CN104795548A - Multi-phase separation silicon-based alloy used as negative electrode material of lithium battery - Google Patents
Multi-phase separation silicon-based alloy used as negative electrode material of lithium battery Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
A silicon, tin, and aluminum (or other proper metal) granular compound is prepared, and the compound is used together with a metal current collector in batteries of a lithium ion battery pack or a lithium-sulphur battery pack as a negative electrode consitituent with enhanced lithum embedding capacity and endurance. The electrode material makes silicon exist in different amorphous phases in a substrate in which crystal tin and crystal alumimum are separated. Even though different tin and alumimum phases provide electron conductivity, in operation of the batteries, each phase is suitable for embedding and taking off of lithum, and all interactions reduce mechanical damages of the material to the largest extent when the battery is repeatedly charged and discharged. Other metal suitable for the compound with silicon and tin comprises copper and titanium.
Description
The application is the part continuity on September 16th, 2011 submits to, name is called " silicon-tin composite be separated as lithium ion battery negative material ", sequence number is No.13/234209, existing U.S. Patent Application Publication No. is No.2013-0071736.The full content of this application is incorporated to herein as a reference.
Technical field
The present invention relates to the preparation of negative material, this material is applicable to the battery pack using lithium electrode, as Li-ion batteries piles and lithium-sulfur cell group.More particularly, the present invention relates to preparation and the purposes of complex components (compositions), this complex components comprises and is embedded into tin and another metal as aluminium, the crystalline state of separating of copper or titanium or amorphous nano size mutually in amorphous silicon phase nanoscale island.This complex components is prepared into particle by fast solidification technology, and is used for the loop embedding of lithium in the operation of lithium battery as negative material and deviates from.In this compound, the suitable atomic ratio of silicon, tin and other metallic element of at least one and the combination of each phase size make the lithium embedding recruitment in the electrochemistry circulation repeated, and less to the damage of particle negative material.
Background of invention
Li-ion batteries piles is used as electronic power storage system of powering with hybrid electric vehicle.These battery pack comprise and are set to specify electromotive force to provide the multiple suitably interconnected electrochemical cell of scheduled current.In each this battery, along with electron stream is delivered to external loading from battery pack, such as traction motor, lithium is transported to containing lithium electrolyte solution the positive pole accepting lithium ion by anhydrous with lithium ion form from negative pole.Be applicable to, to be permeated by electrolyte solution and the porous septum material that can pass through lithium ion is transported in the electrolyte for preventing the short circuit physical contact between electrode.Graphite is used as negative material, is bonded in the Thin electrode layers on copper current collector.In the charging process of battery, lithium is embedded into (lithiumation, formation LiC in graphite
6, about 372mAh/g), and deviate from from graphitic carbon in electric discharge (de-lithium) process.The granular materials be applicable to for receiving and store embedded lithium in each battery discharge procedure is used as positive electrode.The example of this positive electrode material comprises lithium and cobalt oxides (LiCoO
2), spinel-type lithium transition-metal oxide, as spinel lithium manganese oxide (LiMn
xo
y), polyanionic type lithium, as nickel, cobalt and manganese oxide [Li (Ni
xmn
yco
z) O
2], LiFePO4 (LiFePO
4), or lithium fluophosphate (Li
2fePO
4or the mixture of these materials any F).The positive electrode be applicable to is bonded on aluminium collector usually used as thin layer.The electrochemical potential of this lithium ion battery is usually in the scope of about 2 to 4.5V.
The use of Li-ion batteries piles in motor vehicles power electric motors, makes the battery pack needing larger weight and/or volume capacity.Although graphitic carbon is durable and effectively embeds negative material for the lithium of lithium ion battery, embed for this lithium, it has relatively little capacity.Embed for lithium, compare graphite, other potential negative material is if silicon is (for Li
15si
4theoretical capacity 3600mAh/g) and tin (for Li
22sn
5theoretical capacity 992mAh/g) there is much bigger theoretical capacity.But in lithiumation and de-lithium process, the change in volume that silicon reaches maximum 300 volume % causes break (fracture) of activated silica material, and/or with the loss of conductivity additive or collector electrical contact.Tin has same large volumetric expansion problem when lithiumation, cause capacity sharply to reduce.
Lithium-sulfur cell group such as Li-ion batteries piles is rechargeable.They are famous with its high-energy-density.The low atomic weight of lithium and the medium atomic weight of sulphur make the weight of lithium-sulfur cell group relatively light.The same with lithium ion battery, anode or the negative pole of lithium-sulfur cell also need lithium.In lithium-sulfur cell discharge process, lithium is dissolved into electrolyte from anode surface, at electrolyte (such as, the alkali metals polysulfide salt of melting or liquid state) in be transported to negative electrode (positive pole during battery discharge) by porous septum, it comprises polysulfide sulphur (such as S
8).After arriving negative electrode, polysulfide is progressively reduced into lithium sulphur component (such as, Li by lithium atom
2s
3).When lithium-sulfur cell recharges, this chemical change reverses.The light weight of lithium-sulfur cell and high-energy-density make lithium-sulfur cell group unify as vehicle powertrain the good candidate of other power consumpting device.
Because the Basic Mechanism of the battery capacity loss caused of breaking of electrode material in its battery is with the minimizing of electric conducting material electrical contact and irreversibly consumes active lithium to form the formation on the new surface of new solid electrolyte interface.This two problems reduces the Efficient Cycle capacity of battery pack.Need a kind of more effectively, in lithium ion battery negative, use mode or the material forms of silicon or tin.
Summary of the invention
The present invention relates to following [1]-[20]:
[1] lithium ion or lithium-sulphur making active materials for use in secondary electrochemical cells or a battery pack, comprises the negative pole component using lithium; In battery or batteries charging process, lithium is embedded in negative pole component, and in battery or battery power discharge process, lithium is deviate from from this negative pole component; Negative material comprises silicon, tin and is selected from the compound of the second metallic element of aluminium, copper and titanium, this compound feature be also silicon, tin and the second metal be present in respectively separately mutually in, tin phase and the second metallic element are crystallization or amorphous mutually, and silicon is amorphous mutually.
[2] lithium ion as described in [1] or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the second metallic element is aluminium.
[3] lithium ion as described in [1] or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the compound of silicon, tin and the second metallic element is by the silicon of 20-80 atomic percent, the tin of 20-60 atomic percent and the second metallic element composition of 1-30 atomic percent.
[4] lithium ion as described in [1] or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the feature of the compound of silicon, tin and the second metallic element is the amorphous silicon phase nanoscale island that is dispersed in the matrix of tin phase and the second metallic element phase.
[5] lithium ion as described in [1] or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the feature of the compound of silicon, tin and the second metallic element is the tin phase crystal of size all in 20 nanometer to 50 nanometer range and the second metallic element phase crystal.
[6] lithium ion as described in [1] or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the compound of silicon, tin and the second metallic element forms adhesive film by the surface that silicon, tin and the second metallic element is splashed to the metal collector of negative material, and the film thickness of sputtering is about at most 5 microns.
[7] lithium ion as described in [2] or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the compound of silicon, tin and aluminium by forming adhesive film by silicon, tin and sputtered aluminum to the surface of the metal collector of negative material, and the film thickness of sputtering is about at most 5 microns.
[8] lithium ion as described in [1] or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the compound of silicon, tin and the second metallic element is formed by the melt liquid of silicon, tin and the second metallic element being rapidly solidificated into the solid particle of the compound that is separated of silicon, tin and the second metallic element, if needed, this solid particle size is decreased to about 1-5 micron, and sticks in the metal collector of negative material.
[9] lithium ion as described in [1] or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the compound of silicon, tin and aluminium is formed by making the melt liquid of silicon, tin and aluminium be rapidly solidificated into the solid particle of the compound that is separated of silicon, tin and aluminium, if needed, this solid particle size is decreased to about 1-5 micron, and sticks in the metal collector of negative material.
[10] lithium as described in [1]-sulphur making active materials for use in secondary electrochemical cells or battery pack, before battery or battery pack initial charge, negative material comprises the compound containing the silicon embedding lithium, tin and the second metallic element.
[11] lithium ion or lithium-sulphur making active materials for use in secondary electrochemical cells or a battery pack, comprise negative pole component and anode constituents; In battery or batteries charging process, by transporting lithium containing lithium electrolyte, lithium being embedded in negative pole component and deviating from from anode constituents; In battery or battery power discharge process, by transporting lithium containing lithium electrolyte, lithium is made to deviate from from negative pole component and be embedded in anode constituents; Negative material comprises silicon, tin and is selected from the compound of the second metallic element of aluminium, copper and titanium, this compound feature be also silicon, tin and the second metallic element be present in respectively separately mutually in, tin phase and the second metallic element are crystallization or amorphous mutually, and silicon is amorphous mutually.
[12] lithium ion as described in [11] or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein said second metallic element is aluminium.
[13] lithium ion as described in [11] or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the compound of silicon, tin and the second metallic element is by the silicon of 20-80 atomic percent, the tin of 20-60 atomic percent and the second metallic element composition of 1-30 atomic percent.
[14] lithium ion as described in [11] or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the feature of the compound of silicon, tin and the second metallic element is the amorphous silicon phase nanoscale island that is dispersed in the matrix of tin phase and the second metallic element phase.
[15] lithium ion as described in [11] or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the feature of the compound of silicon, tin and the second metallic element is the tin phase crystal of size all in 20 nanometer to 50 nanometer range and the second metallic element phase crystal.
[16] lithium ion as described in [11] or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the compound of silicon, tin and the second metallic element forms adhesive film by the surface that silicon, tin and the second metallic element is splashed to the metal collector of negative material, and the thickness of the film of sputtering reaches at most about 5 microns.
[17] lithium ion as described in [12] or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the compound of silicon, tin and aluminium by forming adhesive film by silicon, tin and sputtered aluminum to the surface of the metal collector of negative material, and the thickness of the film of sputtering reaches at most about 5 microns.
[18] lithium ion as described in [11] or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the compound of silicon, tin and the second metallic element is formed by making the melt liquid of silicon, tin and the second metallic element be rapidly solidificated into the solid particle of the compound that is separated of silicon, tin and the second metallic element, if needed, this solid particle size is decreased to about one to five micron, and sticks in the metal collector of negative material.
[19] lithium ion as described in [12] or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the compound of silicon, tin and aluminium is formed by making the melt liquid of silicon, tin and aluminium be rapidly solidificated into the solid particle of the compound that is separated of silicon, tin and aluminium, if needed, this solid particle size is decreased to about one to five micron, and sticks in the metal collector of negative material.
[20] lithium as described in [11]-sulphur making active materials for use in secondary electrochemical cells or battery pack, before battery or battery pack initial charge, this negative material comprises the compound containing the silicon embedding lithium, tin and the second metallic element.
According in embodiments of the invention, by elemental silicon (metalloid element) and tin and another kind of metallic element being combined the negative material for lithium battery group forming a kind of improvement as mutually mixed but immiscible solid phase of separating.The second metallic element combined with silicon and tin be chosen as be suitable for lithium spread in the mixture and with solid state si and tin unmixing substantially.Such as, in the practice of the invention, element aluminum, copper or titanium can combine with silicon and tin.Preferred aluminium.
In a preferred embodiment, form the particle composites (or membrane complex of sputtering) of silicon, tin and aluminium, wherein, silicon, aluminium and tin are present in each particle of compound with what separate mutually separately.Aluminium and tin are conduction mutually, and each in three-phase all can accept the embedding of lithium atom and deviate from.It is nanometer to the three-phase of micron (or being of a size of feature with phase in compound) or heterogeneous structure that this compound is formed as feature phase length or diameter, and by controlling synthesis technique to produce lower than due to repeatedly embedding of lithium and the mixed phase size of the critical dimension of micro-crack that formed and realize in mixed phase.
In a preferred embodiment, form (confined) grain structure closed, wherein, in tin phase and the matrix (or boundary layer) of aluminium phase (or other metal element phase of separating combined with silicon and tin) of separating, island silicon is mutually for separately.This microstructure has several advantage: (1) tin phase and aluminium conduct electricity mutually separately, this makes electronic energy get to reach the island silicon phase particle that can keep sufficient lithium atom, (2) lithium in tin and aluminium (or being selected for other metallic element combined with tin) than spreading faster in silicon, this can be reduced by silicon, the concentration gradient of the lithium ion of the larger composite particles of tin and aluminium, thus effectively reduce the stress spreading and cause, to alleviate breaking of larger composite particles, (3) if cracked in composite material, relatively soft aluminium and tinbase matter are tended to absorb elastic strain energy and prevent any micro-crack from spreading mutually, and (4) silicon, aluminium and the immiscible characteristic of tin and being separated decreases electrochemistry sintering to greatest extent, thus prevent particles coalesce, otherwise damage causing the Quick mechanical of electrode material.In addition, can show as passivation layer (passivation layer) in the thin oxide layer of silicon phase and Metal Phase (especially aluminium) interface self-assembling formation, improve coulombic efficiency and also can prevent electrochemical dissolution, impel Charger transfer to the surface of combination electrode material.
The phase separated particles compound of particle form can such as by preparing even (or homodisperse) liquid mixture rapid solidification (such as, melt spinning) of element aluminum, tin and silicon.In another example, by with predetermined ratio on suitable surface, the phase-separated mixtures of the aluminium separated as cosputtering on copper current collector, tin and silicon source and codeposition aluminium, tin and silicon forms as electrode film the compound that is separated.If sputtering sedimentation thing to be atom uniform, by heated substrate (such as, being up to about 500 DEG C) or realize being separated of silicon, tin and the second metallic element by another post growth annealing.
Usually, preferred preparation is by aluminium (and/or copper, the titanium of the silicon of about 20-80 atomic percent, the tin of about 20-60 atomic percent and about 1-30 atomic percent, or other metallic element accepting lithium be applicable to) compound that is separated of component, for the negative material of lithium ion battery or lithium-sulfur cell.
According to the embodiment of the present invention, by the atomic ratio of silicon/tin/aluminium in adjustment tin-silicon-aluminium compound, the mechanical loss being used alone pure tin or pure silicon and carrying out producing when lithium embeds can be alleviated thus.With the silicon/tin/aluminum ratio be applicable to, the matrix that the amorphous phase bunch be separated with silicon embeds crystallization or amorphous tin and crystallization or amorphous aluminium mutually in and occur.The negative material of gained shows the lithium charge storage significantly improved and the cyclical stability of brilliance.
Therefore, according to the embodiment of the present invention, the compound that is separated of silicon, tin and aluminium (or other second metallic element) is formed as the layer of relative thin on suitable collector paper tinsel or sheet, as the negative material of battery in Li-ion batteries piles or lithium-sulfur cell group.Like this, by using the combination that is separated of this silicon, tin and aluminium, the lithium intercalation capacity of each battery increases, thus improves volume and/or the gravimetric of Li-ion batteries piles or lithium-sulfur cell group.
By the detailed description to embodiment of the present invention practice following in specification, other object of the present invention and advantage will be apparent.
Brief Description Of Drawings
Fig. 1 is the enlarged diagram of a small amount of electrochemical cell of exemplary lithium-ion device.Each battery thin, the positive pole of rectangle negative pole, analogous shape and folder barrier film between electrodes, this negative pole can comprise the silicon be separated, tin and the second metallic composite in the present invention.
Fig. 2 is the cross sectional view of the further amplification Sum decomposition of the electrochemical cell of shown in Fig. 1.Fig. 2 also show the metal collector supporting each electrode material.The element of battery is shown separately for example, and they compress contact in fact face-to-face, and electrode material is formed in or adheres on their respective collectors.
Fig. 3 is the schematic diagram of the scanning electron microscopy picture (SEM) based on silicon-Xi composite sample.This SEM image has been labeled the compound that is separated (such as, the Si for representative silicon, tin and the aluminium of example
50sn
25al
25compound, wherein subscript represents component atomic percentage numerical value) configuration of surface.Original silicon-Xi composite sample is by making from the sputtering target sputtered silicon of separating and tin to form film in copper bar substrate.Silicon is considered to be present in mutually in the matrix of aluminium phase and tin phase with island.
Fig. 4 is for the Si as anode material in using pure lithium as the half-cell of counterelectrode
50sn
25al
25the compound of component, the left longitudinal axis is specific capacity (mAh/g), and the right longitudinal axis is coulombic efficiency (CE) vs. trunnion axis is cycle-index, and it reaches at most the figure of about 500 primary cell circulations.Electrolyte solution is the 1MLiPF containing 10% fluoroethylene carbonate additive
6ethylene carbonate and dimethyl carbonate (1: 1v/v).Carry out at circulating in 25 DEG C.Solid data represents than charging capacity (mAh/g) data point.Long-short dash line represents the data point than discharge capacity (mAh/g).Isometric dotted line represents the data point of CE.
Fig. 5 is for the Si as anode material in using pure lithium as the half-cell of counterelectrode
50sn
25cu
25the compound of component, the left longitudinal axis is specific capacity (mAh/g), and the right longitudinal axis is CE vs. trunnion axis is cycle-index, and it reaches at most the figure of about 500 primary cell circulations.Electrolyte solution is the 1MLiPF containing 10% fluoroethylene carbonate additive
6ethylene carbonate and dimethyl carbonate (1: 1v/v), carry out at circulating in 25 DEG C.Solid data represents than charging capacity (mAh/g) data point.Long-short dash line represents the data point than discharge capacity (mAh/g).Isometric dotted line represents the data point of CE.
Fig. 6 is for the Si as anode material in using pure lithium as the half-cell of counterelectrode
50sn
25ti
25the compound of component, the left longitudinal axis is specific capacity (mAh/g), and the right longitudinal axis is CE vs. trunnion axis is cycle-index, and it reaches at most the figure of about 500 primary cell circulations.Electrolyte solution is the 1MLiPF containing 10% fluoroethylene carbonate additive
6ethylene carbonate and dimethyl carbonate (1: 1v/v), carry out at circulating in 25 DEG C.Solid data represents than charging capacity (mAh/g) data point.Long-short dash line represents the data point than discharge capacity (mAh/g).Isometric dotted line represents the data point of CE.
Fig. 7 is for the Si as anode material in adopting pure lithium as the half-cell of counterelectrode in Fig. 4
50sn
25al
25the additional cycles of the compound of component, the left longitudinal axis is specific capacity (mAh/g), and the right longitudinal axis is CEvs. trunnion axis is cycle-index, and it reaches at most the figure of about 2000 primary cell circulations, carries out at circulating in 25 DEG C.Solid data represents than charging capacity (mAh/g) data point.Long-short dash line represents the data point than discharge capacity (mAh/g).Isometric dotted line represents the data point of CE.
Embodiment
Fig. 1 describes the example of the exemplary of Li-ion batteries piles 10 and generalization.Li-ion batteries piles 10 shown here comprises several that supported by metal collector respectively, thin rectangle electrochemical battery cell 12.Electrochemical battery cell 12 is stacked alongside in a modular construction, and in this example, it is for being connected in parallel.Li-ion batteries piles 10 can be formed by the electrochemical cell of multiple similar electric serial or parallel connection, to form the Li-ion batteries piles had for the voltage and current capacity needed for application-specific.Should be understood that shown here Li-ion batteries piles 10 is only schematic presentation.Fig. 1 is for illustrating relative position and the Physical interaction of the multiple parts (that is, electrode and barrier film) forming electrochemical battery cell 12; It is not intended to the relative size of the parts of informing electrochemical battery cell, limits the quantity of electrochemical battery cell 12 in Li-ion batteries piles 10, or the various structures configuration that limiting lithium ion cell group 10 can present.
Be included in the electrochemical cell 12 (representing 1) in Li-ion batteries piles 10, comprise negative pole 14, positive pole 16 and the barrier film 18 between two relative electrodes 14,16.Negative pole 14, positive pole 16 and barrier film 18 are all infiltrated by liquid electrolyte solution, and this liquid electrolyte solution can transport lithium ion between electrode 14,16.Comprise the negative metal collector 20 (being generally copper) of negative lug 22 between the back-to-back negative pole 14 of adjacent electrochemical cell 12.Equally, the side of the positive electrode metal collector 24 (being generally aluminium) of positive pole ear 26 is comprised between adjacent positive pole 16.Negative lug 22 is electrically connected to negative terminal 28, and positive pole ear 26 is electrically connected to positive terminal 30.Each electrode material 14,16 is usually formed at or adheres in its corresponding metal collector 20,24.Metal collector 20,24 and electrode 14,16 thereof press relative to barrier film 18 by the compression stress of usual applying, to make between adjacent contact parts interracial contact closely.Negative terminal 28 and positive terminal 30 are connected to electrical source consumption type load (electrical power consumingload) 50.Such as, the battery pack be applicable to comprising multiple similar single battery can be used for for traction motor is powered, with the wheel of driving machine motor vehicle.In this battery pack, multiple battery is arranged in parallel connection in groups with electricity, and to provide suitable power capacity, multiple groups are connected in series, to provide suitable voltage potential.
The cross sectional view of the decomposition of metal collector 20,24 that Fig. 2 illustrates in general electrochemical battery cell 12 and is associated.Relative to the position of barrier film 18, negative pole 14 comprises inner surface 32, outer surface 34.Positive pole 14 comprises inner surface 36 and outer surface 38 equally.As shown in the figure, negative pole 14 inner surface 32 can but non-essentially comprise the two-dimensional surface area larger than the inner surface 36 of positive pole 16.When being assembled in electrochemical battery cell 12, the inner surface of negative pole and positive pole 14,16 32,36 facing with each other, and be pressed towards negative side first type surface 40 and the side of the positive electrode first type surface 42 of barrier film 18 respectively.Along the whole interface of the appropriate section on barrier film 18 first type surface 40,42 and electrode 14,16 inner surface 32,36, this pressing engages and is roughly uniformly.Negative side metal collector 20 is formed at or is connected to the outer surface 34 of negative pole 14, and side of the positive electrode metal collector 24 is formed at or is in electrical contact with the outer surface 38 of positive pole 16.In embodiments of the invention, compound tin-silicium cathode material is directly formed on the surface of copper negative current collector 20.Both metal collector 20,24 are all engaged, so that effectively collect and conduct free electron with its respective electrode outer surface 34,38 by obvious interface region.
In multiple Li-ion batteries piles, the element of electrochemical cell 12 is by making it usually thin and the material of flexibility is made.With illustrative examples form, the typical thickness (T in Fig. 2) of electrochemical cell 12, it extends to the outer surface 38 of positive pole 16 from the outer surface 34 of negative pole 12, is approximately 80 μm to 350 μm.Each electrode 14,16 thick about 30 μm to 150 μm, thick about 20 μm to 50 μm of barrier film 18.Metal collector 20,24 thick about 5 μm to 20 μm.The element of electrochemical cell 12 and the relative thin of metal collector 20,24 that is associated thereof and the feature of flexibility, make it can be rolled-up according to design specification and spatial limitation, folding, bending, or otherwise operate and form multiple lithium ion battery structure.Li-ion batteries piles 10 such as, can comprise and multiplely different be assembled, shear, align and electrochemical cell 12 placed adjacent one another, or in alternate embodiments, this battery 12 can obtain from repeatedly folding back and forth pantostrat itself.
Although Li-ion batteries piles has obtained development and application, such as, be the power supply such as traction motor of motor vehicle, also in consideration, lithium-sulfur cell group be used for this kind of application at present.As described, lithium-sulfur cell also adopts negative pole (anode) containing lithium and electrode material, and the electrochemical function of electrode material and lithium ion battery or battery electrode is similar.Therefore, no matter whether negative material is for Li-ion batteries piles or lithium-sulfur cell group, and silicon-Xi-the second metal component further described in this specification and micro-structural are all applicable to the embedding of lithium.When preparation has the negative pole of silicon-Xi-aluminium of the present invention (or other second metal) composite layer as negative material, be necessary to provide the lithium of scheduled volume to the introducing in the electrode material of battery.In a preferred embodiment, such as by electrochemistry insert, plating, vacuum moulding machine or suitable electrolyte exist under contact with lithium metal physics, the lithium of specified amount can be introduced (lithiumation) in silicon-tin composite material.In another embodiment, before the element assembling of lithium-sulfur cell, the lithium of appropriate amount can be incorporated in the positive electrode of sulfur-bearing.During the battery or battery pack initial charge of assembling, lithium will be carried by electrolyte and be embedded into comprehensive silicon-tin negative pole material.
Embodiments of the present invention are intended to for the negative pole of lithium ion electrochemical cells forms higher current capacity and more durable material.Prepare silicon, tin and the second metal compound that is separated as aluminium, copper or titanium for this purpose.
Prepare the complex components of second metal (for supplementary tin) of the silicon of 50 atomic percents of element form, the tin of 25 atomic percents and 25 atomic percents.Described second metal is aluminium, copper or titanium.These compounds are respectively by title Si
50sn
25al
25, Si
50sn
25cu
25and Si
50sn
25ti
25.Respective compound codeposition in 1000 gamma sputtering systems (Surrey Nanosystems, UK) is that element laminated film is formed.In each preparation process, coarse Copper Foil is used to provide good bonding between silicon-Xi-the second metallic film and copper current collector of sputtering.Deposition plasma for often kind of composition material (silicon, tin and aluminium or copper or titanium) adopts RF (for silicon) and DC power supply (for metallic element) to produce respectively, is applied to three magnetic control rifles under the argon gas stream of 14sccm.Control the deposition rate of silicon, tin and the second metallic element respectively, to obtain the different atomic ratios of these elements of afore mentioned rules.Dynamic pressure in film growth course is 3mTorr, and substrate keeps at room temperature.
Ex-situ X-ray diffraction (XRD) is for studying the structure of the film be deposited on copper current collector.All samples all uses Cu K α radiation to detect in the surface detector diffractometer system (GADDS) of Bruker AXS.Diffraction image acquisition time is 5 minutes, and it adopts 0.5-mm pointing instrumentation, and sample and detector distance are 150mm.The component of each sample pad is determined by probe-microanalyser (EPMA), and the JEOL 2100F AC transmission electron microscope worked under the sample simultaneously utilizes 200kV characterizes.High angle annular dark field (HAADF) detector is utilized to collect the image of scanning transmission electron microscope (STEM).
All electrochemistry experiments all under ambient temperature (25 DEG C), be full of in the glove box of argon gas Coin-shaped battery in carry out.Pure lithium metal is adopted to test for half-cell as counterelectrode.Electrolyte solution is the 1MLiPF containing 10% fluoroethylene carbonate additive
6ethylene carbonate (EC) and dimethyl carbonate (DMC) (1: 1v/v).Celgard3501 (1 μm of thick polypropylene microporous film, porosity is 40%) is as barrier film.The constant current test of all samples all adopts Arbin BT-2000 battery pack testing station with the cyclical voltage of 10mV to 1.5V (relative to Li/Li
+electrode) carry out.
XRD result comprises the strong Cu diffraction maximum observed from substrate and shows and severally shows that tin is the Xi Feng of crystal mutually.According to concrete sample, also can be observed strong aluminium peak, copper peak or titanium peak.The diffraction maximum of silicon do not detected, this shows the amorphous state feature of Si.This is in accordance with expectation, because form crystalline phase to too low being not enough to of depositing temperature silicon.In checked any sputtered samples, do not observe the peak representing other any silicon-Xi phase or silicon-aluminium phase or silicon-copper phase or silicon titanium phase, this clearly illustrates that silicon and two metal ingredients are separated, and this is consistent with the unmixability of known silicon, tin, aluminium, copper and titanium.This nanostructure caused by being separated is very crucial to significantly improving its chemical property.Integrated mechanism will further describe in this manual.
Based on known Scherrer formula, the tin be estimated to from X-ray diffractogram and the average crystalline size of aluminium are about 20 to 50nm.
Fig. 3 is silicon and the SEM image of tin composite of sputtering, and it is schematically marked, to show shape and the position of island silicon phase and tin and aluminum matrix phase.Black island bunch is the crystal grain of silicon phase.Lighter image boundary around silicon crystal grain is the combination of shelly microstructure separately mutually, and it is formed with aluminium mutually by the tin separated.In the forming process of composite material, aluminium and tin tend to wetting silicon particle, form metal oxide layer in the interface of phase.The existence of interface metal oxide improve first time charge-discharge cycles efficiency and with metacyclic stability.SEM image also indicates extra random nun's thread, and it is drawn from the top of image to bottom through matrix phase.This extra line represents undesirable micro-crack in composite material.This micro-crack is non-existent, and is avoided by shown component and microstructure.The diffusion of lithium in tin and aluminium is faster than it in silicon, and this makes being more evenly distributed of lithium in compound.Because the concentration gradient of lithium is lower, the stress produced in composite construction is less.Do not wish micro-crack in negative material, because they can affect the function of material.
To Si
50sn
25al
25the compound of component is tested as the anode material in the half-cell of counterelectrode as the pure lithium of employing.Electrolyte solution is the 1MLiPF of the fluoroethylene carbonate additive containing 10 volume %
6ethylene carbonate and dimethyl carbonate (1: 1v/v), carry out at circulating in 25 DEG C.The Si measuring lithium to be embedded is operated to battery
50sn
25al
25the specific capacity of the compound of component is (at Si
50sn
25al
25ratio charging capacity between component charge period, with every gram of lithium milliamperemeter per hour).In contrary circulation, to battery-operated for by lithium from Si
50sn
25al
25remove in component.Fig. 4 is for the Si as anode material in adopting pure lithium as the half-cell of counterelectrode
50sn
25al
25the compound of component, the left longitudinal axis is specific capacity (mAh/g), and the right longitudinal axis is CE (coulombic efficiency) vs. trunnion axis is cycle-index, and it reaches at most the figure of about 500 primary cell circulations.Solid data represents than charging capacity (mAh/g) data point.Long-short dash line represents the data point than discharge capacity (mAh/g).Isometric dotted line represents the data point of CE.Can find out, after 10 circulations, the coulombic efficiency of battery operation remains on more than 99.5%.In whole 500 circulations, during discharge and recharge, the specific capacity of composite material remains on 1200-1600mAh/g.
Fig. 7 gives the Si adopted as the above-mentioned preparation of anode material in using pure lithium as the half-cell of counterelectrode
50sn
25al
25the additional data that the more multi cycle (reaching maximum 2000 charge/discharge cycle) of component obtains.After the circulation several times started, during charge and discharge cycles, specific capacity value maintains about 1180mAh/g, until about 1600 circulations.After 5 circulations, coulombic efficiency remains on more than 99.5%.
To the Si as anode material in using pure lithium as the half-cell of counterelectrode
50sn
25cu
25the compound of component is tested.Electrolyte solution is the 1MLiPF of the fluoroethylene carbonate additive containing 10 volume %
6ethylene carbonate and dimethyl carbonate (1: 1v/v), carry out at circulating in 25 DEG C.Si for determining lithium to be embedded is operated to battery
50sn
25cu
25the specific capacity of component is (at Si
50sn
25al
25than charging charge capacity between component charge period, with every gram of lithium milliamperemeter per hour).In contrary circulation, to battery operate for by lithium from Si
50sn
25cu
25remove in component.Fig. 5 is for the Si as anode material in using pure lithium as the half-cell of counterelectrode
50sn
25cu
25the compound of component, the left longitudinal axis is specific capacity (mAh/g), and the right longitudinal axis is CE (coulombic efficiency) vs. trunnion axis is cycle-index, and it reaches at most the figure of about 200 primary cell circulations.Solid data represents than charging capacity (mAh/g) data point.Long-short dash line represents the data point than discharge capacity (mAh/g).Isometric dotted line represents the data point of CE.Can find out, after 20 circulations, the coulombic efficiency of battery operation remains on more than 99%.During discharge and recharge, the specific capacity of composite material starts from the level of about 800mAh/g.Subsequently owing to forming intermetallic compound between copper and tin, it experienced by continuous print and reduces.
To the pure lithium of use as the Si as anode material in the half-cell of counterelectrode
50sn
25ti
25the compound of component is tested.Electrolyte solution is the 1MLiPF containing 10 volume % fluoroethylene carbonate additives
6ethylene carbonate and dimethyl carbonate (1: 1v/v), carry out at circulating in 25 DEG C.Si for determining lithium to be embedded is operated to battery
50sn
25ti
25the specific capacity of component is (at Si
50sn
25ti
25ratio charging capacity between component charge period, with every gram of lithium milliamperemeter per hour).In contrary circulation, to battery operate for by lithium from Si
50sn
25ti
25remove in component.Fig. 6 is for the Si as anode material in using pure lithium as the half-cell of counterelectrode
50sn
25ti
25the compound of component, the left longitudinal axis is specific capacity (mAh/g), and the right longitudinal axis is CE (coulombic efficiency) vs. trunnion axis is cycle-index, and it reaches the figure of about 200 primary cell circulations at most.Solid data represents than charging capacity (mAh/g) data point.Long-short dash line represents the data point than discharge capacity (mAh/g).Isometric dotted line represents the data point of CE.Can find out, after 50 circulations, the coulombic efficiency of battery operation remains on more than 99%.During discharge and recharge, the specific capacity of composite material about starts from 800mAh/g.Intermetallic compound subsequently owing to being formed between titanium and tin, specific capacity experienced by continuous print and reduces.
Experimental data given by Fig. 4-7 shows, in tested three kinds of combinations, the combination of the silicon tested, tin and aluminium behaves oneself best.The nanostructure that silicon-Xi-the second metallic element complex components that these test charts understand keeps it to be separated and the importance being formed at the suitable oxide skin(coating) on material surface.
In above-mentioned example, composite negative pole material obtains by independent component is splashed to copper foil current collector.Silicon-Xi-the second metal component be separated is also by obtaining the improving uniformity of melt rapid solidification of the silicon of proper proportion, tin and aluminium (or analog).Usually be preferably formed the tin of the silicon of about 20-80 atomic percent, about 20-60 atomic percent, and the aluminium of about 1-30% atomic percent, copper, titanium or other suitable accepted lithium and with the compound of one of silicon and the immiscible metal of tin.Such as, use the example of the compound of silicon, tin and aluminium, this process can be carried out as follows:
1. described in book as described above, by predetermined atomic ratio, together with silicon, tin are melted in aluminium.
2. melt progressively rapid solidification to form particle, sheet or band.
3. such as under being low to moderate low temperature suitable between-30 DEG C lower than 0 DEG C, under an inert atmosphere, by low temperature ball milling, particle is pulverized, to avoid particulate oxidation, thus form the particle of full-size 1-5 microns (or less) of roughly uniform shapes.
4. in certain embodiments, if needed, particle can be annealed, and is embedded into tin and aluminium and separates the amorphous silicon phase nanoscale island in phase matrix by being formed and bring out and be separated.The composite particles of this silicon, tin and the aluminium that are separated is considered to the active material for lithium ion battery negative.
5. the particle of active material is adhered to applicable metal collector, preferably copper collector, forms negative pole.Such as, the particle of active electrode material can mix with the polymer adhesive be applicable to, if weight ratio is poly-inclined (two) PVF (PVDF) or mosanom and the carbon black (Ampereconductors) of 80: 10: 10.Inertia carrier fluid can temporarily for dispersed mixture on one or two relative surface of thin current collector band.Removing carrier fluid, mixture sticks on the surface of current collector film together with polymer adhesive.Due to carbon black pellet, the conductivity of silicon-Xi-aluminium compound improves further.
Therefore, the film that copper current collector is separated suitably to be formed in presumptive area and to have the thickness determined, for being assembled into the negative material in lithium ion electrochemical cells or lithium-sulfur electrochemical cells.During electrode manufactures or during other operation of initial charge or battery, lithium can be incorporated in silicon-Xi-aluminium compound.Select total amount and the lithium content thereof of negative material, to provide the electrode capacity of expectation.
Describe embodiments of the present invention for purpose of explanation, it not limits the scope of the present invention.
Claims (10)
1. lithium ion or lithium-sulphur making active materials for use in secondary electrochemical cells or a battery pack, comprises the negative pole component using lithium; In battery or batteries charging process, lithium is embedded in negative pole component, and in battery or battery power discharge process, lithium is deviate from from this negative pole component; Negative material comprises silicon, tin and is selected from the compound of the second metallic element of aluminium, copper and titanium, this compound feature be also silicon, tin and the second metal be present in respectively separately mutually in, tin phase and the second metallic element are crystallization or amorphous mutually, and silicon is amorphous mutually.
2. lithium ion as claimed in claim 1 or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the second metallic element is aluminium.
3. lithium ion as claimed in claim 1 or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the compound of silicon, tin and the second metallic element is by the silicon of 20-80 atomic percent, the tin of 20-60 atomic percent and the second metallic element composition of 1-30 atomic percent.
4. lithium ion as claimed in claim 1 or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the feature of the compound of silicon, tin and the second metallic element is the amorphous silicon phase nanoscale island that is dispersed in the matrix of tin phase and the second metallic element phase.
5. lithium ion as claimed in claim 1 or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the feature of the compound of silicon, tin and the second metallic element is the tin phase crystal of size all in 20 nanometer to 50 nanometer range and the second metallic element phase crystal.
6. lithium ion as claimed in claim 1 or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the compound of silicon, tin and the second metallic element forms adhesive film by the surface that silicon, tin and the second metallic element is splashed to the metal collector of negative material, and the film thickness of sputtering is about at most 5 microns.
7. lithium ion as claimed in claim 2 or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the compound of silicon, tin and aluminium by forming adhesive film by silicon, tin and sputtered aluminum to the surface of the metal collector of negative material, and the film thickness of sputtering is about at most 5 microns.
8. lithium ion as claimed in claim 1 or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the compound of silicon, tin and the second metallic element is formed by the melt liquid of silicon, tin and the second metallic element being rapidly solidificated into the solid particle of the compound that is separated of silicon, tin and the second metallic element, if needed, this solid particle size is decreased to about 1-5 micron, and sticks in the metal collector of negative material.
9. lithium ion as claimed in claim 1 or lithium-sulphur making active materials for use in secondary electrochemical cells or battery pack, wherein the compound of silicon, tin and aluminium is formed by making the melt liquid of silicon, tin and aluminium be rapidly solidificated into the solid particle of the compound that is separated of silicon, tin and aluminium, if needed, this solid particle size is decreased to about 1-5 micron, and sticks in the metal collector of negative material.
10. lithium ion or lithium-sulphur making active materials for use in secondary electrochemical cells or a battery pack, comprise negative pole component and anode constituents; In battery or batteries charging process, by transporting lithium containing lithium electrolyte, lithium being embedded in negative pole component and deviating from from anode constituents; In battery or battery power discharge process, by transporting lithium containing lithium electrolyte, lithium is made to deviate from from negative pole component and be embedded in anode constituents; Negative material comprises silicon, tin and is selected from the compound of the second metallic element of aluminium, copper and titanium, this compound feature be also silicon, tin and the second metallic element be present in respectively separately mutually in, tin phase and the second metallic element are crystallization or amorphous mutually, and silicon is amorphous mutually.
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