CN104247089B - Hybrid energy storage device - Google Patents

Abstract

A kind of novel mixing lithium-ion anode material, this mixing lithium-ion anode material is based on the silicon shell of coating coaxial on carbon nano-fiber (CNF) array being vertically arranged.Unique cup-shaped stacking graphite microstructure makes the exposed CNF array being vertically arranged become effective Li⁺Insert medium.The Li of high reversible⁺It is inserted and removed from being observed under high power speed.More importantly, the CNF core with mechanically stable of highly conductive selectively supports the amorphous silicon shell of coaxial coating, and this amorphous silicon shell has much higher theoretical specific capacity by forming the alloy of abundant lithiumation.The skin effect of close proximity insertion medium is propped up the interpolation of coordination site and is caused mixing arrangement, and this mixing arrangement includes the advantage of battery and capacitor.

Description

Hybrid energy storage device

Cross-Reference to Related Applications

The application is:

In the U.S. Non-provisional Patent patent application serial numbers 13/779,571 that on February 27th, 2013 submits to Continuation application；

U.S. Non-provisional Patent patent application serial numbers 13/725,969 in December in 2012 submission on the 21st Part continuation application；And

Require rights and interests and the priority of following U.S. Provisional Patent Application:

In on February 27th, 2012 submit to 61/603,833,

In on March 23rd, 2012 submit to 61/615,179,

In on July 3rd, 2012 submit to 61/667,876,

In 61/677,317 and that on July 30th, 2012 submits to

In submission on January 14th, 2013 61/752,437.

The disclosure of the patent application of all of above-mentioned interim and non-provisional is accordingly by being incorporated by Herein.

Background

Invention field

The present invention is at the neck of the energy storing device including but not limited to battery, capacitor and fuel cell In territory.

Correlation technique

Rechargeable lithium ion battery will be in portable electric appts, electric tool and future The crucial electrical energy storage device of supply of electric power in electric vehicle.Carry high specific energy capacity, charging/ The velocity of discharge and cycle life are critical to they wider applications.

In the lithium ion battery of current business, graphite or other carbonaceous materials are adequately inserted by formation LiC₆Compound and be used as the anode with the theoretical capacity limits of 372mAh/g.On the contrary, Silicon is by forming the metal Li of abundant lithiumation_4.4Si and there is the theory ratio of much higher 4,200mAh/g Capacity.But, the silicon of lithiumation up to～300% large volume expand and cause and inevitably led in the past Causing the great structural stress of fracture and mechanical breakdown, this significantly limits the life-span of silicon anode.

General introduction

In some embodiments, the mixing during a kind of energy storage device is included in high-performance lithium ion anode Core-shell structure copolymer NW (nano wire) structure, this be by combine coaxially be coated with the vertical of amorphous si-layer Carbon nano-fiber (VACNF) array of arrangement.The CNF being vertically arranged includes the carbon nanometer of many walls Pipe (MWCNT), the CNT of these many walls uses the plasma activated chemical vapour deposition of direct current biasing (PECVD) method selectively grows in Copper base material.The carbon nano-fiber grown by the method (CNF) can have the external morphology of uniqueness, they are different from common MWCNT by this form Hollow structure with conventional solid carbon nanofiber.One of distinguishing characteristics be these CNF selectively It is made up of a series of bamboo shape nodes crossing main hollow centre passage.This micro structure can be returned Because of the conical graphite cup stacking discussed further in elsewhere herein.Under bigger length scale, It is evenly distributed and divide the most each other that the CNF of these PECVD-growth is typically orthogonal to substrate surface From.They may without any entanglement or have minimum entanglement, and therefore formed be referred to as VACNF battle array The brush-like structure of row.Individually the diameter of CNF can be selected as providing desired mechanical strength with VACNF array is made to be firm and it can be kept complete by siliceous deposits and wet electro-chemical test Property.

The multiple embodiments of the present invention includes the supporting wire of the several types in addition to VACNF. These supporting wires can include, such as nano wire, carbon plate or other structures described herein.Other are real Scheme of executing does not includes any supporting wire and changes into using binding agent.

The multiple embodiments of the present invention includes a kind of energy storage system, and it includes conductive base；? Multiple carbon nano-fibers being vertically arranged of growth on base material, this carbon nano-fiber includes multiple many walls CNT；And electrolyte, this electrolyte includes one or more charge carriers.

The multiple embodiments of the present invention includes a kind of energy storage system, and it includes conductive base；? Multiple carbon nano-fibers being vertically arranged of growth on base material；And insert material layer, this insertion material Layer is disposed on the plurality of carbon nano-fiber being vertically arranged and is configured with every gram of insertion Material about lithium ion memory capacity between 1,500 and 4,000mAh.

The multiple embodiments of the present invention includes a kind of energy storage system, and it includes conductive base；? Multiple carbon nano-fibers being vertically arranged of growth on base material；And insert material layer, this insertion material Layer is disposed on the plurality of carbon nano-fiber being vertically arranged and is configured such that at 1C and 3C Charge rate under the ion storage capacity of this insertion material be about identical.

The multiple embodiments of the present invention includes a kind of method producing energy storing device, the method bag Offer base material is provided；Growing carbon nano-fiber on base material, this carbon nano-fiber has cone-in-cone (stacked-cone) structure；And insertion material is applied to carbon nano-fiber, this insertion material quilt It is configured to the insertion of charge carrier.

The multiple embodiments of the present invention includes a kind of energy storage system, comprising: include one or The electrolyte of multiple charge carrier；Conductive base；Attach to multiple supporting wires being vertically arranged of base material； Insert material, its be disposed in supporting wire each upper and being configured in the main body inserting material The most reversibly member of adsorption charge carrier；And binding agent, its be disposed in insertion material on and Including multiple nano-particle, each nano-particle is configured to supply skin effect and props up coordination site, this table Face effect props up the faradic interaction that coordination site is configured on nano grain surface The member of adsorption charge carrier.

The multiple embodiments of the present invention includes a kind of energy storage system, comprising: include one or The electrolyte of multiple charge carrier；Conductive base；Attach to multiple supporting wires of base material；Insert material, It is disposed in supporting wire each upper and being configured in the main body inserting material reversibly The member of adsorption charge carrier；And binding agent, it is disposed on insertion material and includes multiple Skin effect props up coordination site, and this skin effect is propped up coordination site and is configured to promote that charge carrier is inserted into slotting Enter in material.

The multiple embodiments of the present invention includes a kind of energy storage system, comprising: include one or The electrolyte of multiple charge carrier；Conductive base；Inserting material, it is configured to insert most Enter the member of reversibly adsorption charge carrier in material；And binding agent, it is disposed in insertion material Go up and include that nano-particle, each nano-particle are configured to supply skin effect and prop up coordination site, should Skin effect props up the faradic phase interaction that coordination site is configured on nano grain surface With the member that electronics is supplied to charge carrier.

The multiple embodiments of the present invention includes a kind of energy storage system, comprising: negative electrode；And Anode, it is by including electrolyte and the cathodic disbonding of one or more charge carriers, and this anode includes Inserting material and multiple nano-particle, this insertion material is configured to insert charge carrier and first Under reaction electromotive force, electronics being supplied to this charge carrier, this nano-particle includes skin effect Zhi Peiwei Point, this skin effect is propped up coordination site and is configured to be supplied to by electronics electric charge load under the second reaction electromotive force Body, the absolute difference between the first reaction electromotive force and the second reaction electromotive force is less than 2.4V.

The multiple embodiments of the present invention includes a kind of system, comprising: at charge storage devices Anode at set up the instrument of potential gradient, this anode includes electrolyte, multiple skin effect Zhi Peiwei Point, insertion material and base material；Electrolyte is received in propping up coordination site in skin effect one The instrument of charge carrier；Connect for propping up in coordination site from skin effect at charge carrier Receive the instrument of electronics；And for inserting the instrument receiving charge carrier at material.

The multiple embodiments of the present invention includes a kind of method producing energy storing device, the method bag Include: conductive base is provided；Base material grows supporting wire；It is applied to insertion material support Nanowire Dimension, this insertion material is arranged to the insertion of charge carrier；And by multiple skin effects Zhi Peiwei Point is applied for close proximity and inserts material.

The multiple embodiments of the present invention includes a kind of method producing anode, and the method includes: provide Conductive base；Jointing material, skin effect being propped up coordination site and insert material mixing, this surface is imitated Coordination site should be propped up be configured to accept electronics and this insertion from charge carrier under the first reaction electromotive force Material is configured to accept charge carrier or accept electronics from charge carrier under the second reaction electromotive force；And And jointing material, skin effect are propped up coordination site and inserts material and be applied to base material.

The multiple embodiments of the present invention includes a kind of method producing energy storing device, the method bag Include: conductive base is provided；Supporting wire is provided；Insertion material is applied to supporting wire, this insertion material It is arranged to the insertion of charge carrier；And skin effect is propped up coordination site and adds supporting wire to.

The multiple embodiments of the present invention includes a kind of method making charge storage devices charge, the method Including: setting up electromotive force between the negative electrode and anode of charge storage devices, this charge storage devices includes Electrolyte；Skin effect at anode is arranged site and is received the first charge carrier of electrolyte；By sun The electron transfer of pole is to the first charge carrier；The second electricity inserting reception electrolyte at material at anode Charge carrier；And electronics is transferred to the second charge carrier from inserting material.

The multiple embodiments of the present invention includes a kind of method making charge storage devices charge, the method Including: setting up potential gradient at the anode of charge storage devices, this anode includes electrolyte, has Skin effect is propped up multiple nano-particle of coordination site, is inserted material and base material；In skin effect Zhi Peiwei The first charge carrier of electrolyte is received in point one；Electronics is propped up coordination site from skin effect One at transfer to the first charge carrier；The second charge carrier is received at the insertion material of anode； And electronics is transferred to the second charge carrier from inserting material.

Accompanying drawing is sketched

Figure 1A and 1B illustrates the CNF array of the multiple embodiments according to the present invention, this CNF Array is included on base material multiple CNF of growth.

Fig. 2 A-2C illustrates multiple perpendicular under different conditions of the multiple embodiments according to the present invention The CNF of in line row.

Fig. 3 A-3C illustrates the details of the CNF of the multiple embodiments according to the present invention.

Fig. 4 illustrates the schematic diagram of the cone-in-cone structure of the CNF of the multiple embodiments according to the present invention.

The electrification of that Fig. 5 A-5C illustrates the multiple embodiments according to the present invention～3 μm length CNF Learn characteristic.

Fig. 6 A-6C illustrates the scanning of the CNF of 3 μm length of the multiple embodiments according to the present invention Electron microscope image.

Fig. 7 A-7C illustrates the use of the multiple embodiments according to the present invention and comprises as lithium-ion electric The result that the CNF of the silicon layer of pond anode obtains.

How Fig. 8 illustrates the capacity of the CNF array of the multiple embodiments according to the present invention with charging Rate changes.

Fig. 9 illustrates the Raman spectrum of the CNF array of the multiple embodiments according to the present invention.

Figure 10 A-10C show the multiple embodiments according to the present invention 15 charge-discharge cycles Period Li⁺Insert-take out capacity and the change of coulombic efficiency.

Figure 11 A-11C shows the CNF array recently prepared of the multiple embodiments according to the present invention Scanning electron microscope image.

Figure 11 D shows the cross section of the nanofiber/silicon compound comprising more than one CNF.

Figure 12 illustrates the carbon of the fiber including 10 μm length of the multiple embodiments according to the present invention Nanofiber array.

Figure 13 illustrates the method for the production CNF array of the multiple embodiments according to the present invention.

What Figure 14 A illustrated the multiple embodiments according to the present invention includes power reinforcing material CNF。

Figure 14 B illustrates the power illustrated in Figure 14 A of the multiple embodiments according to the present invention to be strengthened The details of material.

Figure 14 C illustrates the power illustrated in Figure 14 A of the multiple embodiments according to the present invention to be strengthened The alternative details of material.

What Figure 15 illustrated the multiple embodiments according to the present invention includes power reinforcing material and by inserting Enter the electrode surface of the CNF not arranged of material coating.

Figure 16 illustrates including power reinforcing material, not arranging of the multiple embodiments according to the present invention The CNF arranged and the electrode surface inserting material (free intercalation material) freely.

What Figure 17 illustrated the multiple embodiments according to the present invention includes that inserting material and power strengthens Material and without the electrode surface of CNF.

Figure 18 illustrate the multiple embodiments according to the present invention include be arranged to close proximity The skin effect of CNF props up the electrode surface of coordination site.

Figure 19 and 20 illustrate the multiple embodiments according to the present invention include be arranged to closely connect The nearly skin effect inserting material freely props up the electrode surface of coordination site.

Figure 21 illustrates the method for the assembling electrode surface of the multiple embodiments according to the present invention.

Figure 22 illustrates the method for the operation charge storage devices of the multiple embodiments according to the present invention.

Describe in detail

Figure 1A and 1B illustrates the CNF array 100 of the multiple embodiments according to the present invention, should CNF array 100 is included on conductive base 105 multiple CNF 110 of growth.In figure ia, CNF array 100 is shown as in lithium taking-up (electric discharge) state, and in fig. ib, CNF array 100 It is shown as inserting (charging) state at lithium.CNF in these and other embodiment discussed herein 110 are selectively vertically arranged.Use the plasma activated chemical vapour deposition of direct current biasing (PECVD) method grows CNF 110 in Copper base material 105.As discussed above, the method is passed through The CNF 110 of growth can have and includes and fold cup or cone or the similar conical graphite of spirillum is tied Unique form of structure stacking.This create the trickleest structure promoting that lithium inserts.This structure It is referred to as " cone-in-cone " structure in elsewhere herein.Under bigger length scale, these CNF 110 It is typically orthogonal to substrate surface evenly distributed and the most separated from one another.The individually diameter energy of CNF Enough it is selected as providing desired mechanical strength so that CNF array 100 is firm and can pass through silicon Deposition and the circulation of wet electrochemistry keep its integrity.Crystal seed layer is alternatively used for making CNF 110 exist Grow on base material 105.In use, CNF array 100 is placed in and contacts with electrolyte 125, should Electrolyte 125 comprises one or more charge carriers, such as lithium ion.CNF 110 is configured to make Some electrolyte 125 are arranged between CNF 110 and/or can be by between CNF 110 Gap arrives base material 105.

In Figure 1A and 1B the diameter of single CNF 110 of diagram be nominally at 100 to 200nm it Between, but between 75 to 300nm or the diameter of other scopes is possible.CNF 110 is along it Length is selectively taper.The CNF 110 using technology discussed herein to produce has along axle Conductivity (the σ=～2.5x10 of color⁵S/m) and with base material 105 firm Ohmic contact is formed.CNF It is the most thinning to be formed that open space between 110 can make silicon layer 115 deposit on each CNF Coaxial shell and great majority are at the tip 120 of CNF 110.This being designed to makes whole silicon layer 115 It is electrically connected by CNF 110 and during charge-discharge cycles, keeps fully activity.Lithium and silicon layer The expansion that the alloying of 115 occurs with radial direction, such as, can be perpendicular to the long size of CNF 110 Easily it is accommodated.The charging of the CNF 110 of the CNF 110 without silicon coating and silicon coating can be compared With discharge capacity and cyclical stability.The interpolation of silicon layer 115 provides under C/2 speed paramount 3938mAh/g_SiSignificant Li⁺Insert (charging) capacity and keep after 110 circulations 1944mAh/g_Si.This charge/discharge rates and corresponding capacity are significantly higher than use silicon nanowires or mixed Close the former structure of Si-C nanostructured.Figure 1A and 1B is perspective view.

In multiple embodiments, from 0.01 until 0.5,1.0,1.5,2.5,3.0,4.0,10, 20, the nominal silicon thickness of 25 μm (or more) can be deposited on the CNF 110 of 3 μm length with shape Become the CNF array 100 of those of diagram in such as Figure 1A and 1B.Similarly, in multiple enforcement In scheme, from 0.01 until 0.5,1.0,1.5,2.5,3.0,4.0,10,20,25 μm (or more Many) nominal silicon thickness can be deposited on the CNF 110 of 10 μm length to form CNF array 100. In some embodiments, the nominal thickness of silicon average distance between 0.01 μm and CNF 110 Between.

Use CNF array 100, paramount～4 under C/2 speed, the lithium of 000mAh/g specific discharge capacity Ion storage is obtained.Under equal-wattage speed, this capacity is significantly higher than uses single silicon nanowires Or those capacity that other silicon nanostructure carbon mixs obtain.Improve performance owing to due to This mixture structure is collected by the effective charge of CNF 110 and short Li⁺Path and abundant The silicon shell of activation.Good cyclical stability is proved in 110 circulations.In various embodiments In, the memory capacity of the lithium ion of CNF array 100 storage be every gram of silicon about 750,1500,2000, 2500, in 3000,3500 or 4000mAh, or arbitrary scope between these values.As herein Using, term " nominal thickness " (such as silicon) produces described thickness on base material 105 The amount of the silicon of silicon flat bed.Such as, the nominal thickness of the silicon of 1.0 μm is if silicon is deposited directly to base material The amount of the silicon of the silicon layer of 1.0 μ m-thick is caused on 105.Report nominal thickness, because it can be easily Methods known in the art are used to be measured by weight.The nominal thickness of 1.0 μm will cause at CNF The less thickness of 110 upper silicon layers 115, because silicon is distributed on the larger area on CNF 110 surface On.

Fig. 2 A-2C illustrates the average fibre with about 3 μm of the multiple embodiments according to the present invention The CNF array 100 of dimension length.Fig. 2 A-2C is scanning electron microscope (SEM) image.Figure 2A shows multiple CNF 110 being vertically arranged without silicon layer 115.Fig. 2 B shows and includes Multiple CNF 110 being vertically arranged of silicon layer 115.Fig. 2 C show experience 100 lithiums charging- To take out multiple CNF 110 being vertically arranged of (electric discharge) state after discharge cycles.CNF 110 is steady Admittedly attach to Copper base material 105 and be essentially homogeneously vertically arranged, and be randomly dispersed in substrate surface On.The sample used in our current research has 1.11x10⁹CNF/cm²Averaged areal density (from SEM Image top view calculates), correspond to～the average nearest neighbor distance of 330nm.CNF 110 in Fig. 2 Average length be～3.0 μm and > length of the CNF of 90% is in the range of 2.5 to 3.5 μm.Directly Footpath from～80nm expand to 240nm, have～the meansigma methods of 147nm.At most advanced and sophisticated 120 inverted Tear-drop shaped Raney nickel is present at the tip of each CNF 110, covers in the center of CNF Empty passage, this promotes CNF 110 tip-growth during PECVD process.Raney nickel nanometer The size of grain defines the diameter of each CNF 110.The longer CNF 110 of at most 10 μm is also made It is used in some researchs will discussed in part below.

In multiple embodiments, average nearest neighbor distance can 200-450nm, 275-385nm, Change between the distance of 300-360nm or similar.Additionally, the average length of CNF 110 can be about Between 2-20,20-40,40-60,60-80,80-100,100-120,120-150 (μm) or more Greatly.Standard carbon nano-fiber such as 1 millimeter long is known in the art.In multiple embodiments, Average diameter can change between about 50-125,100-200,125-175 (nm) or other scopes.

Unbodied silicon layer 115 passes through magnetron sputter deposition on CNF array 100.Brush and sac like The open architecture of CNF array 100 make silicon engage deep down into arrival this array in and between CNF 110 produce Raw conformal structure is possible.As a result, at CNF tip, define the silicon coating of thickness, exist subsequently CNF forms the most thinning coaxial silicon shell compared with the surrounding of lower part, presents and is similar to the interesting of cotton swab Taper nucleocapsid structure.The amount of siliceous deposits uses quartz crystal microbalance (QCM) to lead to during sputtering The nominal thickness crossing silicon fiml in the plane characterizes.Li⁺Insert/take out capacity to be normalized as by nominal The total siliceous amount that thickness obtains.Under the nominal thickness of 0.50 μm, the CNF 110 of silicon coating is fine Ground is separated from one another, forms open nucleocapsid CNF array structure (shown in Fig. 2 B).This structure permits Permitted electrolyte and freely arrived the whole surface of silicon layer 115.In the embodiment shown in the drawing, with should Compare by the average diameter of before silicon layer 115～147nm CNF 110, average tip diameter For～457nm.The silicon thickness of the average radial at most advanced and sophisticated 120 is estimated as～155nm.This substantially than The silicon thickness of the nominal of 0.50 μm is much smaller, because most of silicon is along the total length distribution of CNF.? In the embodiment substituted, see at 10-1000,20-500,50-250,100-200 (nm) model Enclose interior or other silicon thicknesses radially of different range.As elsewhere herein is discussed, CNF 110 Cone-in-cone provide extra fine structure for silicon layer 115.This cone-in-cone structure is selectively spiral growth The result of pattern, when with cross-sectional view, this spiral growth mode produces cone-in-cone structure.

Perspective electron microscope (TEM) image in Fig. 3 A-3C further illustrates silicon coating The CONSTRUCTED SPECIFICATION of CNF 110.～the tip 120 of CNF 110 of 210nm diameter give birth to immediately above Produce～the silicon layer 115 of 390nm silicon.A diameter of～the 430nm of the largest portion of the silicon layer 115 of cotton swab shape, This largest portion occurs near the least significant end of most advanced and sophisticated 120.Coaxial silicon layer 115 around CNF 110 Display has the featheriness quality of the contrast of regulation, obvious with the uniform silicon deposits on tip Different (see Fig. 3 A).This is likely to the cone-in-cone microstructure of CNF 110 of PECVD-growth Result.This is different from such CNF 110 and includes the uneven folded cup along CNF 110 central shaft The document of the graphite-structure of shape.The use of this change of the diameter of CNF 110 is 2010 10 The U.S. Patent Application Serial Number 12/904,113 owned together that the moon 13 was submitted to is disclosed in advance. In figure 3b it can clearly be seen that cone-in-cone structure is formed by more than the graphite linings of ten layers of cup-shaped, as by Dotted line is pointed out.Owing to electron beam needs to penetrate CNF or the Si-CNF mixture of hundreds of nanometer thickness, Resolution and the contrast of Fig. 3 B and 3C are limited, but use less in this architectural feature and document The high-resolution TEM research of CNF is consistent.The structure of this uniqueness produces broken along CNF sidewall Broken graphite edge bank, this broken graphite edge bank causes the nucleation rate of change also during siliceous deposits Therefore silicon layer 115 density on CNF 110 sidewall is regulated.The density of regulation causes by Fig. 3 A (100nm²) silicon structure of ultra-high surface area pointed out of frame 310.The penniform silicon knot of silicon layer 115 Structure provides outstanding lithium ion interface, and this lithium ion interface causes the highest lithium capacity and also by electricity Son transfers to CNF 110 rapidly.In Fig. 3 A, the dark area at most advanced and sophisticated 120 is for CNF The Raney nickel of growth.Other catalyst can also be used.

Fig. 3 B and 3C is that before lithium inserts/take out circulation, (3B) and lithium insert/take out after circulation (3C) The image of record.Sample in Fig. 3 C is to take off lithiumation (electric discharge) from electrochemical cell when it is removed State.Dotted line in Fig. 3 B is the visually oriented of the cone-in-cone graphite linings in CNF 110.Fig. 3 C In long dotted line represent the sidewall surfaces of CNF 110.

As elsewhere herein is discussed, the cone-in-cone structure of CNF 110 differs greatly from conventional carbon and receives Mitron (CNT) or graphite.Relative to CNT or the nano wire of standard, this cone-in-cone structure causes The Li improved⁺Insert, even if being not added with silicon layer 115.Such as, the cone-in-cone graphite-structure of CNF 110 is permitted Permitted Li⁺(and not only at end) it is inserted in graphite linings by the sidewall of CNF 110.Through each The Li of the wall of CNF 110⁺Transfer path is the shortest (to have D in some embodiments ～290nm), it is totally different from from the opening conventional seamless CNT (CNT) Long path.Fig. 4 illustrates the schematic diagram of the cone-in-cone structure of CNF 110.In this special embodiment In, the meansigma methods of parameter is: CNF radius r_CNF=74nm, CNF wall thickness t_w=～50nm, graphite Coning angle θ=10 °, and graphite cone length D=t_w/ sin θ=290nm.

Fig. 5 A-5C illustrates～the electrochemical properties of CNF 110 of 3 μm length.This characteristic illustrates pass In the phenomenon that Fig. 4 describes.Fig. 5 A shows under 0.1,0.5 and 1.0mV/s scan rate relative to Li/Li⁺ The cyclic voltammogram (CV) from 1.5V to 0.001V of reference electrode.Lithium dish is used as electrode. Data obtain from second time circulation and are normalized to the geometrical surface exposed.Fig. 5 B show C/0.5, Electrostatic charging-discharge curve under C1, C/2 Power Ratio, corresponds respectively to 647,323 and 162mA/g (being normalized to the carbonaceous amount estimated) or 71.0,35.5 and 17.8 μ A/cm²(it is normalized to geometry table Area) electric current density.Fig. 5 C shows the insertion under C/1 recharge-discharge rate relative to period With taking-up capacity (to left vertical axis) and coulombic efficiency (to right vertical axis).(C/1 discharge rate =1 hour, C/2 discharge rate=120 minute, 2C=C/0.5=30 minute, etc.).

The new half-cell assembled typically shows compared to Li/Li⁺Reference electrode, uncoated CNF 110 The open circuit potential (OCP) of anode is～2.50 to 3.00V.Measure between 0.001V and 1.50V CV show the Li when electrode potential is below 1.20V⁺Insertion starts.From OCP to 0.001V Circulation for the first time includes the protective layer being decomposed to form necessity by solvent, salt and impurity, i.e. solid electrolytic Matter mesophase (SEI), and therefore present big cathode current.CV subsequently show less but more Stable electric current.When electrode potential extends to negative value, with Li⁺On the cathode current that insertion is correlated with is slow Rise, until sharp-pointed negative electrode peak occurs at 0.18V.After electrode potential arrives the lower limit of 0.001V To on the occasion of reverse, as by continuous print anode current and pointed out at the broad peak of 1.06V, at up to 1.50V Gamut in observe that lithium takes out.

The CV feature of CNF array 100 and segmentation are inserted into graphite and Li⁺It is slowly diffused into CNT's The CV feature of those CNF arrays 100 of hollow channel is slightly different.Enter into CNF's 110 Lithium ion inserts the unique structure being likely due to CNF 110, is passed through the graphite from sidewall Insertion between Ceng.TEM image in Fig. 3 C shows the graphite stack in the cone-in-cone in CNF 110 It is stacked in Li⁺Insert-take out during circulating the most destroyed, it is likely that due to Li⁺Occur substantially during insertion Long-pending change.Some fragments and nano-particle as white object are in CNF 110 inside and in outside Surface is observed.

Electrostatic charging-discharge curve in Fig. 5 B shows when Power Ratio increases to C/0.5 from C/2 Time (C/0.5 is also referred to as " 2C "), Li⁺Memory capacity reduces.(special in order to be easier to compa-ratios Not for higher than those of C/1), we use fraction representation method C/0.5 to replace at document in this article In more commonly used " 2C ".Li⁺It is inserted and removed from capacity and is normalized to the matter of the CNF 110 estimated Amount (1.1 × 10⁴g/cm²), the CNF structure that the quality of this CNF 110 arranges according to hollow vertical with Following mean parameter calculates: length (3.0 μm), density (1.1 × 10⁹The every cm of CNF²), external diameter (147nm) and inner hollow diameter (49nm, external diameter～1/3).The solid graphite wall of CNF 110 close Spend a holiday and be set to and graphite (2.2g/cm³) identical.Under normal C/2 speed, inserting capacity is 430mA h g^-1And taking-up capacity is 390mA h g^-1, both are slightly higher than the theoretical value 372mA h g of graphite^-1, Perhaps, this is formed and Li owing to SEI⁺Irreversibly it is inserted in the hollow cell in CNF 110. Under whole Power Ratio, find take out capacity more than inserted value 90%, and when Power Ratio from C/2 inserts capacity and takes out capacity reduction～9%, when Power Ratio is from C/1 when increasing to C/1 Insert capacity when increasing to C/0.5 and take out capacity reduction～20%, equaling to graphite electrode.

Charged-discharge cycles, under C/1 speed after 20 circulations, finds to insert capacity from 410mA h g^-1Slightly it is down to 370mA h g^-1, and take out capacity and be maintained at 375mA h g^-1With 355mA h g^-1 Between.In addition in front twice circulation owing to forming SEI on CNF 110 surface, total coulomb is imitated Rate (that is, taking out capacity and the ratio inserting capacity) is～94%.Known SEI film is in initial circulation Period is easily formed on carbon anode, and it allows lithium ion to spread, but electric insulation, cause string Connection resistance increases.TEM image (Fig. 3 C) and SEM image (Fig. 6 A) show at recharge-discharge During circulation, uneven thin film deposition is on CNF 110 surface.In some embodiments, SEI serves as Sheath is to increase the mechanical strength of CNF 110, by such as in the research using other polymer coatings The cohesion capillary force of the solvent observed is to prevent them from collapsing into microbundle.

The CNF 110 of the 3 μm length that Fig. 6 A-6C illustrates the multiple embodiments according to the present invention sweeps Retouch electron microscope image.Fig. 6 A shows de-lithiumation (electric discharge) state after inserting/take out circulation CNF 110.Fig. 6 B shows the CNF including silicon layer 115 of de-state of lithiation after 100 circulations 110.Fig. 6 C shows the CNF 110 including silicon layer 115 of state of lithiation after 100 circulations.This A little images are the perspective views of 45 degree.

Fig. 7 A-7C illustrates and uses the CNF 110 including the silicon layer 115 as anode of lithium ion battery The result obtained.These results use the nominal silicon thickness of 0.50 μm to obtain.Fig. 7 A shows 0.10, 0.50 and 1.0mV s^-1Relative to Li/Li under sweep speed⁺1.5V and 0.05V between circulation Voltammogram.Measure and carry out after sample 150 charge-discharge cycles of experience, and show in each scanning The data of second time circulation under speed.Fig. 7 B show C/0.5, C/1 and C/2 Power Ratio, 120 Electrostatic charging-the discharge curve of sample under secondary circulation.All curves are taken in the second time under each ratio Circulation.Fig. 7 C shows that two CNF arrays 100 of the function as charge-discharge cycles number (are used as Electrode) be inserted and removed from capacity (to left vertical axis) and coulombic efficiency (to right vertical axis). The C/10 speed that is first utilized in the first CNF array 100 circulates next time, in C/5 speed once Circulation, twice circulation regulation under C/2 speed.Then the remainder circulated 96 times is at C/2 Insert ratio and C/5 takes out and tests under ratio.Closed square and hollow square represent insertion capacity respectively With taking-up capacity.Second electrode is first with each comfortable C/10, C/5, C/2, C/1, C/0.5, C/0.2 Twice circulation regulation under speed.Subsequently ensuing 88 times are circulated in and test under C/1 speed.Two The coulombic efficiency of individual electrode represents with solid diamond (the first electrode) and open diamonds (the second electrode), Major part overlapping 99%.

CV in Fig. 7 A presents the feature closely similar with the feature of silicon nanowires.Compared to not The CNF array 110, Li of coating⁺The cathodic wave inserted and Li⁺The anode ripple both of which taken out is shifted to relatively Low value (respectively lower than～0.5 and 0.7V).After application silicon layer 115, peak current density increases by 10 To 30 times and it is directly proportional to sweep speed.It is apparent that the Li that alloy is formed⁺It is inserted in silicon than inserting In uncoated CNF faster, uncoated CNF is limited to the Li between graphite linings⁺Slow Diffusion.In the previous studies of pure silicon nano wire, do not observe～0.28V at negative electrode peak.Generation Three anode peaks that table Li-Si alloy is transferred in amorphous silicon are similar to those using silicon nanowires, Although moving 100 to 200mV to relatively low potential.

What Fig. 7 B showed includes that the electrostatic charging-discharge curve of the CNF array of silicon layer 115 includes two Significantly feature: (1) even after 120 circulations under C/2 speed, it is thus achieved that～3000mA h (g_Si)^-1 High Li⁺Insert (charging) and take out (electric discharge) capacity；And (2) are at C/2, C/1, C/0.5 Li under Power Ratio⁺Capacity is almost identical.In other words, C/1 and C/0.5 is increased to when charge rate from C/2 Time, the capacity as the CNF array 100 of electrode operation does not decline.About these charge rates, In multiple embodiments, capacity is hardly dependent on charge rate.CNF array 100 including silicon layer 115 Total Li⁺Memory capacity is higher about 10 times than the CNF array 100 lacking silicon layer 115.Even if charging follows The low potential limit of ring increases to 0.050V from 0.001V, and this still can occur.Therefore, Li⁺Insert Amount in CNF core is it appear that insignificant.Specific capacity, should by only calculating divided by siliceous amount Siliceous amount is from the nominal thickness measured and 2.33g cm^-3Bulk density calculate.This method is chosen Suitable tolerance as the theoretical value of the specific capacity Yu volume silicon comparing silicon layer 115.Deposition is had The CNF 110 of 3.0 μm length of the silicon layer 115 of 0.456 μm nominal thickness, the actual matter of silicon layer 115 Metric density is～1.06 × 10^-4g cm^-2, equal to the mass density (～1.1 × 10 of CNF 110^-4g cm^-2)。 In Fig. 7 B, corresponding coulombic efficiency is more than 99% under whole three Power Ratio, is much higher than and does not contains The coulombic efficiency of the CNF 110 of silicon layer 115.

Fig. 8 illustrate the capacity of the CNF array 100 of the multiple embodiments according to the present invention how with Charge rate changes.Show the data of multiple period.Fig. 8 show as set hour in reach Total capacity (C/h, such as total capacity/hour) required for the making of function of charge rate (C ratio) Average specific discharge capacity with one group of circulation of same current ratio.Vertical line concentrates on C/4,1C, 3C And 8C.CNF array 100 first with each comfortable C/8, C/4, C/2, C/1, C/0.8, C/0.4 and Twice Cyclic Symmetry ground regulation under C/0.16 speed, and circulate in C/1 at ensuing 88 times subsequently Test under symmetrical ratio.It is recycled to 200 circulation repeat the above steps from 101 times.Follow at 201 times Ring starts, electrode with C/4, C/3, C/2, C/1, C/0.75, C/0.66, C/0.50, C/0.33, Five Cyclic Symmetries ground under each in C/0.25, C/0.20 and C/0.15 are circulated, and exist subsequently Circulate in for ensuing 45 times and test under C/1 symmetry ratio.From be recycled to for 301 times 400 circulations with And it is recycled to 500 circulation repeat the above steps from 401 times.When C ratio is with 32 times of changes, The change of capacity is little (< 16%).After circulating at 100 times, when C ratio becomes 8C from 3C, The capacity that electrode display increases.Therefore, charge rate causes the capacity improved faster.At height ratio and Under both relatively low-ratio (C/4 and 8C), it is thus achieved that high power capacity (> 2,700mAh/g).Work as C ratio Increasing, the capacity under the ratio of more than 3C increases.Specific capacity is due to the decline of period The correctable factor known.

CV and recharge-discharge are measured both and are pointed out Li⁺Being inserted in silicon layer 115 is quick and high reversible , it is the desired feature of high performance lithium ion battery anode.This is used under different test condition two Two long circulating test of individual identical sample proves (see Fig. 7 C) further: (1) with In the C/2 speed inserted and the slow asymmetric test of the C/5 speed for taking out；And (2) with Fast symmetrical test in the C/1 speed being inserted and removed from both.Two data sets show to be adjusted except initial Joint circulates the external of (under different low-ratio, the former 4 circulations and 12 circulations of the latter) In long circulating > coulombic efficiency of 98%.In slow asymmetric test, insert capacity and only decline 8.3%, From the 3643mA h g when the 5th circulates^-1To the 3341mA h g when the 100th circulation^-1。 Even under C/1 charging-discharging rates, insert capacity and only decline 11%, from when circulating for the 13rd time 3096mA h g^-1To the 2752mA h g when the 100th circulation^-1.Between the two data set Li⁺The difference of capacity is mainly ascribable to initial adjustment parameter and the change to sample of the little sample. This is by insertion-the taking-up appearances during regulation circulations several before in fig. 7 c under C/10 and C/5 speed The similar value of amount is pointed out.Ratio (the C/0.5 of the 9th time of sample #2 and the 10th time circulation faster And the C/0.2 of the 11st time and the 12nd time circulation) be found to be harmful and cause capacity irreversible Decline.But, become stable at longer circulation rear electrode.As Fig. 7 B shows, be used in through Go through the charge-discharge curves of the sample #1 measurement after 120 circulations in C/2, C/1 and C/0.5 speed Under almost identical.This is that the charge rate about four times changes.

3000 to 3650mA h g^-1In the range of silicon layer 115 specific capacity and document in general introduction The peak of amorphous silicon anode is consistent.It should be noted that the whole silicon in CNF array 110 Shell is to Li⁺Insertion is active and keeps the capacity of almost 90% in 120 circulations, according to our institute Knowing, in addition to flat ultra-thin (< 50nm) silicon fiml, this has never been realized before.Disclosed herein Specific capacity is significantly higher than other nanostructured silicon materials of use reported under similar Power Ratio Specific capacity, including with silicon nanowires under C/2 speed～2500mA h g^-1With under C/1 speed ～2200mA h g^-1, and with the carbon nano-fiber of random orientation-silicon core-shell structure copolymer nano wire in C/1 speed Under rate～800mA h g^-1.It is apparent that relative to prior art, be such as included in the present invention many The coaxial core-shell structure copolymer nano thread structure on the CNF 110 separated well planted in embodiment carries The charging-discharging rates strengthened, the Li the most completely of silicon are supplied⁺Memory capacity and long circulation life.

As seen in figure 7 c, the highest insertion capacity (～4500mA h g^-1) always initial Circulation is observed, its relatively after the high 20-30% of circulation.By contrast, taking-up value is followed whole In ring the most stable.The especially big capacity that inserts is attributable to the combination of three irreversible reactions: (1) shape Become (tens nanometers) thin SEI (surface electrode mesophase) layer；(2) lithium be present in silicon face On SiO_xReaction (SiO_x+2xLi→Si+xLi₂O)；And (3) will have higher theory Capacity (～4200mA h g^-1) starting crystals silicon coating change into there is relatively low capacity (< 3800mA h g^-1) amorphous silicon.TEM image (Fig. 3 C) and SEM image (Fig. 6 B) display are being filled After electricity-discharge cycles, uneven SEI can be deposited on the surface of silicon layer 115.When CNF battle array When row 110 experience the expansion-contraction circulation of the large volume occurred during charge-discharge cycles, this Resilient SEI film can help to be fixed on CNF 110 surface silicon layer 115.At Fig. 6 B and The significant difference between SEM image in 6C shows the lithiumation (charging) relative to non-lithiated state The big expansion of the silicon layer 115 of state.Although (some expansions are likely due to when electrochemical cell is split Unload during imaging, to pass through the air oxidation to lithium.) note, at initial charge-discharge cycles period SEI Generation cause the difference seen in the silicon layer 115 between Fig. 3 A and 3B.In figure 3b, silicon Interacting with electrolyte to produce SEI, this SEI is filled with the gap between feathery structure.Should Interaction can include mixing, chemical reaction, Charged Couple, encapsulate and/or similar effect.Cause This, silicon layer 115 looks like more uniform in figure 3b.But, silicon layer 115 includes handing over now The silicon layer (feathery structure) of fork and SEI layer.Every layer in these layers intersected can be the most several Ten nanometers.SEI layer can be ion permeability material, its be electrolyte and silicon layer 115 (or other Electrode material) between the product of interaction.

Crystal and the impalpable structure of silicon shell are manifested by Raman spectrum.As it is shown in figure 9, include silicon layer The former CNF array 100 of 115 shows corresponding with amorphous silicon 350 to 550cm^-1In the range of Overlapping multiple broadbands and corresponding with nanocrystalline silicon at 480cm^-1The higher sharp-pointed band at place.? After recharge-discharge test, sharp-pointed peak disappears, and broadband is merged at 470cm simultaneously^-1That locates is unimodal. Exposed CNF 110 does not shows any feature in this range.Crystalline silicon peak is from monocrystal silicon (100) The peak that wafer is measured moves down～40cm^-1And move down from other microcrystalline silicon materials～20 to 30cm^-1.This The mobile much smaller crystalline size and big unordered of being likely due to.Initial silicon layer 115 is likely to Nanocrystal in the amorphous ground substance being associated by the TEM image being embedded into Fig. 3 A mesoptile shape Composition.After initially circulation, si-nanocrystals changes into amorphous silicon, with the TEM after loop test Image is consistent (see Fig. 3 B and 3C).But, (big compared to the big longitudinal dilatation of pure silicon nano wire To 100%), silicon layer 115 does not slides along CNF.Therefore, silicon layer in 120 circulations 115 are firmly adhered to CNF 110.At Li⁺Silicon shell volume during insertion changes and passes through expanded radially Being controlled, CNF-silicon interface keeps complete simultaneously.

The multiple embodiments of the present invention includes the CNF 110 with different length and silicon thickness of the shell.When The factor that can control when producing CNF 110 is the open space between each CNF 110, example As, the average distance between CNF 110 in CNF array 100.When charging, this space Allowing silicon layer 115 expanded radially, this space provides stability the most in some embodiments.Because Optimal electrode structure depends on length and the thickness of silicon layer 115 of CNF 110, so sometimes Expect to use longer CNF 110 and thicker silicon layer 115 to obtain higher total Li⁺Storage is held Amount.Longer CNF 110 associates with bigger memory capacity.Figure 10 A-10C display uses sinks respectively The CNF 110 of three 10 μm length of the long-pending silicon layer 115 having 0.50,1.5 and 4.0 μm nominal thickness Sample Li in 15 charge-discharge cycles⁺Insert-take out capacity and the change of coulombic efficiency.? Under the C/10 speed of circulation for the first time and under the C/5 speed of second time circulation after regulation, no Symmetrical ratio (C/2 is used for taking out for insertion and C/5) is in the survey with the sample #1 in Fig. 7 C Measure similar using with in Posterior circle.The program provides the coulomb effect of almost 100% during circulating Rate and minimum decline.During sputtering, nominal thickness uses quartz crystal microbalance in site measurement.

Up to 3597mA h g is obtained respectively with the silicon layer 115 of 0.50 and 1.5 μ m-thick^-1And 3416mA h g^-1Specific capacity, this silicon layer 115 with 0.50 μ m-thick on the CNF 110 being used in 3.0 μm length Specific capacity closely similar (see Fig. 7 C).In 15 times circulate, capacity is kept approximately constant.But, The electrode having 4.0 μm nominal silicon thicknesses shows only 2221mA h g^-1Notable the lowest specific capacity.This Show that silicon layer 115 starts contacting one another from neighbouring CNF 110, limits them and enter owing to expanding Expanding and restriction lithium diffusion between CNF 110 of one step.As a result, the only a fraction of of silicon coating It is active in lithium inserts.The sample of the stability silicon layer 115 thinner than having of circulation is the most more Difference.

Same amount of Si (500nm on the CNF array 110 of CNF 110 including 10 μm length Nominal thickness) give the Li of CNF 110 with 3 μm length⁺Memory capacity (3643mA h g^-1, see Fig. 7 C) Li of nearly identical amounts⁺Memory capacity (3597mA h g^-1, see Fig. 6 a), although carbonaceous amount More than more than 3 times.This is very strong evidence, and the contribution of CNF 110 is calculating Li⁺In storage being can Ignore.Few Li⁺It is likely that ion is inserted in the CNF 110 in silicon coated sample, This contributes to the stability of the structure during repeatedly charge-discharge cycles.

Li in three samples associated very well with the structure of three samples⁺The change of storage specific capacity The SEM picture illustrated by Figure 11 A-11C shows.Figure 11 A-11C shows freshly prepd CNF array 100 (～the long CNF of 10 μm 110 on) scanning electron microscope image.Use (a) 0.50 μm, B the nominal silicon thickness of () 1.5 μm and (c) 4.0 μm generates silicon layer 115, nominal silicon thickness is in deposition Period uses quartz crystal microbalance in site measurement.All images are 45 ° of perspective views.In 0.50 μm At nominal silicon thickness, find that the average tip diameter on the CNF of 10 μm length is～388nm, far Less than on the CNF 110 of 3.0 μm length～the average diameter of 457nm.Silicon layer 115 is thinner but edge The 10 long CNF of μm 110 more uniformly to spread.

It should be noted that growth 10 μm CNF 110 spend 120 minutes, this is growth 3 μm CNF About six times of times of 110 are long.Some Raney nickels pass through NH during long PECVD₃Slowly It is etched, causes being continuously reduced and causing cone point 120 (such as Figure 12 institute of nano nickel particles size Show).The length change of CNF 110 increases also as long CNF 110.These factors reduce jointly The screen effect of most advanced and sophisticated 120.As a result, even under 1.5 μm nominal silicon thicknesses, it is coated with silicon layer The CNF 110 of 115 is well with separated from one another.1.5 μm silicon on 10 μm CNF arrays 100 The SEM of SEM image (Figure 11 B) and 0.50 μm silicon on 3.0 μm CNF arrays 110 Image (Fig. 2 B) is closely similar.But when nominal silicon thickness increases to 4.0 μm, and silicon layer 115 is obvious And combine with each other and fill the most of space (see Figure 10 C) between CNF 110.Which reduce appearance Receive the free space needed for the volumetric expansion of silicon layer 115l.As a result, Li⁺Storage specific capacity is remarkably decreased.

Figure 11 A and 11B each includes the CNF 110 of approximately same number, but has in Figure 11 B There is the most less visible cusps 120.This is because silicon layer 115 can be formed includes single CNF Nanofiber/the silicon compound of 110 (its cross section shows in figure ia).Or, silicon layer 115 The Nanowire of two, three or more CNF 110 being included under single silicon covering can be formed Dimension/silicon compound.These two or more CNF 110 during silicon layer 115 deposition process are gathered in one Occur when rising.Nanofiber/silicon compound is the continuous silicon layer including encapsulating one or more CNF 110 The structure of 115.Cross section including the nanofiber/silicon compound of two CNF 110 is schemed at Figure 11 D Show.In multiple embodiments, the nanofiber/silicon compound of at least 1%, 5% or 10% includes many In a CNF 110.

In multiple embodiments, there is the CNF array 100 of 0.50 and 1.5 μm nominal silicon thicknesses Example be respectively provided with 3208 ± 343 and 3212 ± 234mA h g^-1Comparable quality-specific volume Amount.The sample with 4.0 μm nominal silicon thicknesses produces 2072 ± 298mA h g^-1Much lower appearance Amount.Thinner silicon coating is fully activation and the maximum lithium insertion appearance providing amorphous silicon to give Amount.On the other hand, area-specific capacity is along with silicon thickness is from the 0.373 ± 0.040 of 0.50 μm silicon thickness mA h cm^-2Proportionally increase to the 1.12 ± 0.08mA h cm with 1.5 μm silicon thicknesses^-2But, Decline to produce the 1.93 ± 0.28mA h cm with 4.0 μm nominal silicon thicknesses from linearity curve^-2.Substantially Ground, under this thickness, the only a fraction of of the thick extra silicon in silicon coating plays an active part in lithium storage. The thickness of 4.0 μm is more than the average distance between CNF 110.In electrochemical results and Figure 11 C In SEM image, the structure of display is consistent, and the space between its display CNF 110 is substantially filled.

In the multiple embodiments of the present invention, the structure of CNF array 100 is included on CNF 110 About 200 silicon layers arriving 300nm radial thickness, this CNF 110 has about 30-40,40-75,75-125 The length of micron (or bigger or their combination) and about～the diameter of 50nm.Some embodiment party In case, these CNF arrays 100 grow on a conductive foil, this conductive foil have～10 microns～10-20 Thickness in the scope of micron～10-50 micron or bigger.In multiple embodiments, silicon is (quite In 1.5 μm nominal thickness in the plane) it is deposited on the CNF 100 of 10 μm length to form CNF Array 100.This is done and keeps having and the opening of the most fine separate single CNF 110 simultaneously The vertical-type core-shell structure copolymer nano thread structure put so that lithium ion can permeate the CNF between CNF 110 Array 100.The combination construction of this uniqueness allows silicon layer 115 at Li⁺It is inserted and removed from period radially Direction free wxpansion/contraction.Even obtain under C/1 speed and have 3000 to 3650mA h g^-1's The high-performance lithium storage of quality-specific capacity.This capacity is desired with amorphous silicon from similar mass Big value matches, and this shows that this silicon layer 115 fully activates.Structure energy nano-structured for this 3D Substantial amounts of silicon materials are enough made effectively to electrically connect the Li simultaneously keeping short⁺Insert-take out path.As a result, exist In 120 charge-discharge cycles, the high power capacity close to theoretical limit is possible.When ratio is from C/10 20 times are increased, varying less of capacity to C/0.5 (or 2C).Significantly improved charge rate and power High power capacity under speed and outstanding cyclical stability makes this new structure become for high-performance The optional anode material of lithium ion battery.Identical core-shell structure copolymer concept can be by with TiO₂、LiCoO₂、 LiNiO₂、LiMn₂O₄、LiFePO₄、Li₂O、Li₂O₂Or the like replace silicon shell and be applied to the moon Pole material.

Figure 13 illustrates the method producing CNF array 100 disclosed herein.Base material step is being provided In 1310, it is provided that be suitable for the base material 105 of CNF 110 growth.Base material 105 can include multiple material Material, such as copper.Base material 105 is selectively the conductive foil with thickness described elsewhere herein. In the step 1320 of selectable offer nucleation site, base material 105 provides for CNF 110 The nucleation site of growth.Multiple nucleation material, such as nickel particles are well known in the art.Become Core site selectively so that the density of the average distance produced between CNF 110, such as herein its He provides the density of local teaching.Thering is provided nucleation site step 1320 is that nucleation is not wanted wherein It is selectable for asking in the embodiment of CNF 110 or the growth of analog structure.

In growth CNF step 1330, CNF 110 grows on base material 105.CNF 110 can The most grown to produce cone-in-cone structure or the similar varistructure that elsewhere herein is instructed. CNF 110 can grow to any length of elsewhere herein teaching.Growth selectively uses PECVD method is such as at " A high-performance lithium-ion battery anode based on the core-shell heterostructure of silicon-coated vertically aligned carbon Nanofibers " .J.Mater.Chem.A such as Klankowski, instructs in 2013,1,1055 or quotes Method completes.

In applying silicon layer step 1340, insert material such as silicon layer 115 and be applied to the CNF of growth 110.The material applied can have arbitrary nominal thickness of elsewhere herein teaching to produce tens Or silicon layer 115 thickness of hundreds of nanometer.

In selectable applying PEM step 1345, power reinforcing material (PEM) is added to CNF array 100.This PEM typically comprises binding agent and skin effect props up coordination site, as at this Literary composition discusses in more detail elsewhere.In selectable regulating step 1350, use one or Multiple lithiums insert circulation and regulate the CNF array 100 using step 1310-1340 to produce.

What Figure 14 A illustrated the multiple embodiments according to the present invention includes power reinforcing material 1320 CNF 110.This power reinforcing material 1320 is applied to insert above material as layer, such as at silicon Above layer 115.Figure 14 B illustrates diagram in Figure 14 B of the multiple embodiments according to the present invention The details of power reinforcing material 1320.Power reinforcing material 1320 includes that skin effect props up coordination site 1430 and selectable binding agent 1440.Silicon layer 115 is the only one example inserting material.Work as silicon Layer 115 is used as example herein, it should be understood that other kinds of insertion material can replace silicon or and silicon In conjunction with.Such alternative or extra insertion material include Ag, Al, Bi, C, Se, Sb, Sn and Zn.The CNF 110 illustrated in fig. 14 is typically many CNF in CNF array 100 In 110 one.

In some embodiments, skin effect is propped up coordination site 1430 and is included the surface of nano-particle, should The surface of nano-particle is configured to adsorption charge carrier in faradic interaction, such as with Just redox reaction is stood with charge carrier.Because typically, for these nano-particle, electric charge The faradic interaction domination faradic phase of main body between carrier and nano grain surface Interaction, so they are referred to as " skin effect domination ".Therefore, charge carrier is relative to receiving The main body of rice grain more likely is reacted in surface.Such as, lithium ion will more likely be adsorbed onto nanometer On particle surface rather than be absorbed in the main body of nano-particle.These nano-particle are sometimes referred to For surface oxidation reduction granule.Faradic interaction causes pseudocapacitors (pseudo Capacitor), pseudocapacitors can store the electric charge of substantial amounts of loose combination and therefore provide significantly Power density.Under fake capacitance, electronics is exchanged (such as, being supplied to).In this case, Between charge carrier to nano-particle.When some electromotive forces cause charge carrier in nano-particle When inserting, this props up main body and the energy not constituting interaction at coordination site 1430 in skin effect Enough degrade some type of nano-particle.Faradic interaction is owing to electrochemistry interacts Make the interaction of electric charge transfer (such as, being supplied to).

The nano-particle propping up coordination site 1430 including skin effect can be made up of transition metal oxide, Such as TiO₂、Va₂O₅、MnO、MnO₂, NiO, tantalum oxide, ruthenium-oxide, rubidium oxide, oxidation Stannum, cobalt oxide, nickel oxide, copper oxide, ferrum oxide and/or analog.They can also be by metal nitrogen Compound, carbon, activated carbon, Graphene, graphite, titanate (Li₄Ti₅O₁₂), crystalline silicon, stannum, germanium, Metal hydride, iron phosphate, polyaniline, mesocarbon and/or analog composition.Should be understood that and have The mixture of desired faradic character above-mentioned and/or other material can be included in table Face effect is propped up in coordination site 1430.In multiple embodiments, these nano-particle diameter can be little In 1,2,3,5,8,13,21 or 34 nanometers.The lower limit of nanoparticle size is composition material The function of size of molecule.Nano-particle includes at least some molecule.Less size provides may The bigger surface volume ratio of adsorption site.But, the granule only including a pair molecule has reduction Stability.Nano-particle is selectively multilamellar.Such as, they can be included in transition metal Co、Ni、Mn、Ta、Ru、Rb、Ti、Sn、V₂O₂, TiO on FeO, Cu or Fe core₂ Layer (or any other nano material discussed herein) or the Graphene on the core of some other materials / graphite linings.In some embodiments, different core material affects the reaction electromotive force of surfacing.Table Face effect is propped up the amount of coordination site 1430 and is selectively selected according to desired power and energy density. Such as, the greater number of skin effect of insertion material by having every quality prop up coordination site 1430 can To obtain bigger power density, or prop up coordination site 1430 more by the skin effect with every quantity Substantial amounts of insertion material can obtain more substantial energy density.Some embodiments of the present invention excellent Gesture it is possible to obtain high-energy and power density in history simultaneously.

By the Adsorption on Surface charge carrier at nano-particle, before charge carrier can provide such as The power density that only electricity container obtains.This is because the release of electric charge is not dependent on the expansion of charge carrier Dissipate but depend on inserting material.It addition, be placed as closely by skin effect being propped up coordination site 1430 Close to inserting material, charge carrier can move to skin effect from insertion material and prop up coordination site 1430 (or moving directly to electrolyte).This causes the energy density equal to or more than conventional batteries.Battery Energy density and the power density of capacitor obtain in same apparatus.It should be noted that in the electric discharge phase Between, insert the charge carrier in material and can move to skin effect and prop up coordination site 1430 and therefore Recharge to these sites.

In some embodiments, skin effect is propped up coordination site 1430 and is disposed on bigger granule. Such as, particle size can more than 1,10,25,100 or 250 microns (but be generally less than 1 Millimeter).Activated carbon, graphite and Graphene are the materials that can be included in the granule of these sizes. Such as, coordination site is propped up when activated carbon has the skin effect similar to the nano-particle diameter of above-mentioned teaching 1430 pore size time, activated carbon can be included in power reinforcing material 1320.For this The purpose of disclosure, nano-particle is the granule with the average diameter less than 1 μm.

Selectable binding agent 1440 is configured to that skin effect is propped up coordination site 1430 and remains close to Insert material.In some embodiments, skin effect prop up the distribution of coordination site 1430 be spread all over viscous Mixture 1440 is uniform.Such as, propping up the nano-particle of coordination site 1430 including skin effect can be Binding agent 1440 be applied to insert before material mix with binding agent 1440 to produce relatively uniform Distribution.Alternately, nano-particle can be applied to insert material before application binding agent 1440 The surface of material.This can result in compared with the region away from the binding agent 1440 inserting material, connects most The nearly skin effect inserting material props up the bigger concentration of coordination site 1430 (in binding agent 1440). Binding agent 1440 is selectable in embodiments, and wherein skin effect props up coordination site 1430 or phase The nano-particle closed is attached directly to insert material, such as, attach to silicon layer 115.

Binding agent 1440 is permeable (such as, porose) to the charge carrier of electrolyte.Bonding The example of the suitable material of agent 1440 include Kynoar (PVDF), butadiene-styrene rubber, poly-(third Olefin(e) acid) (PAA), carboxymethyl cellulose (CMC) and/or analog.Meet its of tonicity requirements He can be used by binding agent.Binding agent 1440 selectively includes the material increasing its electric conductivity. Such as, binding agent 1440 can include conducting polymer, graphite, Graphene, metal nanoparticle, CNT, carbon nano-fiber, metal nanometer line, super-P (conductive black) and/or analog. Material preferably concentration is high enough that binding agent 1440 is conduction, such as percolation threshold.

Close proximity inserts the skin effect of material (such as, silicon layer 115) and props up adding of coordination site 1430 Add the use without requiring the CNF 110 or any supporting wire being vertically arranged.Such as, Figure 15 diagram The including power reinforcing material 1320 and be coated with by inserting material of multiple embodiments according to the present invention The electrode surface of the CNF 110 not arranged covered.In these embodiments, CNF 110 is the most direct Attach to base material 110, but remain close proximity base material 110 by binding agent 1440.Work as CNF During the example that 110 are used as supporting wire at this, it should be understood that other classes discussed herein in any example The supporting wire of type can be used to supplement or replace the carbon nano-fiber of CNF 110.

Can be such as by first growing the CNF 110 not being attached by Figure 15 embodiment illustrated Produce.Then these are with silicon layer 115 (or some other insertion material) coating so that insert material Material generally contacts with CNF 110 as coat.The CNF 110 being then coated with props up with skin effect Coordination site 1430 and binding agent 1440 mix.Finally, the mixture obtained is disposed in base material 105 On.

Figure 16 illustrate the multiple embodiments according to the present invention include power reinforcing material 1320, The CNF 110 not arranged and the electrode surface inserting material 1610 freely.These embodiment party In case, insertion material 1610 is not necessarily as coating and is arranged in around CNF 110.Insert material 1610 Being freely, it is meant that insertion material 1610 is not limited to CNF 110 surface, but it is also It is to remain close to base material 105 by binding agent 1440.

In Figure 16, embodiment illustrated can be such as by making binding agent 1440, skin effect arrange Site 1430, insertion material 1610 and CNF 110 mix (in any order) production jointly. Then this mixture is applied to base material 105.In these embodiments, CNF 110 is by except viscous Mode outside mixture 1440 can be attached and maybe can be not attached to base material 105.Insert material 1610 Can contact and/or can not contact CNF 110 or base material 105.Similarly, skin effect Zhi Peiwei Point 1430 selectively contacts with base material 105, CNF 110 and/or insertion material 1610.Insert material Material 1610 selectively includes having at least 0.1,0.6,1,1.5,2,3,5,7,9,10, 13, the size of 15,18,21 or 29 μm or any scope between insert material granule, Suspension, bunch and/or drop.In alternative embodiment, other sizes are possible.

Figure 17 illustrate the multiple embodiments according to the present invention include binding agent 1440, surface effect Coordination site 1430 should be propped up and insert material 1610, and there is no the electrode surface of supporting wire.Real at these Executing in scheme, skin effect props up coordination site 1430 and insertion material 1610 is protected by binding agent 1440 Hold as close to base material 11005.

Figure 18 illustrates the electrode surface similar to the electrode surface of diagram in Figure 15.But, by In Figure 18 embodiment illustrated, skin effect is propped up coordination site 1430 and is inserted material at close proximity Concentrate at 1610.Such as, in some embodiments, skin effect props up coordination site 1430 at least 2%, 10%, 25%, 50%, 75% or 85% on the granule contacted with insertion material 1610.? The concentration of the increase that the close skin effect inserting material 1610 props up coordination site 1430 can use herein The method described elsewhere obtains.This causes relative to other volumes in binding agent 1440, Skin effect in the surface inserting material 1610 props up the bigger concentration of coordination site 1430.

Figure 14 C, 19 and 20 respectively illustrate and the electrode table of diagram in Figure 14 B, 16 and 17 The electrode surface that face is similar.But, by these figure embodiment illustrated, according to the present invention's Multiple embodiments, skin effect is propped up coordination site 1430 and is arranged to close proximity and inserts material freely Material.As by Figure 18 embodiment illustrated, in some embodiments, skin effect is arranged At least the 2% of site 1430,10%, 25%, 50%, 75% or 85% connect with inserting material 1610 Touch.In some embodiments, in the insertion material 1610 surface internal ratio of 5 nanometers 10 and 15 That arranges higher concentration between these surfaces of nanometer includes that skin effect props up receiving of coordination site 1430 Rice grain.The concentration energy of the increase of coordination site 1430 is propped up closest to the skin effect inserting material 1610 Enough by selecting nano-particle and insertion material 1610 suitable zeta potential in the solution to obtain, make Obtain nano-particle and form Double layer in the surface inserting material 1610.Zeta potential is the position on surface Put the interfacial bilayer at place relative to the electromotive force away from the point in the bulk liquid on surface.This zeta potential is optional Select higher than 25mV (absolute).In other embodiments, nano-particle is at application binding agent It was applied to insert the surface of material 1610 before 1440.

As in Figure 16-20, the insertion material 1610 of diagram can include begging for herein relative to silicon layer 115 Any single kind of the material of opinion or combination (include or do not include silicon).Similarly, as in Figure 16-20 The CNF 110 of diagram can include any single kind or the combination of polytype fiber discussed herein (include or do not include carbon nano-fiber).Such as, these CNF 110 can include branched fiber, Many walls fiber, line, aeroge, graphite, carbon, Graphene, boron nitride nanotube etc..Herein The skin effect shown in these figures and other figures props up the quantity of coordination site 1430 and CNF 110 For illustration purposes.Such as, in practice skin effect prop up the quantity of coordination site 1430 can be more Many.Similarly, insert material 1610 and the amount of silicon layer 115 and size is for illustration purposes.Can The embodiment substituted can include more or less of amount and greater or lesser size.Equally Ground, the degree of depth of PEM 1420 and the length of CNF 110 can be different to that the degree of depth and the length of display in figure Degree.

In multiple embodiments, the amount of the nano-particle propping up coordination site 1430 including skin effect is permissible The monolayer of the nano-particle being chosen so as to cause on the surface inserting material 1610 or silicon layer 115 At least 0.1,0.5,0.7,0.9,1.1,1.3,1.5,2,3,5,10,25,50 or 100 (or Any scope between) times (as measured in discharge condition).As used herein, 0.1 Monolayer represent 10% and the monolayer of 10 times be 10 layers of monolayer.In multiple embodiments, including table Face effect is propped up the amount of the nano-particle of coordination site 1430 and can be chosen as causing inserting material 1610 At least 1 of nano-particle on surface, 5,10,20,50,100,250 or 500 nanometer layer (or Any combination between) (as measured in discharge condition).As with monolayer or depth survey Other coverage densities are possible.When covering of nano-particle (including that skin effect props up coordination site 1430) When cover degree is close to the monolayer of 1.0 layers, nano-particle can be formed in insertion material 1610 and spreads all over bonding Layer between the charge carrier of the electrolyte that agent 1440 is moved.The most in some embodiments, electricity Solve matter and include that lithium is as charge carrier.Lithium can spread all over binding agent 1440 and moves and stand and surface Effect props up the faradic reaction of coordination site 1430, and wherein electronics props up coordination site 1430 from skin effect In one be supplied to lithium.(such as, this electronics is transferred from base material 105 by inserting material 1610 It is supplied to) to nano-particle.Because nano-particle forms barrier, when this stage of charging process, The most limited amount charge carrier arrives and inserts material 1610.Charging is by propping up coordination site in skin effect Reaction controlling at 1430.In some embodiments, because faradic with charge carrier Before reaction occurs, charge carrier is inserted in insertion material 1610 not necessarily, so charging energy It is enough quick.Skin effect is propped up the existence of coordination site 1430 and is considerably increased the most initial The surface area that can occur of faradic reaction.Skin effect is propped up coordination site 1430 and is promoted electric charge Carrier is inserted in insertion material 1610.Charge carrier can be such as to prop up coordination site 1430 in skin effect The form that place receives is inserted into or is inserted into the alternative form of such as metal-oxide.If with Metal-oxide is inserted into, and the oxygen of oxide can loop back to skin effect domination after the insertion Site 1430.

In some embodiments, because nano-particle forms incomplete barrier, some charge carriers Still (such as, make to include energy storing device charging initial of electrode discussed herein in the charging stage Stage) arrive and insert material 1610.Because the insertion material 1610 of some embodiments, such as silicon Expanding when charge carrier inserts and occurs, the surface area inserting material 1610 also increases.It reduce The surface coverage of nano-particle on the surface inserting material 1610 and reduce nano-particle Form the effectiveness of the barrier of charge carrier.Therefore, when charging is carried out, the bigger number of time per unit The charge carrier of amount can arrive insertion material 1610.This selectively proceeds, until charging by Till reaction controlling in inserting material 1610.The reduction of surface coverage can also increase cruelly The skin effect being exposed on each nano-particle of electrolyte props up the average mark of coordination site 1430.As Phrase used herein " surface coverage " is used to represent the density of the material on surface and permissible It is measured as the quantity (or its mark) of monolayer, is measured as thickness or is measured as concentration etc..

In some embodiments, the energy storage propped up at coordination site 1430 in skin effect occurs in sense The surface reaction of induced current occurs but charge carrier is inserted into and includes that skin effect props up coordination site 1430 Under electromotive force when not occurring in nano-particle.This prevent due to charge carrier be repeatedly inserted into and deviate from and Degraded nano-particle and allow longer cycle life.Under identical electrode, by occurring more Faradic reaction under high electromotive force, is desirable inserting material 1610 internal memory energy storage capacity, This higher electromotive force selectively includes causing charge carrier to be inserted into having skin effect and prop up coordination site Electromotive force in the nano-particle of 1430.This can occur in some embodiments of the present invention, because Potential drop is there is between base material 105 and electrolyte 125.

In a concrete example, wherein lithium is charge carrier, and skin effect props up coordination site 1430 At TiO₂On nano-particle and insert material 1610 mainly silicon.In other embodiments, It will be appreciated that specific voltage depends on that being included in skin effect props up coordination site 1430 and insert material 1610 In chemical substance and during charging occur reaction etc..In multiple embodiments, surface is imitated Should prop up the potential difference values between coordination site 1430 and base material 105 be at least 0.001,0.2,0.3,0.4, 0.5,0.6,0.8,1.0,1.3,1.7,2.0,2.2 or 2.4V or any scope between. Term " electromotive force " is used to refer to the absolute value (such as, │ x │) of electrostatic potential as used herein.

Figure 21 illustrates the method for the assembling electrode surface of the multiple embodiments according to the present invention.This dress The electrode surface joined is used as such as, the anode in battery, capacitor or mixing arrangement.Figure 21 The method of middle diagram is selectively used for producing the multiple electrode that elsewhere herein is discussed.

In base material step 2110 is provided, it is provided that conductive base.Base material step 2110 is provided and provides Base material step 1310 is similar.In base material step 2110 is provided, it is provided that be optionally suitable for CNF 110 or the base material 105 of growth of other supporting wires.As discussed in this article, base material 105 can include many Plant material, such as Cu, Au, Sn etc..Base material 105 selectively includes that elsewhere herein such as is begged for The nucleation site of opinion.

In selectable offer CNF step 2120, it is provided that CNF 110 (or discussed herein appointing What his supporting wire).Produce wherein and there is no the electrode of supporting wire (such as by Figure 17 and 20 Diagram those) embodiment in, it is provided that CNF step 2120 is selectable.Real at some Execute in scheme, provide CNF 110 by growing CNF 110 on base material 105.Some embodiment party In case, providing CNF 110 by adding CNF 110 to mixture, mixture is applied in subsequently To base material 105.In some embodiments, CNF 110 and base material 105 individually produced and with After be attached to base material 105.

Insert in material step 2130 providing, it is provided that insert material 1610.In some embodiments In, insert material 1610 and be applied first to CNF 110.In multiple embodiments, insert material 1610 as using vapour deposition soliquid in a solvent, as such as pastel or the like quilt Apply.

Prop up in coordination site (SEDS) step 2140 providing skin effect, it is provided that skin effect is arranged Site 1430.As elsewhere herein is discussed, skin effect is propped up coordination site 1430 and can be arranged In the structure of nano-particle or bigger, on such as graphite, Graphene or activated carbon.Skin effect is arranged Site 1430 can as use sputtering sedimentation, use plating, use evaporation at binding agent 1140 or Suspension in solvent, it is provided as spraying or the like.In some embodiments, material is inserted The zeta potential of material 1610 is chosen to skin effect and props up coordination site 1430 and concentrate on insertion material The surface of 1610.

Applying in step 2150, inserting material 1610, skin effect props up coordination site 1430 and can The CNF 110 selected is applied to base material 105.These materials can apply with multiple order and combination. Such as, insert material 1610 and can be applied in CNF 110 (having attached to base material 105), Then skin effect is propped up coordination site 1430 and can be applied to insert on material 1610.Alternately, First CNF 110, insertion material 1610 can mix freely, and then skin effect props up coordination site 1430 and binding agent 1140 be added either individually or in combination.Based on teaching herein, this area Ordinarily skilled artisan will understand that in different embodiments, these components can in any order or group Close mixing or add.It addition, component can mix before or after being applied in base material 105.Step Rapid 2110-2150 can be carried out in any order.It it is selectively regulation step after applying step 2150 Rapid 1350.

In some embodiments, the method for Figure 21 diagram includes making with the insertion of the suspension in solvent Material 1610 and skin effect are propped up coordination site 1430 and are mixed with the dispersion of q.s.This dispersion can Selectively put on CNF 110.Then, the solvent of dispersion evaporates from mixture, causes at CNF Powder on 110 or coating.Binding agent 1440 can add before or after putting on CNF 110 To suspension.In some embodiments, what skin effect propped up coordination site 1430 is applied through change It is splashed to the material on base material 105 and occurs in the terminal stage inserting material 1610 deposition.? In these embodiments, such as TiO₂Can be after almost all of insertion material 1610 be deposited It is added to sputter mixture.This produces TiO₂Sputtering layer as inserting on material 1610 Skin effect props up coordination site 1430.

Figure 22 illustrates the method for the operation charge storage devices of the multiple embodiments according to the present invention. The method can such as be used when making charge storage devices charge.In some embodiments, should Method includes making charging device attach to anode and the negative electrode of charge storage devices by line.This fills Electrical storage device makes electromotive force be positioned at anode and negative electrode, causes potential gradient between which.Electromotive force Gradient-driven electronics is in anode.In Figure 22 diagram step occur the most simultaneously, such as it Can relative to each other or occur in the overlapping time simultaneously.

In setting up potential step 2210, electromotive force is based upon at charge storage devices.This electromotive force is permissible Between the anode and negative electrode of charge devices.Such electromotive force will cause the base in charge storage devices Potential gradient between material 105 and electrolyte 125.This potential gradient can produce skin effect domination Potential difference values between site 1430 and the position inserting material 1610.In multiple embodiments, This potential difference values be at least 0.001,0.1,0.3,0.4,0.5,0.8,1.0,1.3,1.7,2.0 or 2.4V or any scope between.

In receiving lithium step 2220, lithium is only that the charge carrier of a kind of possible example is in skin effect Prop up and received at one in coordination site 1430.This charge carrier is selectively spread all over bonding by reception Agent 1440.

In transfer electronics step 2230, electronics props up coordination site 1430 from skin effect and is transferred (example As, it is supplied to) to the charge carrier received in receiving lithium step 2220.This transfer can include Sharing of electronics between coordination site 1430 and charge carrier is propped up in skin effect.Electronics be transferred in Conduct in faradic reaction and typically from base material 105.This transfer is when charge carrier is at table Face effect occurs when propping up the surface of coordination site 1430 and occurs under the electromotive force of this position.Electronics The reaction electromotive force of transfer such as, depends on that the reaction electromotive force of charge carrier and skin effect prop up coordination site The reaction electromotive force of 1430.This reaction electromotive force can depend on skin effect prop up coordination site 1430 and near Both insertion materials 1610.As used herein, term " reaction electromotive force " is used to refer to bright The electromotive force that aobvious speed reacts.The reaction electromotive force of reaction can be by such as at cyclic voltammetry curve In peak illustrate.In another example, there is reaction Li in an electrochemical cell⁺+e^-→Li Or 2Li⁺+MO+2e^-→Li₂O+M (any during wherein M is transition metal discussed herein A kind of) needed for electromotive force be reaction electromotive forces of these reactions.This reaction electromotive force can be highly dependant on The environment that reaction occurs.Such as, second above-mentioned reaction can have in the range of 2-10nm The TiO of diameter₂There is in the presence of nano-particle relatively low reaction electromotive force.Similarly, reaction electromotive force By inserting required energy or coordination site 1430 can be propped up by skin effect and insert material 1610 The impact of close proximity.

In inserting lithium step 2240, lithium is only that the charge carrier of a kind of possible example is inserted in slotting Enter in material 1610.In this step can include the main body that charge carrier transfers to insert material 1610 In portion.Charge carrier can be received as at material 1610 and in receiving lithium step 2220 inserting Prop up, in skin effect, the identical chemical substance received at coordination site 1430, or be alternately The chemical substance produced at coordination site 1430 is propped up in skin effect.Such as, charge carrier can inserted Enter at material 1610 as the oxide propping up the chemical substance received at coordination site 1430 in skin effect (such as, Li₂O etc.) received.

In transfer electronics step 2250, electronics is transferred to insert lithium step from inserting material 1610 The charge carrier of 2240.Electronics is transferred in faradic reaction and typically from base material 105 Middle conduction.This transfer is when charge carrier generation and the electricity in this position when inserting in material 1610 Occur under gesture.The reaction electromotive force of electron transfer can depend on the reaction electromotive force of charge carrier and insert material The reaction electromotive force of material 1610.The electric potential energy of this conduction band is hard to bear to inserting material 1610 and neighbouring table Face effect props up the impact of both coordination sites 1430.The site 1430 of surface domination can promote that lithium is from electricity Solve matter 125 to transfer to insert material 1610.As elsewhere herein is discussed, this moves can be via Such as Li₂The intermediate oxide of O occurs.The work function of this electron transfer can be different to that at transfer electricity The work function of the electron transfer in sub-step 2230.Such as, in multiple embodiments, work function Be at least 0.001,0.1,0.3,0.4,0.5,0.8,1.0,1.3,1.7,2.0 or 2.4V or Any combination between this.In some embodiments, compare during lithium is inserted into insertion material 1610 It is inserted in the main body of the nano-particle including that skin effect props up coordination site 1430 the most relatively Favorably.But, skin effect props up the existence of coordination site 1430, and can to promote that charge carrier is inserted into slotting Enter in material 1610.

If charge carrier is changed into oxide in transfer electronics step 2230, then implement at some In scheme, transfer electronics step 2250 includes making oxygen return to surface effect from inserting material 1610 transfer Coordination site 1430 should be propped up.Inserting this oxygen received at material 1610 as the oxide of charge carrier, Discharge from charge carrier during inserting.It is transferred return skin effect at this oxygen and props up coordination site 1430 After, then this oxygen can be used the further generation of transfer electronics step 2230, i.e. oxygen is by again Circulation.

Although describing of Figure 22 supposes the charge carrier of reception in receiving lithium step 2220 and inserts above The charge carrier entering lithium step 2240 is that two kinds of different single charge carriers (are probably mutually similar Type), but in multiple embodiments, step 2220,2230 and 2240 can be by identical Single charge carrier carry out.Such as, in some embodiments, receive lithium step 2220 to wrap Include reception charge carrier in skin effect props up coordination site 1430.Then, transfer electronics Step 2230 includes that charge carrier and skin effect are propped up coordination site 1430 and reacted to produce intermediate compound The reaction of thing.In some embodiments, this reaction includes 2Li⁺+_MO+2e^-→Li₂O+M (wherein M is any one of transition metal discussed herein and Li₂O is the intermediate produced Compound).In inserting lithium step 2240, midbody compound (such as, Li₂O) it is inserted into Insert in material 1610, or (or two) in the Li in midbody compound are from Li₂In O O transfer to insert material (such as, Li_xSi) atom in.This transfer may cause MO again Raw, this MO is split off in transfer electronics step 2230.It should be noted that in this example, identical Individually Li atom be included in step 2220-2230 and 2240 each in.Transfer electronics step Rapid 2250 is unwanted in these embodiments of the method illustrated by Figure 22.Implement at some In scheme, including such as Li₂The reaction sequence of the intermediate of O and do not include the reaction sequence two of intermediate Person is possible during single charging cycle.

Multiple embodiments illustrate especially herein and/or describe.However, it should be understood that amendment and become Change form by above-mentioned teaching cover and within the scope of the appended claims, without deviating from their essence Refreshing and intended scope.Such as, when example discussed herein concentrates on, there is the CNF of cone-in-cone structure Time, this teaching goes for having the other materials of similar or alternative structure.Similarly, When Copper base material and lithium charge carrier are discussed in this article, other base materials and charge carrier are general to this area Logical technical staff is obvious.Silicon layer 115 selectively by addition to silicon or replacement as silicon The insertion material of thing is formed.Such as stannum, germanium, carbon, graphite, Graphene, silicon, discussed herein its His material or combinations thereof can be used as inserting material.Additionally, aeroge, nano wire, TiO₂ (titanium oxide), metal wire, carbon line or boron nitride nanometer fiber can be used in replacing carbon discussed herein Nanofiber.Binding agent 1440, skin effect are propped up coordination site 1430, are inserted material 1610 and CNF 110 and the relative concentration of other compositions in the drawings can be markedly different from the relative concentration of diagram.

Various energy storing device including capacitor, battery and their mixing can include The electrode instructed herein.These energy storing devices can be used such as, illuminator, portable Electronic equipment, load balancing apparatus, communicator, stand-by power supply, the vehicles and calculating device. Concepts taught herein can be applied to negative electrode and anode under many circumstances.

The embodiment explanation present invention discussed herein.When referenced in schematic describes these enforcements of the present invention During scheme, described method and/or the various amendments of concrete structure and reorganization are to those skilled in the art Member can become obvious.Depend on the teachings of the present invention and improve all of this area by these teachings These amendment, reorganization or version, be considered within the scope and spirit of the invention.Therefore this A little description is not considered as in limiting sense with accompanying drawing, and it should be understood that the present invention is not restricted to institute The embodiment shown.

Claims (89)

1. an energy storage system, including:

Electrolyte, it includes one or more charge carriers；

Conductive base；

Multiple supporting wires；

Inserting material, it is disposed on described supporting wire and is configured at described insertion material Reversibly adsorbing the member of described charge carrier in main body, described insertion material includes having in 0.1 μm And the granule of size between 29 μm；And

Binding agent, it is disposed on described insertion material and includes multiple nano-particle, described in receive Each skin effect that is configured to supply in rice grain props up coordination site, described binding agent be configured to by Described supporting wire remains close to described base material；

Wherein said insertion material is configured to prop up coordination site from described skin effect and receives described electric charge load The oxide of body；

Wherein adjacent to the concentration of described nano-particle of described insertion material relative to away from described insertion material The concentration of the nano-particle of material is bigger.

2. an energy storage system, including:

Electrolyte, it includes one or more charge carriers；

Conductive base；

Multiple supporting wires, it attaches to described base material；

Inserting material, it is disposed on described supporting wire and is configured at described insertion material The member of described charge carrier is reversibly adsorbed in main body；And

Binding agent, it is disposed on described insertion material and includes that multiple skin effect props up coordination site, The plurality of skin effect is propped up coordination site and is configured to promote that described charge carrier is inserted into described insertion In material；

Wherein said insertion material is configured to prop up coordination site from described skin effect and receives described electric charge load The oxide of body；

Wherein said skin effect is propped up coordination site and is disposed on nano-particle and at described binding agent In, the concentration of the described nano-particle of neighbouring described insertion material is relative to away from described insertion material The concentration of nano-particle is bigger.

3. an energy storage system, including:

Electrolyte, it includes one or more charge carriers；

Conductive base；

Inserting material, it is configured to reversibly adsorb described electric charge in the main body of described insertion material The member of carrier；And

Binding agent, it is disposed on described insertion material and includes multiple nano-particle, described in receive Each skin effect that is configured to supply in rice grain props up coordination site, and described skin effect props up coordination site The faradic current being configured on the surface of described nano-particle interacts and makes electronics supply Member to described charge carrier；

Wherein said insertion material is configured to prop up coordination site from described skin effect and receives described electric charge load The oxide of body；

Wherein adjacent to the concentration of described nano-particle of described insertion material relative to away from described insertion material The concentration of the nano-particle of material is bigger.

4. an energy storage system, including:

Negative electrode；And

Anode, it is by electrolyte and described cathodic disbonding, and described electrolyte includes one or more electricity Charge carrier, described anode includes:

Conductive base；

Inserting material, it is configured to insert described charge carrier and under the first reaction electromotive force Electronics is made to be supplied to described charge carrier from described base material,

Multiple nano-particle, it includes that skin effect props up coordination site, described skin effect Zhi Peiwei Point is configured to make electronics be supplied to described charge carrier, described first reaction under the second reaction electromotive force Absolute difference between electromotive force and described second reaction electromotive force is less than 2.4V；

Wherein said insertion material is configured to prop up coordination site from described skin effect and receives described electric charge load The oxide of body；

Wherein adjacent to the concentration of described nano-particle of described insertion material relative to away from described insertion The concentration of the nano-particle of material is bigger.

5. an energy storage system, including:

Electrolyte, it includes one or more charge carriers；

Conductive base；

Multiple supporting wires, it attaches to described base material；

Insert material, its be disposed in described supporting wire each upper and be configured to insert described The member of described charge carrier is reversibly adsorbed in entering the main body of material；And

Multiple nano-particle, described nano-particle is formed between described electrolyte and described insertion material Barrier, each skin effect that is configured to supply in described nano-particle props up coordination site；

Wherein said insertion material is configured to prop up coordination site from described skin effect and receives described electric charge load The oxide of body；

Wherein adjacent to the concentration of described nano-particle of described insertion material relative to away from described insertion material The concentration of the nano-particle of material is bigger.

6. system as claimed in claim 5, wherein said skin effect is propped up coordination site and is configured to lead to Cross the faradic current interaction on the surface of described nano-particle and adsorb the one-tenth of described charge carrier Member.

7. the system as described in claim 5 or 6, wherein said insertion material is configured as electric charge Carrier inserts expansion and described expansion when occurring and reduces the institute on the surface of described insertion material State the surface coverage of nano-particle.

8. system as claimed in claim 7, wherein said expansion reduces described nano-particle and is formed The effectiveness of the described barrier of charge carrier.

9. the system as described in claim 5 or 6, wherein said barrier is to allow some charge carriers Arrive the incomplete barrier of described insertion material.

10. the system as described in any one in claim 1-6, wherein said charge carrier includes Lithium.

11. systems as described in claim 1,2,5 or 6, wherein said supporting wire includes that carbon is received Rice fiber.

12. systems as claimed in claim 11, each in wherein said carbon nano-fiber include with The multi-walled carbon nano-tubes of cone-in-cone structure.

13. systems as described in claim 1,2,5 or 6, wherein said supporting wire includes many walls CNT.

14. systems as described in claim 1,2,5 or 6, wherein said supporting wire is vertically to arrange Row.

15. systems as described in claim 2,5 or 6, wherein by binding agent by described supporting wire Remain close to described base material.

16. systems as described in any one in claim 1-6, wherein said insertion material includes Silicon.

17. systems as described in any one in claim 1-6, wherein said insertion material includes Metal-oxide, carbon, graphite or Graphene.

18. systems as described in any one in claim 1-6, wherein said insertion material includes There is the silicon grain of at least 0.6 μm size.

19. systems as claimed in claim 18, are additionally included in the oxide in described insertion material.

20. systems as described in any one in claim 1-6, wherein said insertion material includes Silicon and oxide.

21. systems as described in claim 1,2,5 or 6, the length of wherein said supporting wire exists Between 3.0 and 200 μm.

22. systems as described in claim 1,2,5 or 6, wherein said supporting wire includes airsetting Glue.

23. the system as claimed in claim 22, also include being disposed in described aeroge is molten Agent.

24. systems as described in any one in claim 1-6, wherein said nano-particle includes Titanium.

25. the system as claimed in claim 22, wherein said nano-particle also includes lithium.

26. systems as described in any one in claim 1-6, wherein said nano-particle includes Lithium.

27. systems as described in any one in claim 1-6, wherein said nano-particle is many Layer.

28. systems as described in any one in claim 1-6, wherein said nano-particle includes Metal.

29. systems as described in any one in claim 1-6, wherein said nano-particle includes Metal-oxide.

30. systems as described in any one in claim 1-6, wherein said nano-particle includes Metal nitride or metal hydride.

31. systems as described in any one in claim 1-6, wherein said nano-particle straight Footpath is between 1 and 34 nanometers.

32. systems as described in claim 1,3 or 4, the concentration of wherein said nano-particle makes Described nano-particle forms barrier between described electrolyte and described insertion material.

33. systems as described in any one in claim 1-6, wherein said insertion material is joined It is set to prop up coordination site from described skin effect and receives the oxidation of lithium.

34. systems as described in any one in claim 1-6, wherein said skin effect is arranged Site includes carbon.

35. systems as described in claim 1,2 or 5, wherein adjacent to described in described supporting wire The concentration of grain is less relative to the concentration away from described supporting wire.

36. systems as described in any one in claim 1-6, wherein said skin effect is arranged Site is disposed in average diameter less than on the nano-particle of 100nm.

37. systems as described in claim 1,2,5 or 6, wherein said supporting wire is directly attached In described conductive base.

38. systems as described in claim 1,2,5 or 6, wherein said supporting wire is conduction.

39. systems as described in any one in claim 1-6, wherein said nano-particle is extremely Few 25% surface being arranged in proximity to described insertion material.

40. systems as described in any one in claim 1-6, the table of wherein said insertion material The concentration of the described nano-particle in 5 nanometers in face more than described surface away from described insertion material The concentration of the described nano-particle between 10 and 15 nanometers.

41. systems as described in any one in claim 1-6, wherein said insertion material is by cloth It is set to so that at described nano-particle, the electronics of supply is conducted through described insertion material from described base material Material.

42. systems as described in any one in claim 1-6, wherein said insertion material and institute State nano-particle and be configured such that described nano-particle promotes that charge carrier is inserted into described insertion material In material.

43. systems as described in any one in claim 1-6, wherein said nano-particle big Majority is disposed on the surface of described insertion material.

44. systems as described in claim 1,2,5 or 6, wherein said nano-particle includes TiO₂ And described insertion material includes silicon.

45. systems as claimed in claim 44, wherein said nano-particle also includes lithium.

46. systems as claimed in claim 45, wherein said supporting wire includes aeroge.

47. systems as described in any one in claim 1-6, wherein said nano-particle includes Activated carbon, graphite or Graphene.

48. 1 kinds of methods producing energy storing device, described method includes:

Produce conductive base；

Grow supporting wire on the substrate；

Insertion material is applied to described supporting wire, and described insertion material is arranged to charge carrier Insert；

Multiple skin effects are propped up coordination site and is applied for described in close proximity inserting material；And

Jointing material is applied to described insertion material；

Wherein, described insertion material is configured to prop up the coordination site described electric charge of reception from described skin effect The oxide of carrier；

Wherein, described skin effect props up the nano-particle that coordination site is disposed in described jointing material On, the concentration of the nano-particle of neighbouring described insertion material is relative to the nanometer away from described insertion material The concentration of granule is bigger.

49. 1 kinds of methods producing anode, described method includes:

Conductive base is provided；

Producing skin effect prop up coordination site and insert the mixture of material, described skin effect props up coordination site It is configured to accept electronics from charge carrier under the first reaction electromotive force and described insertion material is joined It is set to accept described charge carrier or accept electronics from described charge carrier under the second reaction electromotive force；With And

Described mixture is applied to described base material；

Wherein said insertion material is configured to prop up coordination site from described skin effect and receives described electric charge load The oxide of body；

Wherein said mixture also includes that jointing material, described skin effect prop up coordination site and be disposed in institute State on the nano-particle in jointing material, the concentration of the nano-particle of neighbouring described insertion material relative to Concentration away from the nano-particle of described insertion material is bigger.

50. methods as claimed in claim 49, also include:

After applying described mixture, described anode is placed in contact with including the electrolysis of charge carrier Matter；

React under electromotive force from propping up the institute in coordination site in described skin effect described first State a supply electronics in charge carrier；And

The one in described charge carrier is made to be inserted in described insertion material.

51. methods as claimed in claim 49, wherein said mixture also includes the nanometer comprising lithium Granule.

52. methods as claimed in claim 51, wherein said skin effect is propped up coordination site and is included titanium.

53. methods as claimed in claim 49, wherein said skin effect is propped up coordination site and is included titanium.

54. 1 kinds of methods producing energy storing device, described method includes:

Conductive base is provided；

Supporting wire is provided；

Insertion material is applied to described supporting wire, and described insertion material is arranged to charge carrier Insert；

Skin effect is propped up coordination site and adds described supporting wire to；And

Before jointing material is applied to described insertion material, described skin effect is propped up coordination site and is executed It is added to described insertion material；

Wherein said insertion material is configured to prop up coordination site from described skin effect and receives described electric charge The oxide of carrier；

Wherein said skin effect is propped up coordination site and is disposed on the nano-particle in described jointing material, The concentration of the nano-particle of neighbouring described insertion material is relative to the nanometer away from described insertion material The concentration of grain is bigger.

55. methods as claimed in claim 54, also include adding the granule comprising lithium to create sun Pole.

56. methods as claimed in claim 55, also include adding negative electrode and electrolyte to being created Anode to produce described energy storing device.

57. methods as claimed in claim 54, wherein said supporting wire includes aeroge.

58. 1 kinds of methods producing energy storing device, described method includes:

Conductive base is provided；

Supporting wire is provided；

Insertion material adds to described supporting wire, and described insertion material is arranged to charge carrier Inserting and be included in the granule of size between 0.1 and 29 μm, described granule comprises silicon and oxide； And

Binding agent is used to add described supporting wire to described conductive base；

Wherein said binding agent includes multiple nano-particle, and each in described nano-particle is configured to Skin effect is provided to prop up coordination site；

Wherein said insertion material is configured to prop up coordination site from described skin effect and receives described electric charge load The oxide of body；And

Wherein, the concentration of the nano-particle of neighbouring described insertion material is relative to away from described insertion material The concentration of nano-particle bigger.

59. 1 kinds of methods making charge storage devices charge, described method includes:

At the anode of described charge storage devices, set up potential gradient, described anode include electrolyte, There is skin effect prop up multiple nano-particle of coordination site, insert material and base material；

The the first electric charge load receiving described electrolyte in coordination site is propped up in described skin effect Body；

Make electronics transfer to described first electric charge at that described skin effect is propped up in coordination site to carry Body；

The second charge carrier is received at the described insertion material of described anode；And

Electronics is made to transfer to described second charge carrier from described insertion material；

Wherein said insertion material is configured to prop up coordination site from described skin effect and receives charge carrier Oxide；

Wherein adjacent to the concentration of described nano-particle of described insertion material relative to away from described insertion The concentration of the nano-particle of material is bigger.

60. methods as described in any one in claim 48 and 54-58, wherein said supporting wire Including CNT or carbon nanocoils.

61. methods as described in claim 58 or 59, wherein said nano-particle includes titanium.

62. methods as described in claim 58 or 59, are wherein put when described energy storing device During electricity, described nano-particle forms at least one of which monolayer barrier on the surface of described insertion material.

63. methods as claimed in claim 62, also include by making described energy storing device charge Reduce the surface coverage of described nano-particle on the described surface of described insertion material.

64. methods as described in claim 58 or 59, wherein said nano-particle is configured to produce Oxide and the described insertion material of raw described charge carrier are configured to make described charge carrier make Insert for described oxide.

65. methods as claimed in claim 59, also include adding supporting wire to described base material.

66. methods as claimed in claim 58, wherein said supporting wire is being added to described base material Before be coated with described insertion material.

67. methods as described in claim 58 or 59, wherein prop up coordination site in described skin effect Before being applied to described base material, described insertion material is applied to described base material.

68. methods as claimed in claim 59, wherein said first charge carrier includes lithium.

69. methods as described in any one in claim 49-53, wherein said first reaction electricity Gesture and described second reaction electromotive force cause described skin effect to be propped up between coordination site and described insertion material Electrostatic potential difference less than 2.4V.

70. methods as claimed in claim 59, wherein said skin effect is propped up coordination site and is configured to Promote that described first charge carrier is inserted in described insertion material.

71. methods as described in any one in claim 48-59, wherein said skin effect is propped up Coordination site is disposed on the nano-particle including titanium.

72. methods as claimed in claim 58, wherein adjacent to described in the surface of described insertion material Skin effect props up the concentration of coordination site more than the effect of described surface elsewhere in described binding agent The concentration of coordination site should be propped up.

73. methods as claimed in claim 59, wherein receive the described step of described second charge carrier Suddenly the increase of the volume of described insertion material and the described surface effect on described insertion material are caused The reduction of the area density of coordination site should be propped up.

74. methods as described in claim 73, the reduction of wherein said area density causes electric charge to carry Body is inserted into the increase of the speed in described insertion material.

75. methods as claimed in claim 59, wherein said second charge carrier is described first electricity The oxide of charge carrier.

76. methods as claimed in claim 59, wherein said skin effect is propped up coordination site and is configured to Promote that described first charge carrier is inserted in described insertion material.

77. methods as claimed in claim 59, wherein said first charge carrier is inserted into and includes institute State in the main body of the nano-particle that skin effect props up coordination site is thermodynamically than described first electric charge Carrier is inserted in described insertion material less favorable.

78. methods as claimed in claim 59, wherein said first charge carrier and described second electricity Charge carrier is made up of identical chemical substance.

79. methods as described in any one in claim 48-59, wherein said insertion material bag Include Ag, Al, Bi, C, Ge, Sb, Si, Sn or Zn.

80. methods as described in claim 58 or 59, wherein said multiple nano-particle are arranged On the surface of described insertion material.

81. methods as described in any one in claim 48-59, wherein said insertion material quilt It is coated on supporting wire.

82. methods as described in any one in claim 48-59, wherein said insertion material quilt It is coated on the carbon nano-fiber being vertically arranged.

83. methods as claimed in claim 59, wherein make the electronics of described first charge carrier from institute State one transfer that skin effect props up in coordination site and make described electronics from described insertion material Transfer to described second charge carrier occur less than under the reaction electromotive force of 2.4V difference.

84. methods as claimed in claim 59, wherein make described electronics turn from described insertion material Reaction electromotive force when moving on to described second charge carrier be enough to cause described second charge carrier to be inserted into In described insertion material, but it is not enough to cause described second charge carrier to effectively insert described nanometer In granule.

85. methods as claimed in claim 59, wherein receive described second at described insertion material Charge carrier causes the fall of the described surface coverage of the described nano-particle on described insertion material Low.

86. methods as claimed in claim 59, wherein receive described second at described insertion material Charge carrier causes charge carrier to insert the increase of the speed in described insertion material.

87. methods as claimed in claim 59, wherein said skin effect is propped up coordination site and is configured to The oxide and the described insertion material that produce described first charge carrier are configured to reduce described Two charge carriers.

88. methods as claimed in claim 59, also include making oxygen at described insertion material and described table Face effect is propped up and is shifted between coordination site.

89. methods as described in claim 88, wherein said oxygen at described insertion material as institute The oxide stating the first charge carrier is received.