CN106876694A - For the new preprocess method of the active material of lithium ion battery - Google Patents

For the new preprocess method of the active material of lithium ion battery Download PDF

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CN106876694A
CN106876694A CN201611053434.3A CN201611053434A CN106876694A CN 106876694 A CN106876694 A CN 106876694A CN 201611053434 A CN201611053434 A CN 201611053434A CN 106876694 A CN106876694 A CN 106876694A
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negative electrode
pretreated
lithium
anode
lithium ion
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C.弗兰克
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Volkswagen AG
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Volkswagen AG
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • H—ELECTRICITY
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    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
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    • 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
    • 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
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    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract

The present invention relates to a kind of method for manufacturing pretreated negative electrode and a kind of method and a kind of thus obtained lithium ion battery for by pretreated electrode manufacture lithium ion battery.

Description

For the new preprocess method of the active material of lithium ion battery
Technical field
It is used for by pretreated electricity the present invention relates to a kind of method for manufacturing pretreated negative electrode and one kind The method and a kind of thus obtained lithium ion battery of pole manufacture lithium ion battery.
Background technology
Exploitation on alternative energy source is so as to the ultimate challenge of the discharge for reducing the gas for causing greenhouse effects, effectively The application that the obtained energy of storage is used in Mobile solution.Here, to the sphere of action for improving the vehicle that electricity runs The broad interest of the extension of solution and to mobile consumer products battery run time especially constitutes big manufacturer To the basis of the intensive R＆D work of new more effective battery technology.
At present, during lithium ion battery is considered as Mobile solution field, the key technology in especially electronic mobility field. Although in the past marked improvement in the past few years, it is still necessary to continue in manufacturing cost, weight, energy density, security and charging Further improvement in terms of time and cyclical stability.The energy density of commercial li-ion battery it is current in 170Wh/kg extremely Between 280Wh/kg.
Three significant components in lithium ion battery are negative electrodes（Anode）And positive electrode（Negative electrode）And electrolyte composition, The electrolyte composition can realize the reversible transmission between the two electrodes.Anode is main by three important part groups Into i.e. active material --- component, the conductive additive of lithium ion mainly can be reversibly stored wherein（For example it is conductive Carbon）--- the conductive additive improves the electric conductivity of electrode, and binding agent（It is mostly polymer）, the binding agent will be all Component is connected with each other and is played a decisive role for the mechanical stability of electrode.As the work in the anode of commercial batteries unit Property material, the at present carbon of main application form of graphite.In the cathode, lithium metal oxide is used mostly at present as active material Compound, such as cobalt acid lithium LiCoO2, LiMn2O4 LiMnO2, high manganese lithium LiMn2O4Or lithium-nickel-manganese-cobalt oxide LiNi0.33Mn0.33Co0.33O2.By researching and developing novel cathode material, the energy density of lithium ion battery can be further improved.This A little materials have voltage range higher compared to conventional use of cathode material（>4.5V）And referred to as 5V- negative electrodes.Can be pre- The candidate item seen is high-voltage spinel, such as LiMn1.5Ni0.5O4, the compound L i that high-energy is formed2MnO3-LiMO2（M= Mn、Cr、Co、Ni）With lithium metal phosphates LiMPO4（M=Mn、Fe、Co）.
The two electrodes are made up of the non-aqueous electrolyte of liquid or polymer/gel electrolyte is constituted and mutually interconnected Connect.The non-aqueous electrolyte composition of liquid has one or more organic solvent, dissolving lithium salts in organic solvent simultaneously mostly And generally there is additional additive, the additional additive has special feature.Lithium salts is, for example, lithium hexafluoro phosphate （LiPF6）, LiBF4（LiBF4）, lithium perchlorate（LiClO4）, hexafluoroarsenate lithium（LiAsF6）And dioxalic acid lithium borate （LiBOB）, difluorine oxalic acid boracic acid lithium（LiDFOB）, double fluorine sulfimide lithiums（LiFSI）Or double trifluoromethanesulfonimide lithiums （LiTFSI）.Organic solvent is typically the combination of cyclic carbonate salt or line style carbonate, such as propene carbonate（PC）, ethylene Alkene ester（EC）, dimethyl carbonate（DMC）, diethyl carbonate（DEC）And methyl ethyl carbonate（EMC）.
In order to the lithium ion battery for future realizes energy density higher, except research and development new electrode materials and electrolysis Be also there is a possibility outside matter composition, electrode is changed by suitable treatment so that be improvement active material and/or made The particular characteristics of the electrode made.
A kind of option for improving cathode specific capacity is, using element, such as silicon, tin, antimony, aluminium, magnesium and their alloy, The alloy can with lithium constitute compound and can reversibly store compared to the graphitic carbon that is used at present herein it is notable more Many lithiums.Here, silicon has the theoretical capacity of 3578mAh/g at room temperature, and in the case of graphitic carbon it is 372mAh/g.
A big problem in the use of commercial li-ion battery is, the big of lithium can not in the first circulating battery Inverse loss.There is the decomposition of the component in the electrolyte composition of liquid during the first charging cycle, because the component No longer stablize in terms of electrochemistry under the current potential for being used.Then, the product for being produced by reduction decomposition can be deposited On the anode surface and superficial layer is formed, the superficial layer is also referred to as " Solid Electrolyte Interphase：Solid electricity Solution matter interfacial film "（SEI）.In the case of the layer on negative electrode formed by electrolyte components oxidation Decomposition, refer to “Solid Permeable Interface：Solid osmotic interface "（SPI）.The formation of these superficial layers is for lithium ion battery Operation for have the advantage that and shortcoming.In the case where silicon anode or graphite anode is used, superficial layer advantageously causes The solvation shell of lithium ion present in the electrolyte composition of liquid is embedded in lithium（Interkalation）When be broken away.In nothing In the case of superficial layer, it is embedded in graphite through the lithium ion of solvation, this will cause the film of graphite to depart from, namely graphite Damage.Superficial layer formed in the case of one the disadvantage is that, the definite part of the lithium in battery unit in its formation can not It is consumed inversely and is next no longer able to participate in the electric charge transfer between electrode.Its reason is, the superficial layer has and contains The component of lithium.In the battery, therefore being formed for the superficial layer cause capacity and energy density during the first circulating battery Massive losses, this occurs with strengthening again in the case where anode material such as silicon is used.Its reason is, in embedding and removing The big volume range of period silicon.Here, the stability of superficial layer is reduced significantly and the superficial layer must be in the ring of battery Continuously re-formed during changing mechanism.From following：The formation of SEI is the anode with new anode material Current one of main reason of also inadequate cyclical stability.Occur due to the oxidation Decomposition of electrolyte components on the cathode side The formation of SPI, it has slowed down lithium diffusion.Additionally, transition metal is separated from electrode and causes SEI and electrolyte composition portion The enhanced catalytic decomposition divided.Under the operating voltage of the increase in lithium ion battery, additionally, oxygen departs from from crystal structure, The oxygen can carry out other side reactions with electrolyte components.This especially causes negative electrode during the first charge and discharge is circulated Novel high-energy material strong performance reduction and the irreversible loss of lithium.Correspondingly, it is right to exist in the prior art There is the big interest of the battery of specific capacity high in the case of cyclical stability high at the same time.
The T2 of DE 696 05 362 are related to a kind of for pre-processing the work on carbon anode by lithium deactivation and pre-wetted The method at property position.Before lithium ionic cell unit is built, by the carbon in the electrolyte solution that non-aqueous lithium ion is turned on The cathodization active site to deactivate carbon of anode.The pretreatment of the active site in carbon anode is used to especially be charged first Minimized with the irreversible loss of lithium ion is made during discharge cycles.
The B2 of US 8 067 107 disclose a kind of for preparing lithium ion battery consumed or power reduction again Method, wherein after the discharge that electric discharge is constituted with then electrolyte completely of battery, in the cleaning by postcritical liquid Waste products are removed from battery in step, and then adds new electrolyte composition.Original should occur by the method The maximum remanufacturing of beginning battery capacity.
The A1 of WO 2014/150050 are related to a kind of method for pre-processing the negative electrode used in lithium ion battery, its In encapsulate conductive material by ground floor first, the ground floor includes the subgroup element in race IIIB and/or the gold in race IV Category.In a further step, the second layer is coated, the second layer covers at least a portion of ground floor, and its floating coat composition is included Component containing lithium.
The content of the invention
Task of the invention is to provide a kind of method, thus improves the cyclical stability of lithium ion battery.
Task of the invention is solved particularly by the theme of independent claims.
According to the present invention, a kind of method for manufacturing pretreated negative electrode is set, wherein methods described includes following Step, especially comprises the steps of：
a）With relative to Li/Li in pretreatment electrolyte composition+It is the electrochemical window polarization negative electrode of 0.01V to 5.2V；
b）Obtain pretreated negative electrode.
By the polarization of negative electrode, pretreatment electrolyte constitutes the cathode surface for being decomposed and being formed stabilization at least in part Layer, also referred to as " solid osmotic interfacial film " or abbreviation SPI, this battery, preferably lithium ion battery by the negative electrode and anode, Before especially same pretreated anode is set up.By the cathode surface layer for having been formed, minimize or even prevent The further formation of cathode surface layer during the operation of battery namely during multiple charge and discharge process so that minimum Change, preferably prevent to be lost in the irreversible lithium after the first time of battery puts into operation in the first circulating battery.With anode, Especially pretreated anode --- anode has the anode surface of stabilization accordingly --- in combination, can be manufactured on energy Density, capacity, life-span and cyclical stability have the lithium ion battery of the characteristic being obviously improved.
Term is " relative to Li/Li+" be interpreted as according to the present invention, illustrate for electrode relative to reference electrode（As Lithium/the lithium ion of electrode/electrolyte）Polarization of the invention current potential.
In a preferred embodiment, immediately following step a）Ground is cleaned and preferred by least one carbonate solvents It is subsequently dried in step a）The negative electrode of middle pretreatment.In a preferred embodiment, according to step b）By at least one Kind of carbonate solvents are cleaned and are subsequently dried after electrode and obtain negative electrode.By the cleaning by least one carbonate solvents Step, preferably by all undesirable part removals come off from negative electrode so that these dirts do not disturb battery, excellent Select the follow-up operation of lithium ion battery.
Term " lithium ion battery " according to the present invention be not only interpreted as primary lithium ion battery and also be interpreted as secondary lithium from Sub- battery, is preferably understood that secondary lithium battery.Primary lithium ion battery is non-rechargeable ion battery；Secondary electricity Pond is rechargeable ion battery.
Term " different on material " is interpreted as, and two kinds of electrolyte compositions are different in terms of its component and/or concentration.
Term " cathode surface layer "（SPI）The coating of negative electrode is interpreted as, the coating is constituted by pretreatment electrolyte The polarization of middle negative electrode is manufactured.Correspondingly, preferred group through decompose of the cathode surface layer comprising pretreatment electrolyte composition Into part, wherein the part is preferably derived from least one carbonate solvents and at least one lithiumation is closed Thing, and preferably additionally also from least one film forming agent.
Term " anode surface layer "（SEI）The coating of anode is interpreted as, the coating is constituted by pretreatment electrolyte The polarization of Anodic is manufactured.Correspondingly, preferred group through decompose of the anode surface layer comprising pretreatment electrolyte composition Into part, wherein the part is preferably derived from least one carbonate solvents and at least one lithiumation is closed Thing, and preferably additionally also derive from least one film forming agent.
In order to according to step a）Polarized, negative electrode is carried out preferably together with counter electrode with pretreatment electrolyte composition Contact, is preferably immersed in pretreatment electrolyte composition, is preferably uniformly drawn by solution, and the counter electrode is preferably wrapped Containing lithium, stainless steel or platinum or it is made from it.
In another embodiment, in order to be polarized, negative electrode is directly built in lithium-ion electric with corresponding anode Contacted in pool unit and with pretreatment electrolyte composition.
In order in step a）Middle polarization negative electrode, negative electrode is preferably drawn with the speed for determining by pre-processing electrolyte composition Or be positioned at the determination position in pretreatment electrolyte composition, the position is during the whole polarization according to step a Do not change.
Preferably, according to step a）Polarization can closing container in or in following equipment occur, by institute Stating equipment can advantageously implement continuous process.
Preferably, do not pre-process in step a）In negative electrode to be polarized.Therefore, negative electrode is according to step a）Polarization before Not having preferably can be by polarization, preferably by according to step a）Polarization manufacture cathode surface layer.Preferably, in step Rapid a）In negative electrode to be polarized without can be by the cathode surface layer of the manufacture that polarizes.Advantageously, therefore can manufacture especially equal Even cathode surface layer.
Preferably, according to step a）Be polarized in relative to Li/Li+For 0.01V to 5.2V, preferably 0.1V to 5V, preferably Carried out in the electrochemical window of 0.5V to 4.8V.In the case of corresponding current potential, occur present in pretreatment electrolyte composition At least part of, preferably part the decomposition of component, is consequently formed cathode surface layer.
Preferably, according to step a）Be polarized under constant electric current with C/5- speed to C/10- speed relative to Li/ Li+It is wherein 1s to 10h, preferably 1min to 5h, preferably 2min to 4h, preferably 10min to 2h, excellent to be carried out on 0.5V to 5.2V Keep current potential with selecting 15min to 1h.
Term " C- speed " is interpreted as the relative charging current of the theoretic specific capacity at least one battery unit Or discharge current（Unit=A/Ah）.The charging current of 0.75C for example represents, with 0.75A to the battery list of the capacity with 1Ah Unit charges.
According to the present invention, term " xC/yC " expression, the C- speed that there is x when charging and the C- that there is y in electric discharge Speed.
Preferably, negative electrode is pre-processed by least one charge step/discharge step.By at least one charge step/ Discharge step constructs uniform cathode surface layer.
Preferably, at least one charge step/discharge step is implemented with the C- speed of C/5 to C/10.By with C/5 extremely Especially uniform and therefore stabilization the cathode surface layer of at least one charge step of the C- speed of C/10/discharge step construction.
Preferably specify, the constant current ground or real come constant potential ground by applying constant potential in the case of constant current Now according to step a）Polarization.
Preferably, in order to polarize, negative electrode is connected on voltage-stablizer or on galvanostat.
According to step a）Polarization preferably in 1s to 10h, preferably 1min to 5h, preferably 2min to 4h, preferably 10min extremely Carried out on the time period of 2h, preferably 15min to 1h.Alternatively, according to step a）Polarization preferably can reach it is desired Current potential after immediately again removed from the dielectric displacement.
Preferably, according to step a）Polarization at least 15min carry out longly.Obtained by the duration of at least 15min The cathode surface layer of stabilization so that cathode surface layer is almost also without damage during the operation of battery, preferably even no longer It is damaged.
Preferably as step a）In counter electrode, set lithium electrode, preferably platinum electrode or stainless steel electrode. This preferred embodiment in, the part that cathode surface layer is individually made up of pretreatment electrolyte is produced.Side of the invention Therefore method especially has advantages below：Before assembled battery namely in operation battery, especially before lithium ion battery, can be with Pre-processed.Therefore, it is also possible in particular to use counter electrode, such as lithium electrode, stainless steel electrode and platinum electrode, so as to according to step Rapid a）Polarization negative electrode and therefore construction cathode surface layer.Correspondingly, individually pretreatment electrolyte composition can be coordinated To on following, that is, construct highly stable superficial layer.In contrast, in battery, the especially operation of lithium ion battery, it is necessary to will Cyclisation electrolyte composition is also coordinated onto corresponding anode.
Preferably specify, just implementation steps a once）.It is therefore preferred that once apply just constant electric current or The constant current potential of person, so as to the negative electrode that polarizes.
According to step a）Polarization occur preferably in the case of in the absence of insulation component, preferred separator element.Therefore, According to step a）Polarization preferably without separator element.
By according to step a）Polarization realize pretreatment electrolyte composition it is at least one portion, preferably independent one Partial decomposition.Thus some components that will especially pre-process electrolyte composition are embedded into the cathode surface to be formed layer.Therefore, In step a）Middle application pretreatment electrolyte composition composition with implementation steps a）The decomposition at least in part for obtaining afterwards Pretreatment electrolyte constitute different on material.
Preferably specify, by negative electrode in step a）In with pretreatment electrolyte composition contacted and after polarization from Taken out in pretreatment electrolyte composition.
Alternatively, during pretreated negative electrode preferably rests in polarizer apparatus, the polarizer apparatus preferably also may be used simultaneously To be battery, preferably lithium ion battery, and pre-process electrolyte solution by cyclisation electrolyte solution and replace, or To decompose at least in part pretreatment electrolyte composition add other components again, especially at least a kind of lithium compound, so as to because This obtains cyclisation electrolyte composition.
Preferably, in step b）In pretreated negative electrode from pretreatment electrolyte composition in be removed and preferably land productivity Cleaned with least one carbonate solvents and preferably then dried.By cleaning step and drying steps, preferably Ground by it is all it is undesirable come off from negative electrode parts removal so that these dirts do not disturb battery, preferably lithium from The follow-up operation of sub- battery.
Preferably, in step b）In clean pretreated negative electrode by least one carbonate solvents.By by carbon The cleaning step of hydrochlorate solvent, preferably by all undesirable part removals come off from negative electrode so that these are dirty Thing does not disturb battery, preferred lithium ion battery follow-up operation.
Preferably, do not carry out in the method by postcritical liquid, preferably by the clear of postcritical carbon dioxide Wash step.The preferred cleaning of pretreated negative electrode is preferably carried out in the case of without postcritical carbon dioxide.
Preferably, the pretreatment of negative electrode is carried out in the case of without etching and/or without the heating more than 100 °C.Correspondingly, Implement without etching and/or at a temperature of≤100 °C for pre-processing the current method of negative electrode.
Preferably, after the cleaning step in inert environments, namely preferably exist in argon atmosphere or nitrogen scope The drying pretreated negative electrode at a temperature of 20 °C to 25 °C.
Rich nickel material, rich lithium material or high-voltage spinel are used preferably as cathode material.
It is Li [Li preferably as the high-voltage spinel that cathode material is usedxMn(2-x)]O4（0≤x≤1）、Lix [Ni(2-z)Mnz]O4（0≤z≤2）And/or Li [Mn(2-x)Zx]O4（Z=Mg、Al、Ti、Ca、Zn、Co、Cr、Fe、Si、B；0≤x≤ 1）.
The rich lithium material used preferably as cathode material is xLi2MnO3-(1-x)LiMO2（M=Mn、Ni、Co、Cr、 Fe、Al、Si、B、Ti、Ca）And/or xLi2MnO3-(1-x)Li[Co(1-x-y-z)MnxNiyMz]O2（M=Mg、Al、Ti、Ca、Zn、Co、 Cr、Fe、Si、B；0≤x, y, z≤1）.
It is Li [Co preferably as the rich nickel material that cathode material is used(1-y-z)NiyAlz]O2（0≤x, y, z≤1）With/ Or Li [Co(1-x-y-z)MnxNiyMz]O2（M=Mg、Al、Ti、Ca、Zn、Co、Cr、Fe、Si、B；0≤x, y, z≤1）.
Preferably, in the battery, preferably in lithium ion battery, for polarization use following negative electrode：As active material, The negative electrode has at least one lithium metal oxide compound, such as cobalt acid lithium LiCoO2, LiMn2O4 LiMnO2, high manganese lithium LiMn2O4, lithium-nickel-manganese-cobalt oxide LiNi0.33Mn0.33Co0.33O2Or its combination, preferably it is made up of them.
Preferably, in the battery, preferably in lithium ion battery, for polarization use high energy negative electrode, such as such the moon Pole, the negative electrode has high-voltage spinel LiMn1.5Ni0.5O4, high-energy formed compound L i2MnO3-LiMO2（M=Mn、 Cr、Co、Ni）, lithium metal phosphates LiMPO4（M=Mn、Fe、Co）Or its combination, preferably it is made up of them.By by height Can negative electrode be used to polarize, can further improve battery, preferred lithium ion battery energy density.
Preferably, negative electrode additionally has conducting polymer carbon.By the use in the cathode of conducting polymer carbon, favorably Ground ensures the electric conductivity high of negative electrode.
Preferably, negative electrode is made up of at least one lithium metal oxide and the conducting polymer carbon.Polymer is led The combination of electrical carbon and at least one lithium metal oxide advantageously assures that the electric conductivity high of negative electrode.
Following negative electrode is preferably used alternatively as negative electrode：The negative electrode have sulphur as active material of cathode and With conducting polymer carbon, preferably it is made up of the above.
Preferably, pretreatment electrolyte composition includes at least one carbonate solvents and at least one lithium compound, especially It is made up of them.By the presence of at least one carbonate solvents and at least one lithium compound, advantageously construct Highly stable cathode surface layer.
Preferably, pretreatment electrolyte composition is additionally comprising at least one film forming agent.Can be sunk by least one The presence of long-pending film forming agent, advantageously constructs particularly stable cathode surface layer.
Preferably, pretreatment electrolyte composition is by least one carbonate solvents, at least one lithium compound Constituted with least one film forming agent.
Preferably, at least one carbonate solvents are selected from the following group, and described group consists of：Ethylene carbonate （EC）, propene carbonate（PC）, diethyl carbonate（DEC）, dimethyl carbonate（DMC）, fluorinated ethylene carbonate（FEC）, difluoro For ethylene carbonate, vinylene carbonate（VC）, vinylethylene carbonate（VEC）, methyl ethyl carbonate（EMC）With its mixture.
Preferably, at least one lithium compound is selected from the group for consisting of：Lithium hexafluoro phosphate（LiPF6）, two grass Sour lithium borate（LiBOB）, difluorine oxalic acid boracic acid lithium（LiDFOB）, hexafluoroarsenate lithium（LiAsF6）, lithium perchlorate（LiClO4）, it is double Fluorine sulfimide lithium（LiFSI）, it is double（Trimethyl fluoride sulfonyl）Imine lithium（LiTFSI）, LiBF4（LiBF4）, ethylenediamine tetraacetic Lithium acetate（Li-EDTA）, lithium hydroxide（LiOH）, lithium nitrate（LiNO3）, lithium citrate and its mixture.
Preferably, at least one lithium compound is with the amount of 0.01 to 5wt%, preferably 0.5 to 2wt%, preferably 1wt%（Point Not on the gross weight of pretreatment electrolyte composition）It is present in pretreatment electrolyte composition.
Preferably, dioxalic acid lithium borate is with the amount of 0.01wt% to 5wt%, preferably 0.5wt% to 2wt%, preferably 1wt%（Respectively Gross weight on pretreatment electrolyte composition）It is present in pretreatment electrolyte composition.Preferably, lithium nitrate is with 0.01wt% To the amount of 5wt%, preferably 0.1wt% to 1wt%, preferably 0.5wt%（Respectively about the gross weight of pretreatment electrolyte composition）In the presence of In pretreatment electrolyte composition.
Preferably, at least one film forming agent is selected from the group for consisting of：Three pentafluorophenyl boranes（TPFPB）, three （Pentafluorophenyl group）Phosphine（TPFPP）, succinyl oxide, vinylacetate（VA）, 3- hexylthiophenes, hexafluoroisopropanol（HFIP）, carbon Hydrochlorate, ester compounds and its mixture.
Preferably, pretreatment electrolyte composition includes fluorinated ethylene carbonate（FEC）, dioxalic acid lithium borate（LiBOB）With Lithium nitrate, is especially made up of them.
Preferably, pretreatment electrolyte composition includes at least one carbonate solvents, at least one lithium compound and at least A kind of film forming agent, is especially made up of these, wherein at least one carbonate solvents are selected from the group for consisting of：Fluoro carbon Vinyl acetate, difluorinated ethylene carbonate, vinylene carbonate, diethyl carbonate, propene carbonate and its mixture, and its Described at least one lithium compound be selected from the group that consists of：Lithium nitrate, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, Double fluorine sulfimide lithiums and its mixture, and wherein described at least one film forming agent is selected from succinyl oxide.
According to the present invention, pretreatment electrolyte composition and cyclisation electrolyte composition can be identical on material or not Together.Preferably, in step a）The also undecomposed pretreatment electrolyte composition of middle application with it is preferably applying and also without extremely The cyclisation electrolyte composition for partially decomposing is different.By pre-processing electrolyte is constituted and cyclisation electrolyte group Into different material compositions application, the structure that electrolyte composition is coordinated to highly stable cathode surface layer can be pre-processed Make and coordinate onto the anode applied and/or negative electrode of lithium ion battery cyclisation electrolyte composition.
According to the present invention, a kind of method for manufacturing pretreated lithium ion battery is set, methods described include with Lower method and step, especially it is made up of following methods step：
aa）According to this teaching, especially method and step a）And b）Pretreated negative electrode is manufactured,
bb）Anode is provided, and
cc）Build the lithium ion battery with pretreated negative electrode and anode.
In for the method for manufacturing pretreated lithium ion battery, advantageously in method and step a）Middle construction is cloudy Pole superficial layer and minimize or even prevent during the operation of battery namely during multiple charge and discharge process cloudy The further formation of pole superficial layer so that minimize, preferably prevent after the first time of battery puts into operation in the first battery Irreversible lithium loss in circulation.
In another embodiment, for manufacturing the method for pretreated lithium ion battery for providing anode Step bb）Include the manufacture of pretreated anode, the manufacture of the pretreated anode includes following methods step, especially It is made up of following methods step：
i）With relative to Li/Li in pretreatment electrolyte composition+It is the electrochemical window polarization anode of 0.01V to 3V；And
ii）Pretreated anode is obtained, wherein in a preferred embodiment, by least one carbonate solvents Clean and be subsequently dried and obtain pretreated anode after electrode.
In for the method for manufacturing pretreated lithium ion battery, advantageously in method and step a）And i）Middle structure Cathode surface layer and anode surface layer are made, and is minimized or is even prevented during the operation of battery namely repeatedly filling The further formation of cathode surface layer and anode surface layer during electricity and discharge process so that minimize, preferably prevent in battery First time put into operation after in the first circulating battery irreversible lithium loss.
With reference to of the invention or shown for manufacturing the method for pretreated negative electrode according to currently preferred On pre-process electrolyte solution composition technical teaching make it is necessary amendment be also suitable for it is preprocessed for manufacturing Anode method.
Preferably, in step i）Pretreated anode is removed and preferably root from pretreatment electrolyte composition afterwards According to step ii）Cleaned using at least one carbonate solvents and preferably then dried.By by least one carbonic acid The cleaning step of salt solvent, preferably by all undesirable part removals come off from anode so that these dirts Battery, preferred lithium ion battery follow-up operation is not disturbed.
Preferably, do not carry out in the method by postcritical liquid, preferably by the clear of postcritical carbon dioxide Wash step.The preferred cleaning of pretreated anode is preferably carried out in the case of without postcritical carbon dioxide.
Preferably, the pretreatment of anode is carried out in the case of the heating without etching and/or no more than 100 °C.Therefore, use Implement without etching and/or at a temperature of≤100 °C in the current method of pretreatment anode.
Immediately following step bb）Ground, assembles battery to be run, preferably lithium ion battery.Therefore, by anode, preferably through pre- place The anode of reason is incorporated into battery unit, preferably full battery unit or half-cell unit relative to pretreated negative electrode. Between two electrodes, namely it is introduced in anode, between especially pretreated anode and negative electrode, especially pretreated negative electrode Few insulation component, preferably at least one separator element, wherein at least one insulation component is electrolysed with cyclisation Matter composition contact, is impregnated with preferably by it.
Constituted as cyclisation electrolyte, preferably use the electrolyte composition or solid of gel electrolyte composition, liquid Body electrolyte is constituted.Solid electrolyte composition is preferably polymer dielectric composition or ceramic electrolyte composition.
Preferably, cyclisation electrolyte composition has at least one carbonate solvents and at least one lithium compound, excellent Choosing is made from it.
Preferably, at least one carbonate solvents in cyclisation composition are selected from the group for consisting of：Ethylene carbonate Ester（EC）, propene carbonate（PC）, diethyl carbonate（DEC）, dimethyl carbonate（DMC）, fluorinated ethylene carbonate（FEC）, two Fluorinated ethylene carbonate, vinylene carbonate（VC）, vinylethylene carbonate（VEC）, methyl ethyl carbonate（EMC）With its mixing Thing.
Preferably, at least one lithium compound in cyclisation composition is selected from the group for consisting of：Lithium hexafluoro phosphate （LiPF6）, dioxalic acid lithium borate（LiBOB）, difluorine oxalic acid boracic acid lithium（LiDFOB）, hexafluoroarsenate lithium（LiAsF6）, lithium perchlorate （LiClO4）, double fluorine sulfimide lithiums（LiFSI）, it is double（Trimethyl fluoride sulfonyl）Imine lithium（LiTFSI）, LiBF4 （LiBF4）, ethylenediamine tetra-acetic acid lithium（Li-EDTA）, lithium hydroxide（LiOH）, lithium nitrate（LiNO3）, lithium citrate and its mixing Thing.
According to the present invention, a kind of lithium ion battery is set, the lithium ion battery is pre- comprising the warp manufactured according to this teaching The negative electrode for the treatment of.
According to the present invention, a kind of lithium ion battery is set, the lithium ion battery is according to for manufacturing pretreated lithium The method manufacture of ion battery, methods described includes following methods step, is especially made up of following methods step：
aa）According to this teaching, especially method and step a）And b）Pretreated negative electrode is manufactured,
bb）Anode is provided, and
cc）Build the lithium ion battery with pretreated negative electrode and anode.
In the lithium ion battery manufactured according to the method for manufacturing pretreated lithium ion battery of the invention In, advantageously in method and step a）The cathode surface layer of middle construction of stable, thus minimizes or even prevents in battery Operation during namely during multiple charge and discharge process cathode surface layer further formation so that minimize, it is excellent Choosing is prevented in the irreversible lithium loss after the first time of battery puts into operation in the first circulating battery.
According to the present invention, a kind of lithium ion battery is set, the lithium ion battery is according to for manufacturing pretreated lithium The current method manufacture of ion battery, methods described includes following methods step, is especially made up of following methods step：
aa）According to this teaching, especially method and step a）And b）Pretreated negative electrode is manufactured,
bb）The manufacture of pretreated anode is comprised the following steps：
i）With relative to Li/Li in pretreatment electrolyte composition+ It is the electrochemical window polarization anode of 0.01V to 3V；And
ii）Pretreated anode is obtained, wherein in a preferred embodiment, by least one carbonate solvents Clean and be subsequently dried and obtain pretreated anode after anode；And
cc）Build the lithium ion battery with pretreated negative electrode and pretreated anode.
In the lithium ion battery manufactured according to the method for manufacturing pretreated lithium ion battery of the invention In, advantageously in method and step a）And i）Middle construction of stable cathode surface layer and anode surface layer, thus minimize or Person even prevents cathode surface layer and anode surface during the operation of battery namely during multiple charge and discharge process Layer further formation so that minimize, preferably prevent after the first time of battery puts into operation in the first circulating battery Irreversible lithium loss.
There is provided a kind of lithium ion battery according to the present invention, wherein the battery have at least one pretreated negative electrode, Preferably proper what a pretreated negative electrode, at least one insulation component, a kind of cyclisation electrolyte composition and at least Individual anode, especially pretreated anode, preferably proper what a anode, especially pretreated anode.Pretreated negative electrode According to step a in by being constituted in pretreatment electrolyte）Negative electrode is polarized to manufacture.Pretreated anode is by pretreatment electricity According to step i in solution matter composition）Anode is polarized to manufacture.
In a preferred embodiment, electrical insulation parts are separator elements.Preferably, lithium ion battery has extremely A few separator element, preferably at least two separator elements, preferably lucky two separator elements, preferably for each sun Pole-negative electrode preferably proper what a separator element for.Preferably, at least one separator element is constituted with electrolyte It is impregnated with, preferably with every cm at least one separator element preferably in development test battery unit2For 100 μ L extremely The amount of 500 μ L is impregnated with, or preferably with every at least one separator element preferably in full battery unit cm2It is impregnated with for the amount of 5 μ of μ L to 50 L, especially to reduce the weight of battery.Preferably, at least one separator unit Part be micropore, preferably ceramic and heat-resisting diaphragm, the diaphragm is transparent or described diaphragm for ion It is polyolefin separator element.
With reference to it is of the invention or according to the currently preferred method on pretreatment electrolyte solution The technical teaching of composition is also suitable for manufacturing battery, preferably lithium ion battery with making necessary amendment.
Preferred configuration of the invention is drawn by dependent claims.
Brief description of the drawings
The present invention is elaborated according to the following drawings and embodiment.
Here,
Fig. 1 shows there is not pretreated or pretreated rich lithium during charge and discharge in forming step The voltage-capacity curve of the lithium ionic cell unit of NMC negative electrodes；
Fig. 2 shows the from first to the 80th lithium ion of the circulation with not pretreated and pretreated rich lithium NMC negative electrodes The residual capacity of battery.
Specific embodiment
Fig. 1 shows there is not pretreated or pretreated richness during charge and discharge in forming step The voltage-capacity curve of the lithium ionic cell unit of lithium NMC negative electrodes, wherein voltage U are said with volt and specific capacity c with mAh/g It is bright.Here, the lithium ionic cell unit with not pretreated or pretreated NMC negative electrodes in forming step by Fluorinated ethylene carbonate（FEC）, 1wt% dioxalic acid lithium borate（LiBOB）With the lithium nitrate of 0.5wt%（LiNO3）The ring of composition Change effect electrolyte solution under C/15- speed in the voltage range of 4.6-2.5V charging and discharging.Here, curve 1 is retouched The voltage-capacity curve and curve 2 of the lithium ion battery with not pretreated NMC negative electrodes when charging is stated to describe putting The voltage-capacity curve of the lithium ion battery with not pretreated NMC negative electrodes when electric.Curve 3 shows have when charging The voltage-capacity curve and curve 4 of the lithium ion battery of pretreated NMC negative electrodes show electric discharge when have it is preprocessed NMC negative electrodes lithium ion battery voltage-capacity curve.
Diagram 2 show from first to the 80th circulation with not pretreated and pretreated rich lithium NMC lithium from The residual capacity of sub- battery, wherein residual capacity CRIllustrated with % and period n is nondimensional.The pretreatment of NMC negative electrodes exists By fluorinated ethylene carbonate（FEC）, 1wt% dioxalic acid lithium borate（LiBOB）And lithium nitrate（LiNO3）The pretreatment electricity of composition Realized under C/15- speed in solution matter composition.Put completely respectively when the two lithium ion batteries are in 1C/1C- speed and at 23 °C Circulated respectively under electricity 80 times.The residual capacity of the lithium ion battery with not pretreated NMC negative electrodes（Curve 10）Compared to In lithium ion battery with pretreated NMC negative electrodes（Curve 11）Reduce significantly strongerly during circulation change.
Example
Example 1
The LiNO of the LiBOB and 0.5wt.% of 1wt.% is wherein dissolved325mL FEC be used as pretreatment electrolyte composition.In advance Treatment electrolyte composition is filled into container and then corresponding electrode is introduced in pretreatment electrolyte composition in succession And it is connected in potentiostat/galvanostat as working electrode in electrochemistry.Element lithium is used as counter electrode.Anode by The constant current of C/10 is relative to Li/Li+To be polarized on 25mV and the current potential is kept 2 hours.Negative electrode by The constant current of C/10 is relative to Li/Li+To be polarized on 4.8V and it is kept 30 minutes.Then, two electrodes are borrowed DMC is helped to clean.Pretreated electrode is installed in full battery unit after drying, and its mode is, the electrode it Between place separator, the separator is impregnated with 500 μ l electrolyte.Then, battery unit is fast with different C- in electrochemistry Rate is circulated.
Example 2
The LiDFOB and 0.5wt.% that are dissolved with 4wt.% wherein being made up of difluorinated ethylene carbonate and propene carbonate Maleic anhydride 50mL mixtures be used as pretreatment electrolyte composition.The pretreatment electrolyte composition is filled into appearance In device and then by 94wt.% xLi2MnO3(1- x)Li（NiαCoßMnγ）O2, 4wt.% PVDF, 2wt.% conductive black groups Into electrode be introduced in pretreatment electrolyte composition and in electrochemistry be connected to voltage-stablizer/perseverance as working electrode On stream device.Platinum is used as counter electrode.Then, disposably with the constant current of C/5 between 4.6-2.5V polarization cell unit.Electricity It is pressed at 4.6V and is kept for 2 hours.Then, electrode by EMC cleaning, dry and in half-cell unit relative to lithium in electrification Tested on.
Example 3
The 10mL mixtures being made up of FEC/ ethyl fluoroacetates of 4wt.% VTMS and 2wt.% succinyl oxides have been dissolved wherein Pretreatment electrolyte composition as Si/C anodes.Solution be filled into container and soak by 6.7wt.% silicon, The graphite of 83.3wt.%, the PAA binding agents of 2wt.% and 8wt.% conductive black composition anode and as working electrode come Connection.Platinum sheet is used as counter electrode.Electrode is directly relative to Li/Li+To be polarized on 20mV and kept for 4 hours. The 30mL mixtures being made up of ethyl difluoro for wherein having dissolved the hexyl thiophene of the LiDFOB and 2wt.% of 3wt.% are used as The preprocessing solution of high energy negative electrode.The solution is transferred in container and by the LiNi of 90wt.%6Mn2Co2O2, 2wt.% stone The electrode of the conductive black composition of ink, the PVDF binding agents of 4wt.% and 4 wt.% is introduced in solution and in electrochemistry Measured as the working electrode relative to lithium.Half-cell unit is by the constant current charge of C/8 on 4.8V and the electricity Pressure is kept for 5 hours.Two pretreated electrodes are cleaned, dry and then with standard electrolyte（LP71）It is complete It is measured in electrochemistry in battery unit.
Reference numerals list
1. there is the voltage-capacity curve of not pretreated NMC negative electrodes in charging process
2. there is the voltage-capacity curve of not pretreated NMC negative electrodes in discharge process
3. there is the voltage-capacity curve of pretreated NMC negative electrodes in charging process
4. there is the voltage-capacity curve of pretreated NMC negative electrodes in discharge process
10. there is the residual capacity of undressed NMV negative electrodes during circulation change
11. residual capacities during circulation change with the NMV negative electrodes through processing.

Claims (14)

1. the method for being used to manufacture pretreated negative electrode, wherein the described method comprises the following steps：
a）With relative to Li/Li in pretreatment electrolyte composition+It is the electrochemical window polarization negative electrode of 0.01V to 5.2V；
b）Obtain pretreated negative electrode.
2. method according to claim 1, it is characterised in that according to step a）The negative electrode of pretreatment is in step b）In borrowing At least one carbonate solvents are helped to be obtained after cleaning and being subsequently dried electrode.
3. method according to claim 1 and 2, it is characterised in that use rich nickel material, rich lithium material as cathode material Or high-voltage spinel.
4. the method according to any one of the preceding claims, it is characterised in that the pretreatment electrolyte composition includes At least one sprotic carbonate solvents and at least one lithium compound.
5. the method according to any one of the preceding claims, it is characterised in that the pretreatment electrolyte composition is included At least one film forming agent.
6. the method according to any one of the preceding claims, it is characterised in that constant current ground or the setting of constant potential ground are simultaneously And preferably keep according to step a）Current potential.
7. the method according to any one of the preceding claims, it is characterised in that by least one charge step/electric discharge Step pre-processes the negative electrode.
8. the method according in claim 7, it is characterised in that implement at least one with the C- speed of C/5 to C/10 and fill Electric step/discharge step.
9. the method according to any one of the preceding claims, it is characterised in that in step a）In continuously with determine Speed draws at least one negative electrode by the pretreatment electrolyte solution.
10. the method for being used to manufacture pretreated lithium ion battery, methods described includes：
aa）Pretreated negative electrode according to any one of claim 1 to 9 is manufactured,
bb）Anode is provided, and
cc）Build the lithium ion battery with pretreated negative electrode and anode.
11. methods for manufacturing pretreated lithium ion battery according to claim 10, the sun provided in it Pole is pretreated anode and is manufactured by following：
i）With relative to Li/Li in pretreatment electrolyte composition+It is the electrochemical window polarization anode of 0.01V to 3V；
ii）Obtain pretreated anode.
12. methods according to claim 11, it is characterised in that according to step i）The anode of pretreatment is in step ii）In Obtained after cleaning and being subsequently dried electrode by least one carbonate solvents.
A kind of 13. lithium ion batteries, it is manufactured according to any one of claim 10,11 or 12.
A kind of 14. lithium ion batteries, it includes the pretreated negative electrode manufactured according to any one of claim 1 to 9.
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