g six is water-soluble with 15000g deionizations Solution, is obtained colbaltous nitrate solution, by 1093g trisodium Phosphate Anhydrous 10000g deionized water dissolving, obtains trisodium phosphate solution. Under conditions of stirring and nitrogen protection, by the mixing of above two solution, incorporation time is controlled for 2 hours, obtain suspension.So Afterwards the suspension is transferred to into hydrothermal reaction kettle, under conditions of stirring and nitrogen protection, 180 DEG C of heat treatments 10 hours are obtained Precipitation.The precipitate with deionized water is washed to remove sodium ion therein and phosphate radical, spray dried is then passed through at 110 DEG C It is dry obtain eight hypophosphite monohydrates Asia cobalt (normalization formula be Co (PO4)2/3·8/3H2O) powder, measuring wherein particle diameter D50 is 260nm。
The preparation method of hydrated magnesium phosphate includes：By 2560g magnesium nitrate hexahydrates 10000g deionized water dissolving, nitre is obtained Sour magnesium solution, by 984g trisodium Phosphate Anhydrous, 358g disodium hydrogen phosphate dodecahydrates 10000g deionized water dissolving, obtains phosphorus Sour trisodium, disodium hydrogen phosphate mixed solution.Under conditions of stirring, magnesium nitrate solution is mixed with tertiary sodium phosphate, disodium hydrogen phosphate Solution mixing is closed, incorporation time is controlled for 2 hours, suspension is obtained.Then the suspension is transferred to into hydrothermal reaction kettle, is being stirred Under conditions of mixing, 180 DEG C of heat treatments 10 hours are precipitated.By precipitate with deionized water washing with remove sodium therein from Son and phosphate radical, (normalization formula is Mg (PO then to obtain hydrated magnesium phosphate by spray drying at 105 DEG C4)0.6 (HPO4)0.1·3/2H2O) powder, measures wherein particle diameter D50 for 200nm.
The preparation method of the hydrogen titanium of two hypophosphite monohydrate one includes：In 0 DEG C of water-bath and under conditions of 300rpm strong stirrings, will 1900g titanium tetrachloride liquids are slowly added to into the strong phosphoric acid that 2306g mass fractions are 85%, control plus the titanium tetrachloride time is 2 hours, reaction obtained suspension after terminating.Then the suspension is transferred to into hydrothermal reaction kettle, under conditions of stirring, 180 DEG C heat treatment 10 hours, is precipitated.The precipitate with deionized water is washed to remove chloride ion therein, finally at 115 DEG C The lower hydrogen titanium (Ti (HPO of two hypophosphite monohydrate one that drying is obtained by spray drying4)2·2H2O) granule, measures wherein particle diameter D50 For 70nm.
The preparation method of the hydrogen zirconium of one hypophosphite monohydrate one includes：In 0 DEG C of water-bath and under conditions of 280rpm strong stirrings, will 2330g Zirconium tetrachloride. powder is slowly added to into the strong phosphoric acid that 2306g mass fractions are 85%, controls plus the Zirconium tetrachloride. time is 2 hours, reaction obtained suspension after terminating.Then the suspension is transferred to into hydrothermal reaction kettle, under conditions of stirring, 180 DEG C heat treatment 10 hours, is precipitated.The precipitate with deionized water is washed to remove chloride ion therein, finally at 110 DEG C The lower hydrogen zirconium (Zr (HPO of a hypophosphite monohydrate one that drying is obtained by spray drying4)2·H2O) granule, measuring wherein particle diameter D50 is 90nm。
The preparation method of one hydration orthophosphoric acid yttrium includes：By the water Yttrium trinitrate 10000g deionized water dissolving of 3830g six, system Yttrium nitrate solution is obtained, by 1640g trisodium Phosphate Anhydrous 16000g deionized water dissolving, trisodium phosphate solution is obtained.In stirring Under conditions of, by the mixing of above two solution, and it is 5 to adjust mixed system pH value with the strong phosphoric acid that mass fraction is 85%, control Incorporation time processed is 2 hours, obtains suspension.Then the suspension is transferred to into hydrothermal reaction kettle, under conditions of stirring, 180 DEG C of heat treatments 10 hours, are precipitated.The precipitate with deionized water is washed to remove sodium ion therein and phosphate radical, Then a hydration orthophosphoric acid yttrium (YPO is obtained by spray drying at 110 DEG C4·H2O) powder, measuring wherein particle diameter D50 is 350nm。
The preparation method of one hydration orthophosphoric acid scandium includes：By the water Scium nitrate(Sc(NO3)3) 10000g deionized water dissolving of 3390g six, system Scium nitrate(Sc(NO3)3) solution is obtained, by 1640g trisodium Phosphate Anhydrous 16000g deionized water dissolving, trisodium phosphate solution is obtained.In stirring Under conditions of, by the mixing of above two solution, and it is 5 to adjust mixed system pH value with the strong phosphoric acid that mass fraction is 85%, control Incorporation time processed is 2 hours, obtains suspension.Then the suspension is transferred to into hydrothermal reaction kettle, under conditions of stirring, 180 DEG C of heat treatments 10 hours, are precipitated.The precipitate with deionized water is washed to remove sodium ion therein and phosphate radical, Then a hydration orthophosphoric acid scandium (ScPO is obtained by spray drying at 110 DEG C4·H2O) powder, measuring wherein particle diameter D50 is 370nm。
The preparation method of one hydration lanthanum orthophosphate includes：By 4330g lanthanum nitrate hexahydrates 20000g deionized water dissolving, system Lanthanum nitrate hexahydrate is obtained, by 1640g trisodium Phosphate Anhydrous 16000g deionized water dissolving, trisodium phosphate solution is obtained.In stirring Under conditions of, by the mixing of above two solution, and it is 5 to adjust mixed system pH value with the strong phosphoric acid that mass fraction is 85%, control Incorporation time processed is 2 hours, obtains suspension.Then the suspension is transferred to into hydrothermal reaction kettle, under conditions of stirring, 180 DEG C of heat treatments 10 hours, are precipitated.The precipitate with deionized water is washed to remove sodium ion therein and phosphate radical, Then a hydration lanthanum orthophosphate (LaPO is obtained by spray drying at 110 DEG C4·H2O) powder, measuring wherein particle diameter D50 is 380nm。
The preparation method of one hydration cerous orthophosphate includes：By the water cerous nitrate 20000g deionized water dissolving of 4340g six, system Cerous nitrate solution is obtained, by 1640g trisodium Phosphate Anhydrous 16000g deionized water dissolving, trisodium phosphate solution is obtained.In stirring Under conditions of, by the mixing of above two solution, and it is 5 to adjust mixed system pH value with the strong phosphoric acid that mass fraction is 85%, control Incorporation time processed is 2 hours, obtains suspension.Then the suspension is transferred to into hydrothermal reaction kettle, under conditions of stirring, 180 DEG C of heat treatments 10 hours, are precipitated.The precipitate with deionized water is washed to remove sodium ion therein and phosphate radical, Then a hydration cerous orthophosphate (CePO is obtained by spray drying at 110 DEG C4·H2O) powder, measuring wherein particle diameter D50 is 290nm。
The preparation method of one hydration orthophosphoric acid neodymium includes：By the water neodymium nitrate 20000g deionized water dissolving of 4380g six, system Neodymium nitrate solution is obtained, by 1640g trisodium Phosphate Anhydrous 16000g deionized water dissolving, trisodium phosphate solution is obtained.In stirring Under conditions of, by the mixing of above two solution, and it is 5 to adjust mixed system pH value with the strong phosphoric acid that mass fraction is 85%, control Incorporation time processed is 2 hours, obtains suspension.Then the suspension is transferred to into hydrothermal reaction kettle, under conditions of stirring, 180 DEG C of heat treatments 10 hours, are precipitated.The precipitate with deionized water is washed to remove sodium ion therein and phosphate radical, Then a hydration orthophosphoric acid neodymium (NdPO is obtained by spray drying at 110 DEG C4·H2O) powder, measuring wherein particle diameter D50 is 220nm。
The preparation method of one hydration samaric orthophosphate includes：By the water samaric nitrate 20000g deionized water dissolving of 4440g six, system Samarium nitrate solution is obtained, by 1640g trisodium Phosphate Anhydrous 16000g deionized water dissolving, trisodium phosphate solution is obtained.In stirring Under conditions of, by the mixing of above two solution, and it is 5 to adjust mixed system pH value with the strong phosphoric acid that mass fraction is 85%, control Incorporation time processed is 2 hours, obtains suspension.Then the suspension is transferred to into hydrothermal reaction kettle, under conditions of stirring, 180 DEG C of heat treatments 10 hours, are precipitated.The precipitate with deionized water is washed to remove sodium ion therein and phosphate radical, Then a hydration samaric orthophosphate (SmPO is obtained by spray drying at 110 DEG C4·H2O) powder, measuring wherein particle diameter D50 is 250nm。
The preparation method of one hydration orthophosphoric acid gadolinium includes：By the water Gadolinium trinitrate 20000g deionized water dissolving of 4510g six, system Gadolinium trinitrate solution is obtained, by 1640g trisodium Phosphate Anhydrous 16000g deionized water dissolving, trisodium phosphate solution is obtained.In stirring Under conditions of, by the mixing of above two solution, and it is 5 to adjust mixed system pH value with the strong phosphoric acid that mass fraction is 85%, control Incorporation time processed is 2 hours, obtains suspension.Then the suspension is transferred to into hydrothermal reaction kettle, under conditions of stirring, 180 DEG C of heat treatments 10 hours, are precipitated.The precipitate with deionized water is washed to remove sodium ion therein and phosphate radical, Then a hydration orthophosphoric acid gadolinium (GdPO is obtained by spray drying at 110 DEG C4·H2O) powder, measuring wherein particle diameter D50 is 420nm。
The preparation method of one hydration orthophosphoric acid erbium includes：By the water Erbium trinitrate 20000g deionized water dissolving of 4430g five, system Nitrate Solution is obtained, by 1640g trisodium Phosphate Anhydrous 16000g deionized water dissolving, trisodium phosphate solution is obtained.In stirring Under conditions of, by the mixing of above two solution, and it is 5 to adjust mixed system pH value with the strong phosphoric acid that mass fraction is 85%, control Incorporation time processed is 2 hours, obtains suspension.Then the suspension is transferred to into hydrothermal reaction kettle, under conditions of stirring, 180 DEG C of heat treatments 10 hours, are precipitated.The precipitate with deionized water is washed to remove sodium ion therein and phosphate radical, Then a hydration orthophosphoric acid erbium (ErPO is obtained by spray drying at 110 DEG C4·H2O) powder, measuring wherein particle diameter D50 is 320nm。
The preparation method of two hydration Orthophosphoric acid Ferrum includes：By the water ferric nitrate 15000g deionized water dissolving of 4040g nine, system Iron nitrate solution is obtained, by 1640g trisodium Phosphate Anhydrous 16000g deionized water dissolving, trisodium phosphate solution is obtained.In stirring Under conditions of, by the mixing of above two solution, and it is 3 to adjust mixed system pH value with the strong phosphoric acid that mass fraction is 85%, control Incorporation time processed is 2 hours, obtains suspension.Then the suspension is transferred to into hydrothermal reaction kettle, under conditions of stirring, 180 DEG C of heat treatments 10 hours, are precipitated.The precipitate with deionized water is washed to remove sodium ion therein and phosphate radical, Then two hydration Orthophosphoric acid Ferrum (FePO are obtained by spray drying at 110 DEG C4·2H2O) powder, measuring wherein particle diameter D50 is 110nm。
The preparation method of one hydration manganous phosphate includes：By the 50 weight % Mn nitrate aqueous solution 20000g of 3580g Deionized water dilutes, and Mn nitrate solution is obtained, and by 1640g trisodium Phosphate Anhydrous 16000g deionized water dissolving, obtains phosphorus Sour three sodium solutions.Under conditions of stirring, by the mixing of above two solution, and adjust mixed with the concentrated nitric acid that mass fraction is 65% It is 3 to close system pH, controls incorporation time for 2 hours, obtains suspension.Then the suspension is transferred to into hydrothermal reaction kettle, Under conditions of stirring, 180 DEG C of heat treatments 10 hours are precipitated.The precipitate with deionized water washing is therein to remove Sodium ion and phosphate radical, then obtain a hydration manganous phosphate (MnPO at 110 DEG C by spray drying4·H2O) powder, surveys It is 150nm to obtain wherein particle diameter D50.
The preparation method of one hydration orthophosphoric acid nickel includes：By the liquid glauber salt of 2910g six acid Asia nickel 20000g deionized water dissolving, Prepared nitric acid Asia nickel solution, by 1640g trisodium Phosphate Anhydrous 16000g deionized water dissolving, obtains trisodium phosphate solution. Under conditions of stirring, by the mixing of above two solution, and it is with the concentrated nitric acid regulation mixed system pH value that mass fraction is 65% 3, incorporation time is controlled for 2 hours, obtain suspension.Then the suspension is transferred to into hydrothermal reaction kettle, in the condition of stirring Under, 180 DEG C of heat treatments 10 hours are precipitated.The precipitate with deionized water is washed to remove sodium ion therein and phosphoric acid Root, then obtains a hydration orthophosphoric acid nickel (NiPO at 110 DEG C by spray drying4·H2O) powder, measures wherein particle diameter D50 For 120nm.
The preparation method of hydration orthophosphoric acid bismuth includes：The water bismuth nitrate of 4850g five is added into the 20000g that mass fraction is 2% Dissolve in diluted nitric acid aqueous solution, bismuth nitrate solution is obtained, 1640g trisodium Phosphate Anhydrous 16000g deionized water dissolving is obtained To trisodium phosphate solution.Under conditions of stirring, by the mixing of above two solution, and adjusted with the strong phosphoric acid that mass fraction is 85% Section mixed system pH value is 5, controls incorporation time for 2 hours, obtains suspension.Then the suspension is transferred to into hydro-thermal reaction Kettle, under conditions of stirring, 180 DEG C of heat treatments 10 hours are precipitated.The precipitate with deionized water is washed to remove wherein Sodium ion and phosphate radical, then at 110 DEG C by spray drying obtain be hydrated orthophosphoric acid bismuth (BiPO4·2/3H2O) powder, Wherein particle diameter D50 is measured for 450nm.
The preparation method of three hydration orthophosphoric acid copper includes：By 2420g nitrate trihydrate copper 10000g deionized water dissolving, system Copper nitrate solution is obtained, by 1093g trisodium Phosphate Anhydrous 10000g deionized water dissolving, trisodium phosphate solution is obtained.In stirring Under conditions of, by the mixing of above two solution, incorporation time is controlled for 2 hours, obtain suspension.Then by the suspension transfer To hydrothermal reaction kettle, under conditions of stirring, 180 DEG C of heat treatments 10 hours are precipitated.By the precipitate with deionized water washing To remove sodium ion therein and phosphate radical, (normalization is led to then to obtain three hypophosphite monohydrate copper by spray drying at 110 DEG C Formula is Cu (PO4)2/3·H2O) powder, measures wherein particle diameter D50 for 250nm.
The preparation method of two hydration zinc orthophosphates includes：By 2970g zinc nitrate hexahydrates 10000g deionized water dissolving, system Zinc nitrate solution is obtained, by 1093g trisodium Phosphate Anhydrous 10000g deionized water dissolving, trisodium phosphate solution is obtained.In stirring Under conditions of, by the mixing of above two solution, incorporation time is controlled for 2 hours, obtain suspension.Then by the suspension transfer To hydrothermal reaction kettle, under conditions of stirring, 180 DEG C of heat treatments 10 hours are precipitated.By the precipitate with deionized water washing To remove sodium ion therein and phosphate radical, (normalization is led to then to obtain two hypophosphite monohydrate zinc by spray drying at 110 DEG C Formula is Zn (PO4)2/3·2/3H2O) powder, measures wherein particle diameter D50 for 430nm.
Embodiment 1
(1) prepared by battery positive pole piece
By 21500g lithium nickel cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, 625g binding agents HSV900,875g are conductive Agent Super-P and 2000g are hydrated chromic orthophosphate (CrPO4·7/2H2O) powder additive mixes, and concrete grammar is：First with 25000g NMP are 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, hydration chromic orthophosphate (CrPO4·7/2H2O) powder additive with The solution mixing of above-mentioned binding agent, afterwards stirring 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 Spend for 339.3g/m2(in terms of weight of the two-sided surface density of dressing after drying, similarly hereinafter, and on the basis of the dry weight of electrode dressing, add Plus the content of agent is 8 weight %), then dry at 110 DEG C, obtain anode pole piece.
(2) prepared by negative pole piece of battery
By 12285g natural graphite negative electrode materials, 162.5g thickening agent CMC, 162.5g conductive agent Super-P and 780g fourths Benzene elastomer latex binding agent mixes, and concrete grammar is：First with 12500g deionized waters as solvent, by thickening agent CMC dissolvings, and It is respectively that butadiene-styrene rubber emulsion binder, conductive agent Super-P, natural graphite negative electrode material is molten with above-mentioned thickening agent under stirring Liquid mixes, and stirring afterwards forms uniform cathode size；
The cathode size is coated uniformly on the Copper Foil that thickness is 18 μm, coating width is 164mm, the two-sided face of dressing is close Spend for 164.1g/m2(in terms of the weight after drying, similarly hereinafter), then dry at 100 DEG C, obtain cathode pole piece.
(3) assembling of cell
Anode pole piece is cut into the size of 120mm × 160mm as positive pole, by cathode pole piece be cut into 125mm × The size of 164mm, with polypropylene screen as barrier film, is assembled into battery core component as negative pole, in being put into Soft Roll aluminum plastic film battery container, And both positive and negative polarity lug is welded together respectively with aluminum plastic film, during ensure the insulation of lug and battery container, through 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.Subsequently 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, finally take out the gas produced in battery under nitrogen atmosphere protection Go out and by battery secondary sealing, obtain lithium ion battery A1.
Embodiment 2
Method according to embodiment 1 prepares lithium ion battery A2, except for the difference that, in step (1), the system of battery positive pole piece Preparation Method is as follows：
By 21500g lithium nickel cobalt alumina LiNi0.8Co0.15Al0.05O2Positive electrode, 1042g PTFE emulsion binding agent D210, 875g conductive agents acetylene black mixes, and concrete grammar 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；
1000g eight is hydrated into orthophosphoric acid Asia cobalt, and (normalization formula is Co (PO4)2/3·8/3H2O) powder additive, 75gPTFE emulsion binders D210 mixes, and concrete grammar is：First with 2500g water as solvent, by PTFE emulsion binding agent D210 point Dissipate, obtain emulsion, and under agitation by eight hydration orthophosphoric acid Asia cobalts, (normalization formula is Co (PO4)2/3·8/3H2O) powder adds Plus agent mixes with the emulsion of above-mentioned binding agent, stirring afterwards forms uniform additive slurry；
The additive slurry is coated uniformly on into above-mentioned anode pole piece surface, coating width is 162mm, to cover activity Material, the two-sided surface density of dressing is 28.5g/m2(on the basis of the dry weight of electrode dressing, weight % of content 8 of additive), so Dry at 100 DEG C afterwards, obtaining surface-coated has the anode pole piece of additive.
Embodiment 3
Method according to embodiment 1 prepares lithium ion battery A3, except for the difference that, in step (1), the system of battery positive pole piece Preparation Method is as follows：
By 1000g hydrated magnesium phosphates, (normalization formula is Mg (PO4)0.6(HPO4)0.1·3/2H2O) powder additive, 40g Conductive agent Super-P, 50g binding agent HSV900 mixes, and concrete grammar is：First with 2500g NMP as solvent, by binding agent HSV900 dissolves, and under agitation by hydrated magnesium phosphate, (normalization formula is Mg (PO4)0.6(HPO4)0.1·3/2H2O) powder adds Plus agent, conductive agent Super-P mix with the solution of above-mentioned binding agent, stirring afterwards forms 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 29.8g/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 625g binding agent HSV900,875g conductive agents CNT, Concrete grammar 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 into 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 8 weight %), then at 120 DEG C Lower drying, obtains the anode pole piece that aluminium foil is coated through additive.
Embodiment 4
(1) prepared by battery positive pole piece
By 21750g lithium nickel cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, 625g binding agents HSV900,875g are conductive Agent Super-P mixes, and concrete grammar 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 Spend for 312.2g/m2(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 11302g natural graphite negative electrode materials, 149.5g thickening agent CMC, 149.5g conductive agent Super-P, 718g butylbenzene Elastomer latex binding agent and 1040g hydration chromic orthophosphate (CrPO4·7/2H2O) powder additive mixes, and concrete grammar is：First with 13500g deionized waters are solvent, by thickening agent CMC dissolvings, and under agitation respectively by butadiene-styrene rubber emulsion binder, conduction Agent Super-P, natural graphite negative electrode material, hydration chromic orthophosphate (CrPO4·7/2H2O) powder additive and above-mentioned thickening agent Solution mixes, and stirring afterwards forms uniform cathode size；
The cathode size is coated uniformly on the Copper Foil that thickness is 18 μm, coating width is 164mm, the two-sided face of dressing is close Spend for 178.4g/m2(on the basis of the dry weight of electrode dressing, the content of additive is 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, in being put into Soft Roll aluminum plastic film battery container, And both positive and negative polarity lug is welded together respectively with aluminum plastic film, during ensure the insulation of lug and battery container, through 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.Subsequently 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, finally take out the gas produced in battery under nitrogen atmosphere protection Go out and by battery secondary sealing, obtain lithium ion battery A4.
Embodiment 5
Method according to embodiment 1 prepares lithium ion battery A5, except for the difference that, in step (1), by 21967g lithium nickel cobalt manganeses Oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, 639g binding agent HSV900,894g conductive agents Super-P and 1500g are hydrated positive phosphorus Sour chromium (CrPO4·7/2H2O) powder additive mixes, and concrete grammar is：First with 25000g NMP as solvent, by binding agent HSV900 dissolves, and under agitation respectively by lithium nickel cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, conductive agent Super-P, Hydration chromic orthophosphate (CrPO4·7/2H2O) 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 Spend for 332g/m2(on the basis of the dry weight of electrode dressing, the content of additive is 6 weight %), then dries at 110 DEG C, Obtain anode pole piece.
Embodiment 6
Method according to embodiment 1 prepares lithium ion battery A6, except for the difference that, in step (1), by 21033g lithium nickel cobalt manganeses Oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, 611g binding agent HSV900,856g conductive agents Super-P and 2500g are hydrated positive phosphorus Sour chromium (CrPO4·7/2H2O) powder additive mixes, and concrete grammar is：First with 25000g NMP as solvent, by binding agent HSV900 dissolves, and under agitation respectively by lithium nickel cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, conductive agent Super-P, Hydration chromic orthophosphate (CrPO4·7/2H2O) 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, and coating width is 160mm, the two-sided surface density of dressing For 346.8g/m2(on the basis of the dry weight of electrode dressing, the content of additive is 10 weight %), then dries at 110 DEG C, Obtain anode pole piece.
Embodiment 7
Method according to embodiment 2 prepares lithium ion battery A7, except for the difference that, 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 Co (PO to the hydration orthophosphoric acid of 1000g eight Asia cobalt4)2/3·8/3H2O) powder is mixed with the emulsion of above-mentioned binding agent Close, stirring afterwards forms uniform additive slurry.
The additive slurry is coated uniformly on into above-mentioned anode pole piece surface, coating width is 162mm, to cover activity Material, the two-sided surface density of dressing is 20.6g/m2(on the basis of the dry weight of electrode dressing, the content of additive is 6 weight %), Then dry at 100 DEG C, obtaining surface-coated has the anode pole piece of additive.
Embodiment 8
Method according to embodiment 2 prepares lithium ion battery A8, except for the difference that, in step (1), the preparation of additive slurry Method is：First with 3500g water as solvent, by 135gPTFE emulsion binders D210 dispersions, emulsion is obtained, and under agitation will (normalization formula is Co (PO to the hydration orthophosphoric acid of 1000g eight Asia cobalt4)2/3·8/3H2O) powder is mixed with the emulsion of above-mentioned binding agent Close, stirring afterwards forms uniform additive slurry.
The additive slurry is coated uniformly on into above-mentioned anode pole piece surface, coating width is 162mm, to cover activity Material, the two-sided surface density of dressing is 37.8g/m2(on the basis of the dry weight of electrode dressing, the content of additive is 10 weight %), Then dry at 100 DEG C, obtaining surface-coated has the anode pole piece of additive.
Embodiment 9
Method according to embodiment 1 prepares lithium ion battery A9, except for the difference that, in step (1), by 22598g lithium nickel cobalt manganeses Oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, 657g binding agent HSV900,920g conductive agents Super-P and 825g hydration orthophosphoric acid Chromium (CrPO4·7/2H2O) powder additive mixes, and concrete grammar is：First with 25000g NMP as solvent, by binding agent HSV900 Dissolving, and under agitation respectively by lithium nickel cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, conductive agent Super-P, hydration are just Chromium phosphate (CrPO4·7/2H2O) 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 Spend for 322.8g/m2(on the basis of the dry weight of electrode dressing, the content of additive is 3.3 amounts %), 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, except for the difference that, in step (1), by 23183g lithium nickel cobalts Manganese oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, 674g binding agent HSV900,943g conductive agents Super-P and 200g are hydrated positive phosphorus Sour chromium (CrPO4·7/2H2O) powder additive mixes, and concrete grammar is：First with 25000g NMP as solvent, by binding agent HSV900 dissolves, and under agitation respectively by lithium nickel cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, conductive agent Super-P, Hydration chromic orthophosphate (CrPO4·7/2H2O) additive mixes with the solution of above-mentioned binding agent, and stirring afterwards forms uniform positive pole Slurry；
The anode sizing agent is coated uniformly on the aluminium foil that thickness is 25 μm, coating width is 160mm, the two-sided face of dressing is close Spend for 314.7g/m2(on the basis of the dry weight of electrode dressing, the content of additive is 0.8 weight %), 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, except for the difference that, in step (1), by 19981g lithium nickel cobalts Manganese oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, 581g binding agent HSV900,813g conductive agents Super-P and 3625g are hydrated just Chromium phosphate (CrPO4·7/2H2O) powder additive mixes, and concrete grammar is：First with 25000g NMP as solvent, by binding agent HSV900 dissolves, and under agitation respectively by lithium nickel cobalt manganese oxygen LiNi0.5Co0.2Mn0.3O2Positive electrode, conductive agent Super-P, Hydration chromic orthophosphate (CrPO4·7/2H2O) additive mixes with the solution of above-mentioned binding agent, and stirring afterwards forms uniform positive pole Slurry；
The anode sizing agent is coated uniformly on the aluminium foil that thickness is 25 μm, coating width is 160mm, the two-sided face of dressing is close Spend for 365.1g/m2(on the basis of the dry weight of electrode dressing, the content of additive is 14.5 weight %), then at 110 DEG C Drying, obtains anode pole piece.
Embodiment 12
Method according to embodiment 1 prepares lithium ion battery A12, except for the difference that, in step (1), will be hydrated chromic orthophosphate (CrPO4·7/2H2O) powder replaces with the hydrogen titanium (Ti (HPO of two hypophosphite monohydrate one4)2·2H2O) powder.
Embodiment 13
Method according to embodiment 1 prepares lithium ion battery A13, except for the difference that, in step (1), will be hydrated chromic orthophosphate (CrPO4·7/2H2O) powder replaces with the hydrogen zirconium (Zr (HPO of a hypophosphite monohydrate one4)2·H2O)。
Embodiment 14
Method according to embodiment 1 prepares lithium ion battery A14, except for the difference that, in step (1), will be hydrated chromic orthophosphate (CrPO4·7/2H2O) powder replaces with a hydration orthophosphoric acid yttrium (YPO4·H2O) powder.
Embodiment 15
Method according to embodiment 1 prepares lithium ion battery A15, except for the difference that, in step (1), will be hydrated chromic orthophosphate (CrPO4·7/2H2O) powder replaces with a hydration orthophosphoric acid scandium (ScPO4·H2O) powder.
Embodiment 16
Method according to embodiment 1 prepares lithium ion battery A16, except for the difference that, in step (1), will be hydrated chromic orthophosphate (CrPO4·7/2H2O) powder replaces with a hydration lanthanum orthophosphate (LaPO4·H2O) powder.
Embodiment 17
Method according to embodiment 1 prepares lithium ion battery A17, except for the difference that, in step (1), will be hydrated chromic orthophosphate (CrPO4·7/2H2O) powder replaces with a hydration cerous orthophosphate (CePO4·H2O) powder.
Embodiment 18
Method according to embodiment 1 prepares lithium ion battery A18, except for the difference that, in step (1), will be hydrated chromic orthophosphate (CrPO4·7/2H2O) powder replaces with a hydration orthophosphoric acid neodymium (NdPO4·H2O) powder.
Embodiment 19
Method according to embodiment 1 prepares lithium ion battery A19, except for the difference that, in step (1), will be hydrated chromic orthophosphate (CrPO4·7/2H2O) powder replaces with a hydration samaric orthophosphate (SmPO4·H2O) powder.
Embodiment 20
Method according to embodiment 1 prepares lithium ion battery A20, except for the difference that, in step (1), will be hydrated chromic orthophosphate (CrPO4·7/2H2O) powder replaces with a hydration orthophosphoric acid gadolinium (GdPO4·H2O) powder.
Embodiment 21
Method according to embodiment 1 prepares lithium ion battery A21, except for the difference that, in step (1), will be hydrated chromic orthophosphate (CrPO4·7/2H2O) powder replaces with a hydration orthophosphoric acid erbium (ErPO4·H2O) powder.
Embodiment 22
Method according to embodiment 1 prepares lithium ion battery A22, except for the difference that, in step (1), will be hydrated chromic orthophosphate (CrPO4·7/2H2O) powder replaces with two hydration Orthophosphoric acid Ferrum (FePO4·2H2O) powder.
Embodiment 23
Method according to embodiment 1 prepares lithium ion battery A23, except for the difference that, in step (1), will be hydrated chromic orthophosphate (CrPO4·7/2H2O) powder replaces with a hydration manganous phosphate (MnPO4·H2O) powder.
Embodiment 24
Method according to embodiment 1 prepares lithium ion battery A24, except for the difference that, in step (1), will be hydrated chromic orthophosphate (CrPO4·7/2H2O) powder replaces with a hydration orthophosphoric acid nickel (NiPO4·H2O) powder.
Embodiment 25
Method according to embodiment 1 prepares lithium ion battery A25, except for the difference that, in step (1), will be hydrated chromic orthophosphate (CrPO4·7/2H2O) powder replaces with hydration orthophosphoric acid bismuth (BiPO4·2/3H2O) powder.
Embodiment 26
Method according to embodiment 1 prepares lithium ion battery A26, except for the difference that, in step (1), will be hydrated chromic orthophosphate (CrPO4·7/2H2O) powder replace with three hypophosphite monohydrate copper (normalization formula be Cu (PO4)2/3·H2O) powder.
Embodiment 27
Method according to embodiment 1 prepares lithium ion battery A27, except for the difference that, in step (1), will be hydrated chromic orthophosphate (CrPO4·7/2H2O) powder replace with two hypophosphite monohydrate zinc (normalization formula be Zn (PO4)2/3·2/3H2O) powder.
Comparative example 1
Method according to embodiment 1 prepares lithium ion battery D1, except for the difference that, in step (1), is not added with being hydrated orthophosphoric acid Chromium (CrPO4·7/2H2O) powder additive, obtains anode active material slurry, and the anode active material slurry is uniformly coated On the aluminium foil that thickness is 25 μm, coating width is 160mm, and the two-sided surface density of dressing is 312.2g/m2(with the weight after drying Meter), then dry at 110 DEG C, obtain anode pole piece.
Comparative example 2
Method according to embodiment 2 prepares lithium ion battery D2, except for the difference that, in step (1), obtain anode pole piece it Afterwards, eight hydration orthophosphoric acid Asia cobalt is not added when additive slurry is prepared, and (normalization formula is Co (PO4)2/3·8/3H2O) powder Additive, specifically, first with 2500g water as solvent, by PTFE emulsion binding agent D210 dispersions, obtains the emulsion of binding agent, will The emulsion is coated uniformly on above-mentioned anode pole piece surface, and coating width is 162mm, to cover active substance, the two-sided face of dressing Density is 28.5g/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, except for the difference that, in step (1), is preparing additive slurry When does not add hydrated magnesium phosphate, and (normalization formula is Mg (PO4)0.6(HPO4)0.1·3/2H2O) powder additive, will 40g lead Electric agent Super-P, 50g binding agent HSV900 mixing, it is specifically, first with 2500g NMP as solvent, binding agent HSV900 is molten Solution, obtains the solution of binding agent, then mixes conductive agent Super-P with the solution of above-mentioned binding agent, and stirring afterwards forms equal Even 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 29.8g/m2(in terms of the weight after drying), then dries at 120 DEG C, obtains the aluminium foil for processing；
By 21500g cobalt acid lithiums LiCoO2Positive electrode, the mixing of 625g binding agent HSV900,875g conductive agents CNT, Concrete grammar 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 for processing, 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 anode pole piece that aluminium foil was processed.
Comparative example 4
Method according to embodiment 1 prepares lithium ion battery D4, except for the difference that, in step (1), will be hydrated chromic orthophosphate (CrPO4·7/2H2O) powder replaces with chromic orthophosphate (CrPO4) powder (not containing water of crystallization), wherein, chromic orthophosphate (CrPO4) Powder (not containing water of crystallization) will be by being hydrated chromic orthophosphate (CrPO4·7/2H2O) 500 DEG C of heat treatments 8 hours in air atmosphere, Subsequently comminution by gas stream is obtained, and measures wherein particle diameter D50 for 370nm.
Comparative example 5
Method according to embodiment 1 prepares lithium ion battery D5, except for the difference that, in step (1), eight hydration orthophosphoric acid are sub- (normalization formula is Co (PO to cobalt4)2/3·8/3H2O) powder replace with orthophosphoric acid Asia cobalt (normalization formula be Co (PO4)2/3, no Containing water of crystallization) powder, wherein, (normalization formula is Co (PO to orthophosphoric acid Asia cobalt4)2/3, without water of crystallization) and powder is by by eight water (normalization formula is Co (PO to close orthophosphoric acid Asia cobalt4)2/3·8/3H2O) 500 DEG C of heat treatments 8 hours in a nitrogen atmosphere, subsequent gas Stream crushing is obtained, and measures wherein particle diameter D50 for 310nm.
Comparative example 6
Method according to embodiment 1 prepares lithium ion battery D6, except for the difference that, in step (1), hydrated magnesium phosphate (is returned One changes formula for Mg (PO4)0.6(HPO4)0.1·3/2H2O (normalization formula is Mg (PO) to replace with magnesium phosphate4)0.6(HPO4)0.1, Without water of crystallization) powder, wherein, (normalization formula is Mg (PO to magnesium phosphate4)0.6(HPO4)0.1, without water of crystallization) and powder passes through By hydrated magnesium phosphate, (normalization formula is Mg (PO4)0.6(HPO4)0.1·3/2H2O) in air atmosphere 500 DEG C of heat treatments 8 are little When, subsequent comminution by gas stream is obtained, and measures wherein particle diameter D50 for 230nm.
Test example
The abuse test of cell
1st, test is overcharged
By cell (including lithium ion battery A1-A27 obtained in embodiment 1-27 and lithium obtained in comparative example 1-6 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-A27 obtained in embodiment 1-27 and lithium obtained in comparative example 1-6 Ion battery D1-D3) 4.25V is charged to the electric current of 30A, and constant-voltage charge is less than up to electric current under the voltage of 4.25V 1.5A.Battery is extruded 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, the phenomenon in observation and recording process after the completion of extruding.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-A27 obtained in embodiment 1-27 and lithium obtained in comparative example 1-6 Ion battery D1-D3) 4.25V is charged to the electric current of 30A, and constant-voltage charge is less than up to electric current under the voltage of 4.25V 1.5A.Battery is extruded 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, the phenomenon in observation and recording process after the completion of extruding.Respectively take 30 cells do parallel testing.The results are shown in Table 3.
4th, lancing test
By cell (including lithium ion battery A1-A27 obtained in embodiment 1-27 and lithium obtained in comparative example 1-6 Ion battery D1-D3) 4.25V is charged to the electric current of 30A, and constant-voltage charge is less than up to electric current under the voltage of 4.25V 1.5A.With a diameter of 6 millimeters of nails along perpendicular to the direction in battery length and width face, battery is at the uniform velocity passed through with the speed of 25mm/s, And stop one hour, the phenomenon in observation and 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, can significantly improve in the safety of the lithium ion battery for thus preparing, and the additive being introduced into contain There is water of crystallization, when the respective substance without water of crystallization is introduced, under abuse conditions, respective substance cannot effectively absorb battery heat Amount, thus do not have the effect for significantly improving battery security.
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 5.5-10.5 weight %, can further improve the lithium that thus prepares from The safety of sub- battery, and the lithium ion battery for preparing can also be further improved when additive amount further increases Safety under extremely harsh condition.
The results contrast of embodiment 1-4 in table 1-4 and embodiment 12-27 is understood, the additive is hydration orthophosphoric acid Chromium (CrPO4·7/2H2O), (normalization formula is Co (PO to eight hydration orthophosphoric acid Asia cobalts4)2/3·8/3H2) and hydrated magnesium phosphate O (normalization formula is Mg (PO4)0.6(HPO4)0.1·3/2H2During at least one in O), can further improve what is prepared The safety of lithium ion battery.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment Detail, the present invention range of the technology design in, 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 compound mode of energy is no longer separately illustrated.
Additionally, combination in any can also be carried out between a variety of embodiments of the present invention, as long as it is without prejudice to this 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(PO4)a(HPO4)b·cH2O, wherein, M is Group IIA metal element, IB races metallic element, Group IIB metal element, IIIB races gold Category element, Group IVB metallic element, group vib metallic element, VIIB races metallic element, group VIII metal element and metal unit of VA races It is 0, c when at least one element in element, a >=0, b >=0, and a, b are different>0.
2. application according to claim 1, wherein, in additive, the Group IIA metal element is Mg, the IB races gold Category element is Cu, and the Group IIB metal element is Zn, and IIIB races metallic element is Y, Sc, La, Ce, Nd, Sm, Gd and Er In at least one, the Group IVB metallic element is Ti and/or Zr, and the group vib metallic element is Cr, VIIB races gold Category element is Mn, and the group VIII metal element is at least one in Fe, Co and Ni, and VA races metallic element is Bi；
Preferably, the additive is CrPO4·7/2H2O、Co(PO4)2/3·8/3H2O and Mg (PO4)0.6(HPO4)0.1·3/ 2H2At 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 0.05-22 weight %, preferably 3-15 weight %, more preferably 5.5-10.5 weight %.
4. a kind of lithium ion battery electrode sizing agent, it is characterised in that the electrode slurry includes active substance, binding agent, conduction Agent, additive, solvent and optional thickening agent, on the basis of the weight of the active substance, the content of the additive is 0.05-30 weight %, preferably 2-19 weight %, more preferably 6-13 weight %；The additive is M (PO4)a (HPO4)b·cH2O, wherein, M be Group IIA metal element, IB races metallic element, Group IIB metal element, IIIB races metallic element, In Group IVB metallic element, group vib metallic element, VIIB races metallic element, group VIII metal element and VA races metallic element extremely A kind of few element, a >=0, b >=0, and a, b are 0, c when different>0；
Preferably, on the basis of the weight of the active substance, the binding agent is heavy as 0.5-5.5 with the content that butt is counted Amount %, the content of the conductive agent is 0.5-5.5 weight %, and the content of the solvent is 50-220 weight %, the thickening agent Content be 0-3 weight %；
Preferably, in additive, the Group IIA metal element be Mg, IB races metallic element be Cu, 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 gold Category element be Ti and/or Zr, the group vib metallic element be Cr, VIIB races metallic element be Mn, the group VIII metal Element is at least one in Fe, Co and Ni, and VA races metallic element is Bi；It is further preferred that the additive is CrPO4·7/2H2O、Co(PO4)2/3·8/3H2O and Mg (PO4)0.6(HPO4)0.1·3/2H2At least one in O；
Preferably, the active substance is 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, stannum and stannum oxide；
Preferably, the binding agent be polyacrylamide, polyvinylidene fluoride, politef, 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 N-Methyl pyrrolidone, deionized water, tetrahydrofuran, dimethyl sulfoxide, ethanol and isopropanol In at least one；
The thickening agent is at least one in sodium carboxymethyl cellulose, 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 content that the binding agent is counted with butt is described molten as 0.5-12 weight % The content of agent is 90-420 weight %, and the content of the conductive agent is 0-12 weight %；The additive is M (PO4)a (HPO4)b·cH2O, wherein, M be Group IIA metal element, IB races metallic element, Group IIB metal element, IIIB races metallic element, In Group IVB metallic element, group vib metallic element, VIIB races metallic element, group VIII metal element and VA races metallic element extremely A kind of few element, a >=0, b >=0, and a, b are 0, c when different>0；
Preferably, in additive, the Group IIA metal element be Mg, IB races metallic element be Cu, 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 gold Category element be Ti and/or Zr, the group vib metallic element be Cr, VIIB races metallic element be Mn, the group VIII metal Element is at least one in Fe, Co and Ni, and VA races metallic element is Bi；It is further preferred that the additive is CrPO4·7/2H2O、Co(PO4)2/3·8/3H2O and Mg (PO4)0.6(HPO4)0.1·3/2H2At least one in O；
Preferably, the binding agent be polyacrylamide, polyvinylidene fluoride, politef, butadiene-styrene rubber, cellulose base gather At least one in compound, polyvinyl alcohol, polyolefin, Viton and Polyurethane；
Preferably, the solvent is N-Methyl pyrrolidone, deionized water, tetrahydrofuran, dimethyl sulfoxide, 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 contains active substance, binding agent, conductive agent, additive and optionally Thickening agent, the additive be M (PO4)a(HPO4)b·cH2O, wherein, M be Group IIA metal element, IB races metallic element, Group IIB metal element, IIIB races metallic element, Group IVB metallic element, group vib metallic element, VIIB races metallic element, VIII It is 0, c when at least one element in race's metallic element and VA races metallic element, a >=0, b >=0, and a, b are different>0；
Preferably, in the additive, the Group IIA metal element be Mg, IB races metallic element be Cu, the Group IIB Metallic element is Zn, and IIIB races metallic element is at least one in Y, Sc, La, Ce, Nd, Sm, Gd and Er, the IVB Race's metallic element be Ti and/or Zr, the group vib metallic element be Cr, VIIB races metallic element be Mn, the VIII Metallic element is at least one in Fe, Co and Ni, and VA races metallic element is Bi；It is further preferred that the additive For CrPO4·7/2H2O、Co(PO4)2/3·8/3H2O and Mg (PO4)0.6(HPO4)0.1·3/2H2At least one in O；
Preferably, the active substance is 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, stannum and stannum oxide；
Preferably, the binding agent be polyacrylamide, polyvinylidene fluoride, politef, 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 thickening agent be sodium carboxymethyl cellulose, 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 0.05-22 weight %, preferably 3-15 weight %, more preferably 5.5-10.5 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 is coated on a current collector, drying；Or
(1) additive slurry described in claim 5 is coated on a current collector, drying obtains the collector of additive coating；
(2) active material slurry is prepared, the active material slurry includes active substance, binding agent, conductive agent, solvent and optionally Thickening agent, then the active material slurry is coated on the collector of the additive coating that step (1) obtains, drying； Or
(1) active material slurry is prepared, the active material slurry includes active substance, binding agent, conductive agent, solvent and optionally Thickening agent, then by the active material slurry coat 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 in portion and electrolyte, the battery core component includes 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.
CN201611260951.8A 2016-12-30 2016-12-30 Application of additive, electrode slurry, additive slurry, lithium ion battery positive electrode or negative electrode and preparation method therefor, and lithium ion battery Pending CN106601991A (en)

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