CN110100335A - Lithium ion battery and preparation method thereof - Google Patents

Lithium ion battery and preparation method thereof Download PDF

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Publication number
CN110100335A
CN110100335A CN201680091755.4A CN201680091755A CN110100335A CN 110100335 A CN110100335 A CN 110100335A CN 201680091755 A CN201680091755 A CN 201680091755A CN 110100335 A CN110100335 A CN 110100335A
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China
Prior art keywords
lithium
lithium ion
ion battery
anode
cathode
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Inventor
杨军
别依田
张晶晶
窦玉倩
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Robert Bosch GmbH
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Robert Bosch GmbH
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
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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
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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
    • H01M10/056—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
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    • 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
    • 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
    • H01M4/0447—Forming after manufacture of the electrode, e.g. first charge, cycling of complete cells or cells stacks
    • H—ELECTRICITY
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    • H01M4/04—Processes of manufacture in general
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    • H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
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    • 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
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
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    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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    • 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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    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

A kind of new type lithium ion battery is provided, it includes anode, cathode and electrolyte, wherein the anode includes positive electrode active materials and lithium peroxide.Additionally provide the method for preparing lithium ion battery.

Description

Lithium ion battery and preparation method thereof
Technical field
The present invention relates to lithium ion batteries and preparation method thereof.
Background technique
Lithium ion battery is widely used in energy-storage system and electric vehicle now.
For comprising containing lithium anode material (such as LiCoO2Or LiNiO2), without lithium titanate cathode material (such as graphite) and electrolysis The lithium ion battery of liquid, in charging, lithium ion is mobile from positive to cathode.However, mobile lithium ion inevitably connects It is continuous to be reacted with electrolyte.Therefore, lithium is undesirably consumed, and forms solid electrolyte interface (SEI) on cathode.Disappeared The lithium of consumption, not back to anode, leads to the capacity rapid decay of lithium ion battery during after discharge.
It has proposed to be coated with additional lithium powder or lithium nitride on cathode, by cathode prelithiation and compensation capacity is decayed. Then, the cathode of prelithiation is assembled into lithium ion battery.However, since lithium powder has high activity, after prelithiation step Cell manufacturing process require operating environment humidity be well controlled, which increase the preparation costs of lithium ion battery.
Constant demand can provide more attractive and the method for more reliable lithium ion battery.
Summary of the invention
After extensive research, present inventors have developed a kind of new type lithium ion batteries, and it includes anodes, cathode And electrolyte, wherein the anode includes positive electrode active materials and lithium peroxide.
In some instances, the lithium ion battery is prelithiation or non-prelithiation, and is based on positive electrode composition Gross dry weight, the content of lithium peroxide is greater than 0 to the about 20 weight % of weight %, preferably greater than 0 to less than 20, more preferably from about 0.01 weight % to about 5 weight %, even more preferably about 0.01 weight % are to about 1 weight %.
Preparation is additionally provided according to the method for the lithium ion battery of the disclosure comprising:
-- the anode comprising positive electrode active materials and lithium peroxide is provided；With
-- the anode, cathode and electrolyte are assembled into lithium ion battery；Optionally
-- the lithium ion battery is charged, so that lithium ion is released from the lithium peroxide in the anode, and The cathode stores lithium, thus by the cathode prelithiation,
Wherein based on the gross dry weight of positive electrode composition, lithium peroxide is in the battery of the prelithiation or the battery of non-prelithiation In content be greater than 0 to the about 20 weight % of weight %, preferably greater than 0 to less than 20, more preferably from about 0.01 weight % to about 5 weights Measure %, even more preferably about 0.01 weight % to about 1 weight %.
A kind of lithium ion battery is additionally provided, it includes anode, cathode and electrolyte, wherein the electrolyte includes lithium Salt, nonaqueous solvents and lithium peroxide.
Preparation is additionally provided according to the method for the lithium ion battery of the disclosure comprising:
-- the electrolyte comprising lithium salts, nonaqueous solvents and lithium peroxide is provided；
-- the electrolyte, anode and cathode are assembled into lithium ion battery；Optionally
-- the lithium ion battery is charged, so that lithium ion is released from the lithium peroxide in the electrolyte, and Lithium is stored in the cathode, thus by the cathode prelithiation.
The present inventor has found for the first time, it can be advantageous to peroxide is used in the anode or electrolyte of lithium ion battery Change lithium (Li2O2) as by the lithium source of cathode prelithiation.By using lithium peroxide by the cathode prelithiation of lithium ion battery, It can be decayed with compensation capacity, and battery performance (such as irreversible capacity and cyclical stability) can be significantly improved.
For being coated with lithium powder or lithium nitride on cathode in the prior art with by the proposal of cathode prelithiation, on the one hand, lithium Powder releases hydrogen when reacting with water to having high activity in the moisture in atmosphere, therefore when using lithium powder in the battery There are the risks of explosion.Equally, lithium nitride also with the reaction of moisture in air and generate spark.On the other hand, it is applied on cathode Cloth lithium powder is completed by additional spraying, sputtering or deposition step.In order to meet the requirement for implementing the additional step, need Change other components of cathode composition, such as adhesive and solvent.
In contrast, lithium peroxide used in the disclosure is relatively stable to moisture.Even if lithium peroxide is anti-with moisture It answers, the risk for also not generating gas, therefore not exploding which greatly improves production security and reduces production cost. In addition, the introducing of lithium peroxide can be integrated with the addition of other components of positive electrode composition or electrolyte composition, not separately It is outer to need individual step or need special condition, for industrial production, it means that considerable cost savings and International Labour Day About.
Detailed description of the invention
From subsequent detailed description, the other feature and advantage of the disclosure be will become obvious, in conjunction with attached drawing, together The feature of the technology is illustrated in an illustrative manner；Wherein:
Fig. 1 compares the charge/discharge curve with the battery of comparative example preparation in accordance with an embodiment of the present disclosure.
Fig. 2 compares the cycle performance with the battery of comparative example preparation in accordance with an embodiment of the present disclosure.
Fig. 3 compares the charge/discharge curve with the battery of comparative example preparation in accordance with an embodiment of the present disclosure.
Fig. 4 compares the cycle performance with the battery of comparative example preparation in accordance with an embodiment of the present disclosure.
Fig. 5 shows the charge/discharge curve of the battery prepared in accordance with an embodiment of the present disclosure.
Fig. 6 shows the cycle performance of the battery prepared in accordance with an embodiment of the present disclosure.
Fig. 7 compares the charge/discharge curve with the battery of comparative example preparation in accordance with an embodiment of the present disclosure.
Fig. 8 compares the cycle performance with the battery of comparative example preparation in accordance with an embodiment of the present disclosure.
Fig. 9 shows the charge/discharge curve of the battery prepared in accordance with an embodiment of the present disclosure.
Figure 10 shows the cycle performance of the battery prepared in accordance with an embodiment of the present disclosure.
Figure 11 compares the charge/discharge curve with the battery of comparative example preparation in accordance with an embodiment of the present disclosure.
Figure 12 compares the cycle performance with the battery of comparative example preparation in accordance with an embodiment of the present disclosure.
Figure 13 compares the charge/discharge curve with the battery of comparative example preparation in accordance with an embodiment of the present disclosure.
Figure 14 compares the cycle performance with the battery of comparative example preparation in accordance with an embodiment of the present disclosure.
These examples are described referring now to some illustrative examples, and by language-specific used herein.So And, it should be understood that, it is not intended to thus limit the scope of the present disclosure.
Specific embodiment
The disclosure full text, unless otherwise stated, all scientific and technical terminologies should have with it is known to those skilled in the art The identical meaning of meaning.When there are inconsistent, the definition provided in the disclosure should be taken.
It should be appreciated that being to provide for illustrative purposes to the detailed description of all material, method, example and attached drawing , therefore, unless expressly stated otherwise, otherwise these detailed descriptions are not interpreted the limitation to the disclosure.
Herein, term " battery (cell) " and " battery (battery) " are used interchangeably.Term " lithium ion battery (lithium ion cell (or battery)) " can also be abbreviated as " battery (cell) " and " battery (battery) ".
Herein, term "comprising" refers to may include the other ingredients for not influencing final effect or other steps.The art Language cover term " by ... form " and " substantially by ... form ".It may include following spy according to the product of the disclosure and method Sign is made of following characteristics and is substantially made of following characteristics: the essential features and/or limit of the disclosure as described herein System and any additional and/or optional compositions, component, step or limitation as described herein.
Herein, term " positive electrode composition " or " cathode composition ", which are intended to indicate that, is used to form anode sizing agent or cathode The composition of slurry.Anode sizing agent or negative electrode slurry are subsequently applied on corresponding collector and drying is positive or negative to be formed Pole.
Unless otherwise indicated herein or it is apparently contradicted in the context.In the context of the theme of description the application (especially in the context of appended claims) should be interpreted to cover using term "an" (" a ", " an ") and " described " Sheet number and plural number.
Unless otherwise stated, each numberical range in this context is intended to include two endpoints and falls into the number Any number and the subrange being worth in range.
Unless otherwise indicated, otherwise all material and reagent used in the disclosure are all commercially available.
The example of the detailed hereafter disclosure.
Lithium ion battery
In some instances, a kind of lithium ion battery is provided, it includes anode, cathode and electrolyte, wherein the anode Include positive electrode active materials and lithium peroxide.
In some instances, the lithium ion battery is prelithiation or non-prelithiation, and is based on positive electrode composition Gross dry weight, the content of lithium peroxide is greater than 0 to the about 20 weight % of weight %, preferably greater than 0 to less than 20, more preferably from about 0.01 weight % to about 5 weight %, even more preferably about 0.01 weight % are to about 1 weight %.
In some instances, it prepares according to the method for the lithium ion battery of the disclosure and includes:
-- the anode comprising positive electrode active materials and lithium peroxide is provided；With
-- the anode, cathode and electrolyte are assembled into lithium ion battery；Optionally
-- the lithium ion battery is charged, so that lithium ion is released from the lithium peroxide in the anode, and The cathode stores lithium, thus by the cathode prelithiation,
Wherein based on the gross dry weight of positive electrode composition, lithium peroxide is in the battery of the prelithiation or the battery of non-prelithiation In content be greater than 0 to the about 20 weight % of weight %, preferably greater than 0 to less than 20, more preferably from about 0.01 weight % to about 5 weights Measure %, even more preferably about 0.01 weight % to about 1 weight %
In some instances, a kind of lithium ion battery is provided, the lithium ion battery includes anode, cathode and electrolysis Liquid, wherein the electrolyte includes lithium salts, nonaqueous solvents and lithium peroxide.
In some instances, it prepares according to the method for the lithium ion battery of the disclosure and includes:
-- the electrolyte comprising lithium salts, nonaqueous solvents and lithium peroxide is provided；
-- the electrolyte, anode and cathode are assembled into lithium ion battery；Optionally
-- the lithium ion battery is charged, so that lithium ion is released from the lithium peroxide in the electrolyte, and Lithium is stored in the cathode, thus by the cathode prelithiation.
It is surprisingly found by the inventors that by providing the lithium ion battery according to the disclosure, on the one hand, SEI can be stablized, it can It is lost and is decayed with compensation capacity, and battery performance (such as irreversible capacity and cyclical stability) can be significantly improved.It is another Aspect, can be to avoid undesirable Li dendrite.
Lithium peroxide used in the disclosure is relatively stable to moisture.Even if lithium peroxide and reaction of moisture, also do not generate Gas, therefore the risk that do not explode, which greatly improves production security and reduce production cost.
According to the disclosure, lithium peroxide is provided to anode or electrolyte.Due to being wrapped in lithium peroxide and anode or electrolyte The other components contained are compatible, therefore have no need to change the composition of anode or electrolyte.On the contrary, if directly providing peroxide to cathode Change lithium, then needing correspondingly to change includes solvent and adhesive in cathode.
In some instances, it in the step that the anode comprising positive electrode active materials and lithium peroxide is provided, can be used just Pole active material and lithium peroxide form anode sizing agent, and then anode sizing agent can be applied on plus plate current-collecting body.Specifically, Can by other components of lithium peroxide and positive electrode composition (such as positive electrode active materials, carbon material, adhesive, solvent and/or The one or more additives being optionally present) it mixes to prepare anode sizing agent.It then, can be by anode sizing agent such as by coating It is applied on collector, to form the anode containing lithium peroxide.According to the disclosure, it is easy for lithium peroxide to be introduced into anode. The introducing of lithium peroxide is integrated with the addition of other components of positive electrode composition, does not additionally need independent step or needs spy Different condition, for industrial production, it means that considerable cost savings and labour supervision.
It alternatively, can be by positive-active material in the step that the anode comprising positive electrode active materials and lithium peroxide is provided Material is applied on plus plate current-collecting body to form active material layer, then can be applied to lithium peroxide on active material layer to be formed Peroxidating lithium layer.Lithium peroxide is provided in this way to be also easy to carry out.
Prelithiation step
In some instances, the lithium peroxide during several leading charging of lithium ion battery, from anode or electrolyte Extract lithium ion.Meanwhile the peroxide root anion (O in lithium peroxide2 2-) lose electronics and be converted into oxygen.Extracted lithium Ion is inserted into and is stored in cathode.Therefore, cathode is by prelithiation.Several leading charging during cathode prelithiation is also referred to as " forming charging ".During subsequent charge/discharge cycle, the lithium being stored in cathode during forming charging may participate in lithium ion Migration, compensation lithium due to caused by forming SEI layers lose, and stablize SEI layers and reduce capacity attenuation.
According to some examples of the disclosure, can carry out forming charging within the scope of voltage range, that is, blanking voltage.One In a little examples, during charging to lithium ion battery, the upper limit of blanking voltage not less than about 3.8V but can be not greater than about 5V, preferably Not less than about 4.2V but be not greater than about 5V.The upper limit of blanking voltage, which may depend in lithium ion battery, during forming charging includes Positive electrode active materials.Positive electrode active materials will be described below.For example, including lithium nickel cobalt manganese oxide (NCM) in anode Or lithium nickel cobalt aluminum oxide (NCA), as in the case where active material, the upper limit of blanking voltage can not be small during forming charging In about 4.2V but it is not greater than about 5V.It include lithium nickel cobalt manganese oxide/Li in anode2MnO3Compound (also referred to as " rich lithium-NCM ") In the case where as active material, the upper limit of blanking voltage not less than about 4.35V but can be not greater than about during forming charging 5.0V.The upper limit of blanking voltage is fallen within the scope of these during forming charging, on the one hand, lithium peroxide can sufficiently release lithium Ion, on the other hand, anode will not be seriously damaged.
According to some examples of the disclosure, cathode can be by part prelithiation, so as not to compensate only for drawing due to forming SEI The lithium loss risen, but also keep desired lithium migration between positive electrode and negative electrode.
According to some examples of the disclosure, other than the lithium being stored in cathode during prelithiation, cathode can Irreversible capacity (unit: mAh/cm for lithium insertion2) it is positive irreversible capacity (unit: mAh/cm2) about 1 to about 1.2 times, for example, about 1 to about 1.1 times.It is desirable that the irreversible capacity of cathode and the ratio of the irreversible capacity of anode can be 1.However, it is contemplated that the inevitable operating error during preparing battery, the ratio can be greater than 1.If cathode is not The ratio of the irreversible capacity of reversible capacity and anode is less than 1, then excessive lithium metal can be gathered in around cathode, it is undesirable to ground It forms Li dendrite and causes short circuit.If the ratio of the irreversible capacity of the irreversible capacity of cathode and anode is greater than 1.2, bear Pole capacity is excessive, and consumes the irreversible capacity of cathode excessively.
It can be used in energy-storage system and electric vehicle according to the lithium ion battery of the disclosure.
Positive electrode composition
In some examples of the disclosure, before prelithiation, positive electrode composition may include that lithium peroxide is used as cathode The lithium source of prelithiation.After prelithiation, the gross dry weight based on positive electrode composition, positive electrode composition can retain the peroxidating of trace Lithium, for example, about 0.01 weight % are to about 1 weight %.
According to some examples of the disclosure, anode may include positive electrode active materials.In some instances, positive electrode active materials It can be the reversibly de- material inserted and be inserted into lithium ion during charge/discharge cycle.In discharge cycles, it is originated from positive-active The lithium ion of material can migrate back anode from cathode to form positive electrode active materials again.In the anode as alkaline lithium source Positive electrode active materials are compared, and lithium peroxide is referred to alternatively as " additional lithium source " or " supplement lithium source ".
Positive electrode active materials are not particularly limited, can be used and those of be usually used in lithium ion battery positive-active material Material.In some instances, positive electrode active materials may differ from lithium peroxide.In some instances, positive electrode active materials can be Lithium-based active material.In some instances, positive electrode active materials can be selected from lithium metal oxide, lithium metal phosphates, lithium metal Silicate, sulfide and their any combination, preferably lithium-compound transition metal oxide, lithium-transition metal phosphate, lithium Metal silicate, metal sulfide and their any combination.In some instances, positive electrode active materials can be selected from ferric phosphate Lithium, lithium phosphate manganese, lithium phosphate manganese iron and their any combination.In some instances, lithium-compound transition metal oxide can be with It is lithium nickel oxide, lithium and cobalt oxides, lithium manganese oxide, lithium nickel cobalt oxides, Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide (NCM), lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese oxide/Li2MnO3Compound (also referred to as " rich lithium NCM ") or they Any combination.In some instances, metal sulfide can be iron sulfide.In some instances, positive electrode active materials can have There is 1 micron to tens microns of size.
Optionally, anode can additionally comprise the fine grained that partial size is less than positive electrode active materials partial size.In some instances, carefully Particle can have the size less than 1 micron (that is, nanoscale).Fine grained can be selected from transistion metal compound, noble metal, carbon material With their any combination.Fine grained can be commercially available, or can by by relatively large particulate abrasive at small size (for example, by using mill ball) and obtain.These fine graineds can advantageously be catalyzed lithium peroxide and decompose during forming charging For lithium ion.In the case where anode is comprising fine grain situation, because fine grained is used as the catalyst of prelithiation, these fine graineds It can all be present in anode before and after prelithiation.Transistion metal compound may include the 3rd race of periodic table into the 12nd race The compound of any transition metal, such as titanium oxide, zinc oxide, Cu oxide, nickel oxide, molybdenum oxide.Noble metal packet Include gold, silver and platinum group metal (that is, ruthenium, rhodium, palladium, osmium, iridium and platinum).The fine grained of carbon material can be carbon nanotube, hard carbon, ball Shape carbon etc..
In some instances, anode can include two kinds of various sizes of positive electrode active materials simultaneously.In some instances, just It pole can be identical positive living less than 1 micron comprising positive electrode active materials and size having a size of 1 micron to tens microns simultaneously The fine grained of property material.
According to some examples of the disclosure, positive electrode composition also may include carbon material." carbon material " can be carbon elements Material.Carbon material can increase the electric conductivity and/or dispersibility of positive electrode composition.Carbon material is not specifically limited, and can be with Using becoming known for those of lithium ion battery carbon material.In some instances, carbon material can include but is not limited to carbon black, Super P, acetylene black, Ketjen black, graphite, graphene, carbon nanotube, carbon fiber, gas-phase growth of carbon fibre and their group It closes.In some instances, anode may include the mixture of two or more different type carbon materials.In some instances, just Pole can include two kinds of various sizes of carbon materials simultaneously, that is, be not less than 1 micron of carbon material, and identical less than 1 micron or not With the fine grained of carbon material.
According to some examples of the disclosure, positive electrode composition also may include adhesive.Adhesive can be by positive electrode composition Component keeps together, and positive electrode composition is made to be attached to plus plate current-collecting body, when the generating body during duplicate charge/discharge cycle When product variation, the good stability and integrality of anode are helped to maintain, therefore improves the electrochemical properties of final battery, including Cycle performance and high rate performance.Adhesive is not specifically limited, can be used and those of become known in lithium ion battery.? In some examples, adhesive can be polyvinylidene fluoride (PVDF), polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC), It is preferred that PVDF.
According to some examples of the disclosure, positive electrode composition also may include solvent.Solvent can dissolve its of positive electrode composition Its component is to provide anode sizing agent.Then, gained anode sizing agent can be applied on plus plate current-collecting body.Then, it can dry thereon The plus plate current-collecting body of anode sizing agent is applied with to obtain anode.The solvent for including in positive electrode composition is not specifically limited, it can Become known for those of lithium ion battery to use.In some instances, the solvent in positive electrode composition can be N- methyl -2- Pyrrolidones (NMP).
In some instances, positive electrode composition includes lithium peroxide, positive electrode active materials, carbon material, adhesive and solvent. In addition, the other additives being commonly known in lithium ion battery can be optionally employed, as long as they can not adversely damage electricity The expected performance in pond.
The type of every kind of component, shape, size and/or content in positive electrode composition are not particularly limited.
Plus plate current-collecting body is not specifically limited.In some instances, aluminium foil can be used as plus plate current-collecting body.
Cathode composition
Cathode composition according to the disclosure may include negative electrode active material.Negative electrode active material is not specifically limited, Those of known negative electrode active material usually in lithium ion battery can be used.Some examples according to the present invention, cathode are living Property material can be selected from silicon-based active material, carbon-based active material and their any combination.
" silicon-based active material " can be the active material containing element silicon.The example of suitable silicon-based active material may include but It is not limited to silicon, silicon alloy, silica, silicon/carbon complex, silica/carbon complex and their any combination.In some examples In, silicon alloy may include silicon and selected from one of Ti, Sn, Al, Sb, Bi, As, Ge and Pb or various metals.In some examples In, silica can be the mixture more than a kind of Si oxide.For example, silica can be expressed as SiOx, wherein x is averaged Value can be about 0.5 to about 2.
" carbon-based active material " can be the active material containing carbon.Carbon-based active material in cathode can with just The carbon material for including in extremely is identical or different.The example of suitable carbon-based active material may include but be not limited to graphite, graphene, Hard carbon, carbon black and carbon nanotube.
Similar to positive electrode composition, cathode composition also may include carbon material, adhesive and/or solvent.Carbon in cathode Material, adhesive and solvent can respectively in anode comprising those of it is identical or different.In addition, commonly known use can be optionally employed Other additives in lithium ion battery, as long as they can not adversely damage the expected performance of battery.
The type of every kind of component, shape, size and/or content in cathode composition are not particularly limited.
Negative current collector is not particularly limited.In some instances, nickel foil, nickel screen, copper foil or copper mesh may be used as bearing Pole collector.
Electrolyte
Lithium ion battery according to the disclosure may include electrolyte.According to some examples of the disclosure, electrolyte may include Lithium salts and nonaqueous solvents.Lithium salts and nonaqueous solvents are not particularly limited, and can be used usually in the battery it is known that A little lithium salts and nonaqueous solvents.In some instances, it is living to may differ from the anode in lithium peroxide and anode for the lithium salts in electrolyte Property material.According to some examples of the disclosure, lithium salts may include but be not limited to lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), arsenic acid lithium (LiAsO4)、LiSbO4, lithium perchlorate (LiClO4)、LiAlO4、LiClO4, bis- (oxalic acid) lithium borates (LiBOB) and their combination, preferably LiPF6。
According to some examples of the disclosure, nonaqueous solvents can be carbonic ester (that is, nonfluorinated carbonic ester) and perfluorocarbon acid Ester.According to some examples of the disclosure, carbonic ester may include but be not limited to cyclic carbonate, such as ethylene carbonate (EC), carbon Sour Asia propyl ester (PC), butylene carbonate (BC)；Linear carbonates, such as dimethyl carbonate (DMC), diethyl carbonate (DEC), carbon Sour dipropyl (DPC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), ethyl propyl carbonic acid ester (EPC)；And above-mentioned carbonic ester Any combination.According to some examples of the disclosure, fluorocarbons acid esters can be the fluorinated derivatives of above-mentioned carbonic ester, such as fluorine For ethylene carbonate (FEC) and difluoro ethylene carbonate, difluoro dimethyl carbonate (DFDMC).In the disclosure, nonfluorinated carbonic acid The mixture of ester and fluorocarbons acid esters can be described as " partially fluorinated carbonic ester ".Relative to nonfluorinated carbonic ester and partially fluorinated Carbonic ester, fluorocarbons acid esters are properly termed as " fully fluorinated carbonic ester ".
Boryl anion receptor in electrolyte
According to some examples of the disclosure, electrolyte can further include boryl anion receptor.To boryl anion by Body is not specifically limited, and can be used has Lewis acid centers and can be with peroxide radical ion (O in boron atom2 2-, road This easy alkali center) form the borine and borate of complex compound.By using such borine or borate, peroxidating can be increased The dissolubility of lithium in the electrolytic solution, and the dynamics of lithium peroxide removal lithium embedded can be improved, this promotes lithium peroxide to release Lithium ion.It include thermally labile lithium salts (such as LiPF in electrolyte6) in the case where, borine or borate can also stablize anion (such as PF6 5-) and mitigate lithium salts (such as LiPF6) decomposition, otherwise lithium salts decomposition will lead to capacity during charge/discharge cycle Decay and increases impedance.
For example, according to the disclosure, can be used the descriptions such as H.S.Lee by formula (fluorinated alkyl-O)3The boric acid that-B is indicated Salt, by formula (fluoro aryl-O)3The borate that-B is indicated, and by general formula (fluoro aryl)3The borine that-B is indicated (J.Electochem.Soc., 145 (1998), are integrally incorporated herein by reference by the 2813-2818 pages).Show The borate of example property can include but is not limited to (2H- hexafluoro isopropyl) ester of boric acid three (THFPB, [(CF3)2CHO]3) and boric acid B Three (2,4- bis-fluoro ethyls) ester (F2C6H3O)3B, illustrative borine can include but is not limited to three (pentafluorophenyl group) borines (TPFPB,(C6F5)3B)。
Fluoro aryl boron oxalates described in U.S. Patent Application Publication No. US2012/0183866A1 is also useful, The patent application is integrally incorporated herein by reference.Illustrative fluoro aryl boron oxalates can be by following formula table Show:
Wherein R is one or more fluorine-containing parts.The non-limiting example of fluoro aryl boron oxalates may include but It is not limited to pentafluorophenyl group boron oxalates (PFPBO).
The dioxalic acid lithium borate (Lithium bis (oxalato) borate, LiBOB) that can also be indicated using following formula is made For the boryl anion receptor in electrolyte:
In addition, LiODFB (lithium described in U.S. Patent Application Serial Number US 10/625686 Oxaltodifluoroborate, chemical formula LiBF2C2O4, it is abbreviated as LiODFB) and it also is used as the boryl anion in electrolyte Receptor.
Oxalate (such as PFPBO), LiBOB and the LIODFB of fluoroarylboron each contribute to be formed in negative terminal surface more steady Fixed SEI layer improves battery performance so as to reduce the consumption of lithium.
Embodiment
NCM-111: lithium nickel cobalt manganese oxide, positive electrode active materials, are purchased from BASF by D50:12 μm.
Si/C composite material: negative electrode active material, by by nano silicon particles (diameter: 50nm, be purchased from Alfa Aesar) It makes by oneself and obtains with the weight ratio mixing of 1:1 with graphite (reaching Science and Technology Ltd. purchased from section, Shenzhen crystalline substance intelligence).
Super P: superconductive carbon black, carbon material, 40nm are purchased from Timcal.
KS6L: flake graphite, carbon material, are purchased from Timcal by about 6 μm.
Lithium peroxide: for the lithium source of cathode prelithiation, it is purchased from Alfa Aesar.
PVDF: polyvinylidene fluoride, adhesive are purchased from Sovey.
NMP:N- N-methyl-2-2-pyrrolidone N, solvent are purchased from Sinopharm Chemical Reagent Co., Ltd..
Celgard 2325: polypropylene, polyethylene/polypropylene laminate film (PP/PE/PP film), diaphragm are purchased from Celgard.
[positive preparation]
Embodiment 1
In the glove box (MB-10compact, be purchased from MBraun) filled with argon gas, by 938.6mg NCM-111, 26.4mg lithium peroxide, 10mg Super P, 5mg KS6L, 20mg PVDF are added in 450mL NMP.Stirring 3 hours it Afterwards, obtained evenly dispersed slurry is applied on aluminium foil, it is then 6 hours dry in 80 DEG C in a vacuum.It will be coated Aluminium foil takes out from glove box, and the anode pole piece for being cut into multiple 12mm (is abbreviated as NCM-Li2O2Anode pole piece).
[preparation of battery]
In the glove box (MB-10compact is purchased from MBraun) filled with argon gas, using positive pole obtained above Piece assembles button cell (CR2016).Pure lithium metal foil is used as to electrode.By FEC+EMC (volume ratio 3:7, part fluorine The carbonic ester electrolyte of change) in 1M LiPF6As electrolyte.Celgard 2325 (PP/PE/PP film) is used as diaphragm.
Embodiment 2
(NCM-Li is abbreviated as in a manner of identical with described in embodiment 1 to prepare anode pole piece2O2Catalyst anode pole Piece), the difference is that addition 10mg NCM-111 fine grained is as the catalyst to prepare anode sizing agent, and use 928.6mg NCM-111 replaces 938.6mg NCM-111.NCM-111 fine grained has the partial size less than 1 μm.
Embodiment 3
(NCM-Li is abbreviated as in a manner of identical with described in embodiment 2 to prepare anode pole piece2O2Catalyst anode pole Piece), the difference is that replacing 26.4mg lithium peroxide using 24.1mg lithium peroxide.
Embodiment 4
(NCM-Li is abbreviated as in a manner of identical with described in embodiment 2 to prepare anode pole piece2O2Catalyst anode pole Piece), the difference is that replacing 26.4mg lithium peroxide using 50mg lithium peroxide.
Embodiment 5
Battery is prepared in a manner of identical with described in embodiment 4, the difference is that using EC+DMC (1:1 volume, non-fluorine Change carbonic ester electrolyte) in 1M LiPF6As electrolyte.
Embodiment 6
Battery is prepared in a manner of identical with described in above-described embodiment 4, the difference is that (containing using fully fluorinated carbonic ester Have the FEC of 30 volume %) in 1M LiPF6As electrolyte.
Embodiment 7
Battery is prepared in a manner of identical with described in above-described embodiment 2, the difference is that using Si/C composite material as negative Pole.
Embodiment 8
Battery is prepared in a manner of identical with described in above-described embodiment 7, the difference is that using fully fluorinated carbonic ester electricity Solve the 1M LiPF in liquid (FEC containing 30 volume %)6As electrolyte.
Comparative example 1
Anode pole piece (being abbreviated as NCM anode pole piece) is prepared in a manner of identical with described in above-described embodiment 1, unlike 938.6mg NCM-111 is replaced without using lithium peroxide, and using 965mg NCM-111.
Comparative example 2
Battery is prepared in a manner of identical with described in above-mentioned comparative example 1, the difference is that using Si/C composite material as negative Pole.
Comparative example 3
Battery is prepared in a manner of identical with described in above-mentioned comparative example 2, the difference is that using fully fluorinated carbonic ester electricity Solve the 1M LiPF in liquid (FEC containing 30 volume %)6As electrolyte.
[electrochemical measurement]
At 25 DEG C, the cycle performance of each battery is evaluated on Arbin battery test system.
The battery that Fig. 1 compares embodiment 1, prepared by embodiment 2 and comparative example 1 filling in the 1st charge/discharge cycle/ Discharge performance.In the 1st charge/discharge cycle, in 3-4.6V (vs Li/Li+) voltage range in each battery carry out Charge/discharge.In the anode of each battery, the mass loading of NCM is about 10mg/cm2.Specific volume is calculated based on the weight of NCM Amount.NCM-Li compared with the NCM anode in comparative example 1, in embodiment 12O2Improve charging capacity when charging for the first time. With the NCM-Li in embodiment 12O2It compares, the NCM-Li in embodiment 22O2Catalyst anode further improves to be filled for the first time Charging capacity when electric.This is attributed to the decomposition that NCM fine grained has been catalyzed lithium peroxide, thus to cathode provide more lithiums from Son.
Fig. 2 compares the cycle performance of battery prepared by embodiment 1, embodiment 2 and comparative example 1.In the 1st charge/discharge In circulation, in 3-4.6V (vs Li/Li+) voltage range in each battery carry out charge/discharge；Then, in 3-4.3V (vs Li/Li+) normal voltage range in carry out charge/discharge.In the anode of each battery, the mass loading of NCM is about 10mg/ cm2.Specific capacity is calculated based on the weight of NCM.With reference to Fig. 2, it can be seen that the NCM-Li in embodiment 22O2Catalyst anode Show maximum capacity and best stability, and the NCM anode in comparative example 1 shows worst stability.
Fig. 3 compares the charge/discharge performance of battery prepared by embodiment 3 and comparative example 1 in the 1st charge/discharge cycle. Fig. 4 compares the cycle performance of battery prepared by embodiment 3 and comparative example 1.Fig. 5 shows the battery of the preparation of embodiment 4 the 1st Charge/discharge performance when secondary charge/discharge cycle.Fig. 6 shows the cycle performance of battery prepared by embodiment 4.Filled at the 1st time/ In discharge cycles, in 3-4.6V (vs Li/Li+) voltage range in each battery carry out charge/discharge；Then, in 3-4.3V (vs Li/Li+) normal voltage range in carry out charge/discharge.In the anode of each battery, the mass loading of NCM is about 10mg/cm2.Specific capacity is calculated based on the weight of NCM.Fig. 3 to Fig. 6 is demonstrated, NCM-Li2O2The positive ultimate ratio NCM of catalyst is just The extremely significant capacity for improving battery and stability.
Fig. 7 compares the charge/discharge performance of battery prepared by embodiment 5 and comparative example 1 in the 1st charge/discharge cycle. Fig. 8 compares the cycle performance of battery prepared by embodiment 5 and comparative example 1.Fig. 9 shows the battery of the preparation of embodiment 6 the 1st Charge/discharge performance when secondary charge/discharge cycle.Figure 10 shows the cycle performance of battery prepared by embodiment 6.Filled at the 1st time/ In discharge cycles, in 3-4.6V (vs Li/Li+) voltage range in each battery carry out charge/discharge；Then, in 3-4.3V (vs Li/Li+) normal voltage range in carry out charge/discharge.In the anode of each battery, the mass loading of NCM is about 10mg/cm2.Specific capacity is calculated based on the weight of NCM.Fig. 7 to Figure 10 is demonstrated, nonfluorinated carbonic ester, perfluocarbon acid esters It is suitable for prelithiation method with partially fluorinated carbonic ester, and significantly improves the capacity and stability of battery.
It is electrical that Figure 11 compares the discharge/charge of battery prepared by embodiment 7 and comparative example 2 in the 1st charge/discharge cycle Energy.Figure 12 compares the cycle performance of battery prepared by embodiment 7 and comparative example 2.In the 1st charge/discharge cycle, in 2.5- 4.6V(vs Li/Li+) voltage range in each battery carry out charge/discharge；Then, in 2.5-4.2V (vs Li/Li+) Charge/discharge is carried out in normal voltage range.In the anode of each battery, the mass loading of NCM is about 18mg/cm2.It is based on The weight of NCM calculates specific capacity.Compared with the battery of comparative example 2, the NCM-Li of embodiment 72O2Catalyst anode is first Bigger charging capacity is shown when secondary charging, and shows that better capacity is kept in charge/discharge cycle.
It is electrical that Figure 13 compares the discharge/charge of battery prepared by embodiment 8 and comparative example 3 in the 1st charge/discharge cycle Energy.Figure 14 compares the cycle performance of battery prepared by embodiment 8 and comparative example 3.Compared with the battery of comparative example 3, embodiment 8 NCM-Li2O2Catalyst anode shows bigger charging capacity when charging first time, and shows in charge/discharge cycle Better capacity is shown to keep.

Claims (14)

1. lithium ion battery, it includes anode, cathode and electrolyte, wherein the anode includes positive electrode active materials and peroxidating Lithium.
2. lithium ion battery according to claim 1, wherein the lithium ion battery is prelithiation or non-prelithiation, And the gross dry weight based on positive electrode composition, the content of lithium peroxide are greater than 0 to about 20 weight %, preferably greater than 0 to less than 20 weight %, more preferably from about 0.01 weight % are to about 5 weight %, even more preferably about 0.01 weight % to about 1 weight %.
3. lithium ion battery according to claim 1 or 2, wherein the partial size of the positive electrode active materials is 1 micron to several Ten microns.
4. lithium ion battery according to any one of the preceding claims, wherein the anode is also micro- less than 1 comprising partial size The fine grained of rice, and the fine grained is selected from transistion metal compound, noble metal, carbon material and their any combination.
5. lithium ion battery according to any one of the preceding claims, wherein the positive electrode active materials choosing in the anode From lithium metal oxide, lithium metal phosphates, lithium metal silicate, sulfide and their any combination.
6. lithium ion battery according to any one of the preceding claims, wherein the cathode includes negative electrode active material, The negative electrode active material is selected from silicon-based active material, carbon-based active material and their any combination.
7. lithium ion battery according to any one of the preceding claims, wherein the electrolyte includes lithium salts and non-aqueous Agent.
8. lithium ion battery according to any one of the preceding claims, wherein the electrolyte also includes boryl anion Receptor.
9. the method for preparing lithium ion battery according to claim 1 to 8 comprising:
-- the anode comprising positive electrode active materials and lithium peroxide is provided；With
-- the anode, cathode and electrolyte are assembled into lithium ion battery；Optionally
-- the lithium ion battery is charged, to release lithium ion from the lithium peroxide in the anode, and described Cathode stores lithium, thus by the cathode prelithiation,
Wherein based on the gross dry weight of positive electrode composition, lithium peroxide is in the battery of the prelithiation or the battery of non-prelithiation Content is greater than 0 to the about 20 weight % of weight %, preferably greater than 0 to less than 20, more preferably from about 0.01 weight % to about 5 weights Measure %, even more preferably about 0.01 weight % to about 1 weight %.
10. according to the method described in claim 9, wherein by the lithium ion battery charge during, blanking voltage The upper limit is no less than about 3.8V but no more than about 5V, preferably not less than about 4.2V but no more than about 5V.
11. method according to claim 9 or 10, wherein in addition to being stored in the cathode during prelithiation Lithium except, the cathode can be used for lithium insertion irreversible capacity (unit: mAh/cm2) be the anode irreversible appearance Measure (unit: mAh/cm2) about 1 to about 1.2 times, for example, about 1 to about 1.1 times.
12. lithium ion battery, it includes anode, cathode and electrolyte, wherein the electrolyte includes lithium salts, nonaqueous solvents and mistake Lithia.
13. lithium ion battery according to claim 12, wherein the electrolyte also includes boryl anion receptor.
14. the method for preparing lithium ion battery according to claim 12 or 13 comprising:
-- the electrolyte comprising lithium salts, nonaqueous solvents and lithium peroxide is provided；
-- the electrolyte, anode and cathode are assembled into lithium ion battery；Optionally
-- the lithium ion battery is charged, to release lithium ion from the lithium peroxide in the electrolyte, and in institute Cathode storage lithium is stated, thus by the cathode prelithiation.
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