JP6389986B2 - Electrode including color stop - Google Patents

Description

(Cross-reference of related applications)
This application claims priority based on US Patent Provisional Application No. 61 / 254,090, filed Oct. 22, 2009, entitled “Electrodes Including Collar Stop”. No. 392,525, filed February 25, 2009, title of invention “High C
This is a continuation-in-part application of “apacity Electrodes”.
No. 1 / 067,018, filed February 25, 2008, and US Provisional Application No. 61/130
No. 679, filed on June 2, 2008, claiming priority. All of the above provisional US patent applications and US patent applications are hereby incorporated by reference.

  The present invention belongs to the field of electrode technology.

US provisional patent application 61 / 254,090 specification US patent application Ser. No. 12 / 392,525 US Provisional Patent Application No. 61 / 067,018 US Provisional Patent Application No. 61 / 130,679

Various preferred embodiments of the present invention include an electrode that is disposed along a length of the substrate, a support filament connected to the substrate, and the length of the support filament to react with an electrochemical reaction (eg, an ion An interlayer (intercalation) layer comprising a donor acceptor material configured to accept electrons, charge donors and / or charge acceptors, wherein the region of the interlayer adjacent to the substrate is the interlayer layer A lower amount of donor acceptor material as compared to the region distal to the substrate.

Various preferred embodiments of the present invention include a method of producing an electrode, the method comprising receiving a substrate and growing a first region of support filaments coupled to the substrate;
Growing a collar stop at the end of the first region of the support filament, distal to the substrate, the collar stop comprising donor acceptor material reaching the first region A step configured to reduce the amount, and growing a second region of the support filament from the color stop, the second region of the support filament having a diameter smaller than the color stop; Adding a donor acceptor material to the support filament such that a donor material having a thickness greater than that of the first region of the support filament is deposited in the second region of the support filament.

Various preferred embodiments of the present invention include a battery comprising a first electrode and a second electrode, the second electrode being disposed on the support filament, a support filament coupled to the substrate, Proximity to the substrate, including a lower layer of donor acceptor material compared to an interlayer configured to receive electrochemical reactants and a region of the interlayer distal to the substrate And a means for generating the region.

FIG. 6 illustrates the design of a support cap electrode according to various embodiments of the present invention. FIG. 4 illustrates the design of a support collar electrode according to various embodiments of the present invention. FIG. 4 illustrates a design of an electrode with a color stop according to various embodiments of the present invention. FIG. 6 illustrates the design of a support cap and support collar electrode according to various embodiments of the present invention. FIG. 6 illustrates a design of an electrode with a support cap and a color stop, according to various embodiments of the present invention. FIG. 6 illustrates the design of an electrode with a support collar and a color stop, according to various embodiments of the present invention. FIG. 3 illustrates an electrode including an interlayer material according to various embodiments of the present invention. FIG. 3 illustrates an electrode including an interlayer material according to various embodiments of the present invention. FIG. 3 illustrates an electrode including an interlayer material according to various embodiments of the present invention. FIG. 6 illustrates a method of making an extension of an electrode according to various embodiments of the invention. FIG. 6 illustrates the relationship between measured charge capacity versus interlayer material thickness according to various embodiments of the present invention. FIG. 4 illustrates battery cycle life versus temperature and interlayer material thickness according to various embodiments of the invention. FIG. 3 illustrates a battery according to various embodiments of the invention. FIG. 3 illustrates carbon nanofibers grown on a copper substrate, according to various embodiments of the invention. FIG. 3 illustrates carbon nanofibers grown on a copper substrate according to various embodiments of the invention. FIG. 4 illustrates carbon nanofibers grown on a copper substrate and covered with an interlayer material according to various embodiments of the present invention. FIG. 4 illustrates carbon nanofibers grown on a copper substrate and covered with an interlayer material according to various embodiments of the present invention. FIG. 11 illustrates a cross section of an electrode without the interlayer 750 used to collect the data of FIGS. 9 and 10, according to various embodiments of the present invention.

Detailed Description of the Invention
FIG. 1 illustrates an electrode including a support filament 110. The support filament 110 includes a support cap 150. The support cap 150 is optionally an extension of the support filament 110 and is about 1%, 2.5%, 10%, 25%, 40 from the diameter 112 of the support filament.
%, Or a support cap width 157 as large as about 60%. Support filament height 114 includes support cap height 155. In some embodiments, the height of the support cap is 1
55 is at least 250 nm, 500 nm, 2000 nm, or 5000 nm. In other embodiments, the support cap height 155 is at least 1%, 5%, 20%, 30%, or 50% of the filament height 114. The support cap width 157 can be at least 1%, 5%, 15%, 40%, or 75% of the starting position separation distance 126. The start position is the point on the seed layer 122 where growth of the support filament begins. The cross-sectional shape of the support cap 150 (shown in FIG. 1) can be rectangular, triangular, square, circular, or rhombus. Other shapes are possible. The support cap 150 is
The intercalation layer 750 (FIG. 7) is configured to prevent sliding off the unbonded end of the support filament 110.

The support filament 110 includes carbon nanotubes (CNT), carbon nanofibers (CNF), and nanowires (NW).
), Or other nanoscale structures. The material comprising CNTs is generally carbon and can include other materials such as metals, semiconductors, and insulators that are included in the source gas during CNT growth. In addition, the CNTs can be single walled or double walled. C
The material comprising NF is generally carbon and can include other materials such as metals, semiconductors, and insulators that are included in the source gas during CNF growth. CNTs are generally at least 2
It is noted that it has a diameter of nm, 5 nm, 10 nm, 30 nm, or 50 nm. CN
F is generally at least 30 nm, 50 nm, 150 nm, 250 nm, or 750 n
It is marked as having a diameter of m. Nanowires (NW) can be metals (such as gold, copper, or tin) or semiconductors (such as silicon, germanium, InP, GaN, GaP, ZnO), or MnO2, indium tin oxide, ZnO, SnO2. , Fe2O3, In2O3, or Ga2O3. Other materials are possible.

FIG. 2 illustrates an electrode with a support filament 110 that includes a support collar 210. The support collar 210 is optionally an extension of the support filament 110 and has a diameter that is at least 1%, 2.5%, 10%, 25%, 40%, or 60% greater than the diameter 112 of the support filament. In some embodiments, the support collar height 214 is at least 100 nm, 25
0 nm, 500 nm, 2000 nm, or 5000 nm, or larger,
And it can be reduced to 50 nm or smaller. In some examples,
Support collar height 214 is at least 1%, 5%, 1% of support filament height 114.
5%, 40%, or 75%. The width 212 of the support collar is the starting position separation distance 126.
Of at least 1%, 5%, 15%, 40%, or 75%. The shape of the support collar 210 can be rectangular, square, circular, triangular, semi-circular, rhombus, arcuate, or the like. Other shapes are possible. The base distance 216 of the support collar is optionally at least half of the support filament height 114. The base distance 216 of the support collar can be 10%, 30%, or 75% of the height 114 of the support filament. The base distance 216 extends at least 500 nm, 1000 nm, 2500 nm, 50 from the initial position 120.
It can be 00 nm or 12,500 nm. In addition to this, the base distance 216
Can be terminated within a few microns of the extended end 152 of the filament.

FIG. 3 illustrates an electrode with a support filament 110 that includes a color stop 310. The color stop 310 is the support filament 110 in the support filament 110.
An area characterized by a larger diameter than other areas. In some embodiments, the diameter of the collar stop 310 is at least 1%, 2.5 times the diameter of the support filament 110 (eg, the support filament diameter 112) in one or more other regions of the support filament 110.
%, 10%, 25%, 40%, or 60% greater. The diameter of the color stop 310 and the color stop interval 312 are controlled to generate a trunk 350.
This trunk 350 has a reduced donor acceptor material (DAM).
erial) region. The DAM reduction region is a region where the amount of interlayer material is reduced compared to other regions of the support filament, but the interlayer material is not necessarily completely absent. For example, in various embodiments, the donor acceptor material region can be 75%, 50% (by weight per unit area of the support filament 110) relative to other regions of the support filament 110,
It may contain up to 25%, 10%, or 5% interlayer material. (For illustrative purposes, this interlayer material is defined as the material that either provides or accepts charge to complete the external circuit of the electrode. This interlayer material includes charge carriers, charge donors, and / or Alternatively, the charge acceptor is configured to exchange with the surrounding electrolyte, and this interlayer material can optionally be porous to those species, with the color stop spacing 312 being approximately zero. Or at least 10%, 50%, 75%, or 95% of the distance 126 between the initial positions, the color stop 310 can be grown anywhere along the entire length of the support filament 110, for example In some embodiments, the color stop 31
0 is from the initial position 120 to 10000 nm, 5000 nm, 2000 nm, 1000 nm
, 750 nm, 250 nm, 100 nm, 25 nm, or 5 nm or less.

The method of making the color stop 310 is generally the support collar 210 or the support cap 1.
This is the same as the method of manufacturing 50. Methods for controlling the diameter of the support collar 210, support cap 150, and / or color stop 310 include changing the temperature of the source gas, substrate, or reaction chamber (or a combination of the three), or various source gas flow rates. Can be included. For example, these diameters can be controlled by changing the composition of the source gas during the growth of the support filament 110. Support filament 110, collar stop 310, support collar 210, and / or support cap 15
Other ways to control the zero diameter are to apply an electrostatic or dynamic electric field, to apply a static or dynamic magnetic field, or to apply a combination of electric and magnetic fields. Other ways of controlling these diameters will be apparent to those of ordinary skill in the art.

Collar stop 310, support collar 210, and support cap 150 can optionally be made of the same material as support filament 110, depending on the particular process being performed,
Other materials or ratios can be used. For example, different source gases can be used at different processing times to replace methane with acetylene, ethylene, or ethanol (for CNT / CNF growth). In addition, different process gases can be used at different times. For example, argon can be used in place of a processing gas such as ammonia, nitrogen, or hydrogen. Different gas mixing rates can also be used depending on the desired effect. It will be apparent to those skilled in the art of CNT / CNF growth that other source gases and process gases can be used.

The color stop thickness 314 is typically less than a few microns, but can be up to 1%, 5%, 10%, 26%, 50%, or 75% of the support filament height 114. In some embodiments, the color stop thickness 314 is no more than 40%, 20%, 5%, 2%, or 0.25% of the support filament height 114. The cross section of the color stop 310 can be oval, diamond or circular depending on the growth rate of the support filament 110 as seen in the plane of FIG. Other cross-sectional shapes are possible. These shapes and dimensions optionally correspond to the support cap 150 and the support collar 210, and the color stop 31.
Can be given by zero.

The color stop diameter 316 is controlled by the processing method selected to produce the color stop 310. For example, during the growth of the color stop 310, the temperature of the reaction chamber is changed to slow down or accelerate the reaction that creates the support filament 110, thereby causing the support filament 110 to be larger than other regions of the support filament 110. A region having a diameter can be produced. For example, the support filament 110 can include narrower diameter regions separated by a color stop 310 having a relatively larger diameter. Alternatively, the support filament includes a relatively large area between the substrate 124 and the color stop 310 (the color stop 310 can be smaller or substantially the same diameter as this area), and the substrate Distal to 124 can include a smaller diameter region. The support filament diameter 112 is defined as the minimum diameter of the support filament.

The color stop interval 312 includes a start position separation distance 126 and a color stop diameter 31.
6 is controlled. The dimensions of the color stop 310 are selected such that a reduction in DAM adhesion occurs between the color stop 310 and the substrate 124 as compared to the region of the support filament 110 that is distal to the substrate 124. A single support filament 110 can include two or more color straps 310 and / or two or more support collars 210.

In the illustrated embodiment, the trunk 350 has a reduced amount of DAM compared to the portion of the support filament 110 that is substantially free of donor acceptor material or above the collar stop 310 (distal to the substrate). This is the area that has been This means that the color stop diameter 31
6 and the appropriate choice of the color stop spacing 312. For example, the color stop spacing 312 and the color stop diameter 316 may indicate that a particular color stop 310 is
It can be chosen to barely touch its nearest adjacent color stop to effectively create a color stop spacing 312 equal to zero. Alternatively, the color stop interval 312 can be greater than zero. The color stop 310 reaches the region between the color stop 310 and the substrate 124 in the support filament 110.
This forms a barrier that reduces the amount of sliver relative to other portions of the support filament 110.

FIG. 4 shows various embodiments of the present invention, in which the filament 110 has a support cap 150 and a support collar 210 but no color stop 310.

FIG. 5 illustrates various embodiments of the present invention, in which the filament 110 has a support cap 150 and a collar stop 310 but no support collar 210.

FIG. 6 illustrates various embodiments of the present invention, in which the filofilament 110 is shown.
Has a support collar 210 and a color stop 310 but no support cap 150. 4-6 illustrate a support cap 150, a support collar 210, and a color stop 310.
It is illustrated that any combination of can be included on the support filament 110.
These combinations can include one, two, three, or more of these elements. A single support filament 110 can include two or more color stops 310 and / or two or more support collars 210. The positions of the support collar 210 and the color stop 310 can be changed up and down with respect to the positions shown in this figure in the length direction of the support filament 110. The color stop 310 and the support collar 210 are generally cylindrical shapes that are symmetric about the long axis of the support filament 110.

In FIG. 7A, color stop 310, support cap 150, support collar 210, and DA
The interlayer layer containing M is illustrated. This illustration schematically represents the basic function for the color stop 310, for example, the interlayer 750 is mostly deposited / grown on top of the support filament 110 between the support cap 150 and the color stop 310, Below the color stop 310, no DAM / growth (or less deposition / growth) is created, thus creating a DAM reduction region 720 with relatively little or little interlayer material. By appropriate selection of the color stop diameter 316 and the color stop spacing 312, a mask is created such that the minimum (or less) interlayer material reaches the substrate.

The DAM reduction region 720 is a region where the deposition of the interlayer layer 750 is blocked in the support filament 110. In general, the DAM reduction region 720 is adjacent to the seed layer 122.

FIG. 7A also illustrates the usefulness of support cap 150 and support collar 210. Both the support cap 150 and the support collar 210 are characterized by a diameter that is larger than the diameter 112 of the other part of the support filament 110. If the interlayer 750 expands during electrode operation, in some embodiments the interlayer separates from the diameter of the support filament 110. In these embodiments, as long as the support collar width 212 and / or the support cap width 157 is greater than the inner diameter of the expanded interlayer material, the interlayer layer 750 is mechanically constrained to the support filament 110, thereby providing the interlayer material. Ensures that it does not separate from the support filament 110.

Color stop 310 and support collar 210 are optionally the same size and / or shape. One difference between the color stop 310 and the support collar 210 is that the support collar 210
Is located (or otherwise configured) at a location on the support filament 110 that assists adhesion of the interlayer 750 to the support filament 110. For example, the support collar 210 is configured to prevent the interlayer 750 from sliding off the unbonded end of the support filament 110. In contrast, the color stop 310 provides a reduced portion of the interlayer 750 in the support filament 110 in the region between the color stop 310 and the substrate 124 as compared to other portions of the support filament 110. It is located at a position on the support filament 110 that would cause it to occur (otherwise it is configured as such). The support collar 210 can also produce a region of the interlayer 750 that is reduced to a lesser degree.

Free interlayer material 710 is a material that is not stopped by color stop 310 during deposition / growth of interlayer 750. The source of material for the deposition / growth of the interlayer 750 is considered to come generally from above the support filament 110 (at the top of the page), as illustrated in FIGS.

FIG. 7C shows an alternative embodiment of the support filament 110. These examples include examples of support filaments having two or more support collars and tapered shapes. Various different examples of the support filament 110 illustrated in FIGS. 7B and 7C are not typically found on the same electrode. The electrode typically includes one type of support filament 110, support collar 210, support cap 150, and color stop 310 since all support filaments are produced together.
The variations illustrated herein are for illustrative purposes only. Interlayer 75 illustrated in FIGS.
The thickness of 0 is also for illustration purposes only. In the exemplary embodiment, interlayer 750 is significantly thicker than support filament 110. The thickness of the interlayer 750 also changes as charged species are adsorbed and desorbed. In addition, the thickness of the interlayer 750 described in this specification refers to a state where there is no charged species adsorbed or desorbed by the interlayer 750.

FIG. 8 illustrates a method for manufacturing a support filament having an interlayer 750. The first step 801 is to receive the substrate 124. The substrate 124 is optionally copper for the anode (anode) or aluminum for the cathode (cathode). The substrate can be made of other materials depending on the desired application. For example, stainless steel or graphite (graphite) can be used for the substrate. Those skilled in the art of battery design can further specify other materials depending on the desired application.

An optional second step 803 is to clean the substrate. The substrate is washed (803
The purpose is to prepare the substrate for subsequent material deposition and growth in a later processing step. This means removing any organics, oxides, and other contaminants present on the current collector. The method of cleaning the substrate uses a solvent (such as acetone, isopropanol, TEC, or methanol) from a physical method (eg, using an abrasive to remove a thin layer of material exposed to contaminants). ) To apply appropriate preparation to the substrate until chemical methods and / or chemical etching (in the case of copper, citric acid soaking / cleaning that dissolves part of the actual substrate) or for subsequent processing steps Any combination of physical and chemical methods can be used.

The third step 805 is optional seed layer deposition. Seed layer deposition 805 is a processing step that produces a base layer or seed layer 122 for growth of support filament 110. This processing step can be realized by (physical or chemical) vapor deposition / growth methods, liquid deposition / growth methods, or solid phase deposition / growth methods, or any combination thereof.

Physical vapor deposition techniques (transporting the material to be deposited from the material source to the substrate in the gas phase) include thermal evaporation, electron beam evaporation, DC sputtering, DC magnetron sputtering, RF sputtering, pulsed laser deposition, cathodic arc deposition, Etc. can be included. A reactive physical vapor deposition method can also be used, in which an “impurity gas” is injected into the chamber during the growth process so that the layer grows and the “impurity gas” is layered. It is taken in.

Chemical vapor deposition techniques (transporting chemical precursors to the surface in the gas phase, followed by chemical reaction on this surface) are low pressure chemical vapor deposition, plasma enhanced chemical vapor deposition (PECVD), large It may include atmospheric pressure chemical vapor deposition, metal organic chemical vapor deposition, hot wire chemical vapor deposition, ultra-high frequency plasma chemical vapor deposition, microwave plasma chemical vapor deposition, and the like.

Liquid phase growth techniques for forming the seed layer 122 may include plating, electrolytic plating, chemical solution deposition, or the like. Solid phase growth techniques can include focused ion beam deposition. Another possibility for the growth method is a solution containing a liquid and a suspension of appropriately sized particles to be sprayed onto the current collector, after which the substrate is “cured” to remove the carrier solution, Particles remain on the surface of the substrate.

Any combination of the above processing steps can be used to create a suitable seed layer 122 for generating a starting position for growth of the support filament 110.

The fourth step 815 in this process is the generation of the start position. This step depends on the method chosen to produce the seed layer 122. For example, the start position separation distance 12
6 can be determined by the thickness and material selected for seed layer deposition 805.
For example, a 3000 Angstrom nickel / 300 Angstrom chromium seed layer produces several starting positions per square centimeter. Nickel thickness is 2
If reduced to 000 angstroms, the number of starting positions per square centimeter is 3
It will be different from the number of starting positions in 000 Angstrom nickel. If other materials are selected to replace nickel with iron, the resulting starting position per square centimeter will be different. Step 815 is optionally part of step 805.

Solid layer deposition techniques allow for control of the starting position per square centimeter. This technique can be focused ion beam deposition, where the starting position / cm 2 can be controlled directly by the location where the focused ion beam deposits the material or by the nanoparticle suspension, where the starting position / cm2 is controlled by the number of nanoparticles contained in a given volume of suspension. The number of starting positions can also be controlled by the size of the focused ion beam deposition position or the size of the nanoparticles in the solution.

The starting site is typically generated when the reaction vessel in which the electrode is produced reaches the appropriate temperature with the appropriate source gas flow, and this source gas begins to catalyze with the seed layer 122. In this way, a start position is generated, and the growth of the support filament 110 is started.

The fifth step 820 is to grow the support filament 110. There are a number of growth processes available for growing the support filament 110. For example, chemical vapor deposition, thermal chemical vapor deposition, vapor-liquid-solid growth (a type of chemical vapor deposition),
Plasma enhanced chemical vapor deposition is a process in which growth of carbon nanotubes (CNT), carbon nanofibers (CNF), and nanowires (NW) is achieved. It is recognized by those skilled in the art of filament growth that there are other available growth methods.

Examples of source gases that can be used to grow CNT / CNF are carbon monoxide, methane, ethane, ethylene, acetylene, and the like. Other hydrocarbons or inorganic compounds can also be used for the growth process.

Of interest is the plasma enhanced chemical vapor deposition (CVD) method, because the growth of the support filament 110 aligns with the electric field of the plasma, thereby allowing the production of vertically aligned support filaments 110. It depends. Thermal CVD can also produce vertically aligned support filaments 110 under specific processing conditions. Furthermore, water-enhanced CVD allows longitudinally aligned support filaments with very high aspect ratios (length / diameter approximately equal to 1,000,000), allowing very tall support filaments.

It has also been demonstrated that appropriately denatured bacteria and viruses are growing nanowire structures. Such a technique can be used to make the support filament 110.

Some of these techniques can be used together at the same time, with appropriate selection of materials. For example, using bacteria / viruses in the presence of an applied electric field, CNT / CNF
/ NW can be grown to produce vertically aligned support filaments. Another method for growing the support filament 110 is to apply an electric and / or magnetic field during VLS growth to control the trajectory of the growing CNT / CNF / NW, which is the three-dimensionality of the support filament 110. Control the shape. Another technique is to start the growth of CNT / CNF / NW support filament 110 in a reaction vessel operating in PECVD mode, after a specified time, switch the reaction vessel to thermal CVD mode, and again after a specified time, This reaction vessel is connected to PEC
Re-convert to VD mode. It will be apparent to those skilled in the art of CNT / CNF / NW growth that there are other possible combinations that allow proper growth control of the support filament 110.

The height 114 of this support filament 110 is generally determined by the duration of the growth process. The temperature of the reaction vessel, the source gas used, and the combination and strength (or their absence) of the applied electric and magnetic fields can affect the rate and amount of filament growth.

The diameter 112 of the support filament 110 generally depends on the thickness of the seed layer 122 or, if a nanoparticle suspension method is selected to form the seed layer 122, depending on the size of the nanoparticles contained in the suspension. Alternatively, if a focused ion beam deposition method is selected to form the seed layer 122, it depends on the size of the ion beam. The temperature of the reaction vessel,
Source gas used, and combination and strength of applied electric and magnetic fields (or their absence)
Can also affect the diameter of the support filament 110.

Sub-step 820a can be performed during the growing step 820 of the support filament 110, in which the color stop 310 is grown. This can be achieved by changing the temperature of the reaction vessel, the source gas used and its relative composition and flow rate, the direction and strength of the applied electric and magnetic fields (or their absence). The duration of this change is implied and the color stop thickness 314 and the color stop diameter 316 are determined. The color stop interval is controlled by the duration of the aforementioned change to the steady state parameter (and the duration of this change itself) as well as by the starting position separation distance 126. Sub-step 820a can be repeated.

Sub-step 820b can be performed during the growing step 820 of the support filament 110, and if this sub-step grows the support collar 210 and sub-step 820a occurs, this sub-step occurs after sub-step 820a. . Sub-step 820b is accomplished by changing the temperature of the reaction vessel, the source gas used and its relative composition, the combination of applied electric and magnetic fields and the strength (or their absence). The diameter, thickness, and height of the support collar 210 are greatly controlled by changing the parameters described above.

Sub-step 820c can be performed during the growing step 820 of the support filament 110, and the support cap 150 is grown in sub-step 820c and sub-step 820.
If b occurs, this substep occurs after substep 820b. This sub-step can be achieved by changing the temperature of the reaction vessel, the source gas used and its relative composition, the direction and intensity of the applied electric and magnetic fields (or their absence). The diameter, thickness, and height of the support cap 150 are optionally controlled by changing the parameters described above.

Any of the three sub-steps 820a, 820b, and 820c can be performed independently of the presence or absence of the other sub-steps 820a, 820b, and 820c. For example, sub-step 820a is sub-step 820b or sub-step 820.
It can be executed without c. Alternatively, sub-steps 820a and 820c can be performed without performing sub-step 820b, or sub-step 820a
Alternatively, it may be decided to perform sub-step 820b without performing 820c. In addition to this, it is decided not to execute any of the sub-steps 820a, 820b, and 820c, and thereby, the support filler filament 110 in which the change in the diameter of the support filament 110 in the length direction is minimized can be manufactured. it can.

The sixth processing step 825 is to create the DAM reduction region 720, and the DAM reduction region 720 does not correspond to the trunk 350 at all. (Elements 350 and 720
The reason is that the DAM reduction region 720 is created during the deposition of the interlayer 750, while the trunk 350 is defined in relation to the shape of the support filament 110. When the interlayer 750 is added, the trunk 350 becomes the DAM reduction region 720. Specifically, trunk 350 is part of support filament 110, while DAM reduction region 720 refers to a region where interlayer material 750 is reduced or absent. ) The DAM region creation process 825 can be accomplished by several methods, including but not limited to the use of the color stop 310. Examples of such methods include support filament 110 during interlayer material growth and directional deposition (such as evaporation or ion beam deposition).
Including controlling the aspect ratio of the image. Additional methods include electrodeposition and electroless plating on the bottom (base) layer to insulate the trunk 350. A sputtering / light (mild) etch of the masking layer can be performed to open the support filament 110 in preparation for the growth / deposition of the interlayer 750, or the growth parameters of the support filament 110 can be modified ( Advantageous aspect ratios (such as dendritic structures) can also be achieved.
This can be achieved by changing the composition of the source gas and process gas used during growth. Another possible way to create the DAM reduction region 720 is to perform interlayer material deposition and directional etchback (eg, reactive ion etching) to remove the coverage by the interlayer layer 750 from the support filament 110. . The creation of the DAM reduction region 720 may depend on the method and structure selected for CNT / CNF / NW growth and the method and structure selected for interlayer deposition. For example, after depositing the interlayer 750, the DAM reduced region 720 can be created by a suitable directional etch, such as reactive ion etching or inductively coupled plasma etching.

The eighth processing step 830 is to deposit / grow interlayer layer 750. (Note that D
AM refers to materials that donate or accept ions during charging and discharging of battery cells, and the interlayer 750 can provide DAM and other layers that produce adhesion or increased adsorption. A layer or a layer capable of improving conductivity. There may be other purposes for these layers. These additional layers can be above or below the deposited DAM. )

The growth of the interlayer 750 can be achieved by (physical or chemical) vapor deposition / growth, liquid deposition / growth, or solid phase deposition / growth, or any combination thereof.

Physical vapor deposition (transporting the material to be deposited in the gas phase from the material source to the substrate) is thermal evaporation,
Electron beam evaporation, direct current sputtering, direct current magnetron sputtering, high frequency sputtering, pulsed laser deposition, cathodic arc deposition, and the like can be included. Reactive physical vapor deposition can also be used, and the “mixed gas” injected into the combustion chamber during the growth process
Which is incorporated into the formation of this layer.

Chemical vapor deposition techniques (transporting chemical precursors to the surface in the gas phase, followed by a chemical reaction on this surface) include low pressure chemical vapor deposition, plasma enhanced chemical vapor deposition, atmospheric pressure chemical vapor Phase growth method,
Metal organic chemical vapor deposition, hot-wire chemical vapor deposition, ultra-high frequency plasma chemical vapor deposition, microwave plasma chemical vapor deposition, and the like can be included.

It should be noted that more than one material can be deposited simultaneously at any deposition stage.
For example, two (or more) different types of metals such as tin (Sn) and gold (Au) can be deposited / grown simultaneously, and two (or more) such as silicon (Si) and germanium (Ge). )
Different types of semiconductors can be deposited, such as lithium iron phosphate (LiFePO4) and lithium-nickel-cobalt-manganese complex oxide (Li (NiCoMn) O2).
Two (or more) different types of oxides can be grown / deposited. In addition, a plurality of kinds of materials such as a metal and a semiconductor, a semiconductor and an oxide, a metal and an oxide, or a metal, a semiconductor, and an oxide can be mixed. Examples include eutectoid (co-deposition) of silicon (Si) and lithium (Li), eutectoid of silicon (Si) and LiO2 (or SiO2),
And eutectoid of silicon (Si), lithium (Li), and LiO2 (or SiO2). It may be desirable to co-deposit an insulating material such as silicon oxide (SiO 2), silicon nitride (Si 3 N 4). In addition to this, it may be desirable to co-deposit carbon (C).

Interlayer 750 is optionally made by a liquid phase process such as electroless plating or electroplating. The interlayer can also be made by coating the support filaments with a solution containing an interlayer material (such as silicon (Si) or tin (Sn)) suspended in a binder solvent matrix. After appropriate treatment, the solvent is removed from the matrix leaving only the binder and interlayer material, thereby supporting filament 1
10 and an electrode comprising an interlayer material are produced. This technique can also be applied to the cathode. This interlayer may comprise an airgel. When producing the interlayer 750 as a liquid process, the DAM reduction region 720 is optionally created by including a material that repels this liquid in the trunk 350. For example, when water is used, hydrophobic species can be included in the region of the trunk 350. These species can be incorporated into the support filament 110 or can be coated on the surface of the support filament 110.

In some embodiments, the conductivity of the interlayer 750 is controlled by appropriate selection of deposition and growth techniques. For example, in the case of sputtering, by using heavily doped p + or n + silicon, a silicon interlayer having a higher electrical conductivity than undoped silicon is produced. (For example, heavily doped silicon is tens of ohms cm, whereas pure silicon is tens of thousands of ohms cm.) For CVD silicon deposition using silane, the addition of phosphine or arsine is optionally used. Increase the conductivity of the deposited / grown silicon. In various embodiments, the dopant is boron (B), gallium (Ga),
Arsenic (As), phosphorus (P), antimony (Sb), indium (In), thallium (Th),
And / or bismuth (Bi). Other dopants are possible.

In some embodiments, the conductivity of the interlayer 750 is such that during silicon deposition / growth,
Increasing by deposition of metals (but not limited to, for example, gold (Au), tin (Sn), silver (Ag), lithium (Li), or aluminum (Al)). In some embodiments, the conductivity of the interlayer 750 is controlled by ion implantation (implantation). These methods are also possible with other materials selected for the interlayer 750, such as germanium (Ge). In various embodiments, the resulting interlayer layer 750 resistivity is 10 Ωcm, 500 Ωcm, 2000 Ωc.
m, or 12000 Ωcm or less. In another embodiment, the resistivity is 12000 Ωcm or higher.

In some embodiments, step 830 includes post processing of the deposited interlayer 750. By this post-treatment, the crystal structure of the interlayer 750 can be changed. For example, in some embodiments, amorphous silicon is deposited as an interlayer 750, and subsequent processing steps appropriately anneal heat the amorphous silicon, thereby providing a surface on the polysilicon layer and / or interlayer 750. Is made. The resulting structure can include a polysilicon layer on the outer surface and an amorphous silicon layer between the polysilicon layer and the support filament 110. Both silicon layers are considered part of the interlayer 750. This annealing heat treatment can be accomplished by using a high power laser or some other fast high temperature heat source. Such post-deposition post-treatment annealing heating methods optionally include a cathode and / or
Or apply to anode material.

In some embodiments, the deposited interlayer 750 is passivated. In the case of silicon, this passivation can be achieved by annealing as described elsewhere herein, or by oxide, nitride, and / or carbide (carbide) layers of approximately 5 nm, 10 nm, 40 nm, 100 nm, or 250 nm or less. Can be achieved by deposition.
This oxide, carbide, or nitride layer is considered part of the interlayer 750 and can be produced as part of the step 820 of growing the support filament. This oxide or nitride can be grown or deposited by thermal means and standard CVD and PECVD techniques. For example, surface passivation is optionally accomplished by growing carbide on the surface of the interlayer 750. This growth is performed in step 805 of seed layer deposition.
, Starting position creation step 815, and growing support filament step 820, wherein carbides, oxides, and / or nitrides are step 820.
Grow in. In some embodiments, the height of the CNT / CNF / NW grown on the interlayer 750 is at most a few microns and is typically 250 nm or less.

Due to the shape of the support filament 110, the collar stop 310, the support collar 210, and the support cap 150, different amounts of interlayer material can be deposited at different locations along the length of the support filament 110. The deposition / growth method used to make the interlayer 750 optionally relies on surface reactions that initiate and continue the growth process. If the flow rate of the reactants reaching the surface of the support filament 110 is reduced, the deposition / growth rate of the interlayer layer 750 is reduced accordingly.

By way of example and with reference to FIGS. 7A-7C, if the color stop spacing 312 is zero, essentially the surface of the support filament 110 below the color stop 310 is
Reactant does not reach or minimal reactant reaches, thereby supporting filament 11
A DAM reduction region 720 having a small amount of interlayer 750 compared to the other portions of zero is produced.

Another way to ensure deposition / growth of different amounts of interlayer 750 in the length direction of support filament 110 relies on a high aspect ratio of support filament height 114 to starting position separation distance 126. This aspect ratio is 5: 1, 10: 1, 100: 1, 1000: 1,
It can be on the order of 10,000: 1, or 1000000: 1, and in some cases it can be larger. Larger aspect ratios indicate that the reactant is a substrate 124.
Means that the side surface of the support filament has a smaller, close to zero solid angle, so that the amount of growth along the support filament decreases accordingly, thereby causing the interlayer 750 to Produces a DAM reduction region 720 with little or no. Color stop 310 is not required to generate AM reduction region 720.

In step 840, the manufacture of the electrode can be completed. This electrode is optionally contained within the battery.

9A and 9B illustrate the measured capacity of the anode fabricated using the process described herein, where the support filament 110 is carbon nanofiber and the interlayer 75
0 is silicon. FIG. 9A illustrates that the capacitance of the electrode increases with the thickness of the interlayer 750. In FIG. 9B, line 910 illustrates the calculated capacity of the carbide coating alone,
Line 920 illustrates experimental results using a mixture of amorphous and polysilicon. This measurement was performed at a half-cell setting. FIG. 9B shows that compared to a pure graphite-based anode,
The improvement of the charge storage capacity by 5 to 7 times is illustrated. The amount of this improvement depends on the thickness of the interlayer 750 and the type of material.

FIG. 10 shows an interlayer 750 of a battery using an anode manufactured by using the treatment described in this specification.
The measured cycle life versus thickness and temperature is illustrated by comparison with industry standard electrodes.
The support filament 110 is a carbon nanofiber, and the interlayer 750 is silicon. Measurements are taken at two different temperatures in a full battery setting and the cycle is C /
Run at a rate of 2. This data demonstrates a greatly enhanced cycle life at high temperatures compared to the prior art.

FIG. 11 illustrates a battery 1100 according to various embodiments of the present invention. The battery 1100 includes a first electrode 1110 and a second electrode 1120 such as those illustrated in FIGS. 1-8 herein. The second electrode 1120 may or may not include the features illustrated in FIGS.
The battery 1100 further includes a first electrode 111 in a circuit configured to supply power to the load.
A conductor (not shown) configured to couple the zero and the second electrode 1120; The manner in which these conductors can be constructed will be apparent to those of ordinary skill in the art. Battery 1100
Is generally a rechargeable (rechargeable) battery. The first electrode can be configured to operate as an anode or a cathode.

FIG. 12A is an image of an electrode in which the height 114 of the support filament 110 is 3.5 μm. FIG. 12B is an image of an electrode where the height 114 of the support filament 110 is 17.5 μm. The support filaments of FIGS. 12A and 12B do not include an interlayer material.

FIG. 13A is an image of an electrode in which the height 114 of the support filament 110 is 3.5 μm and 0.25 μm of silicon is deposited as an interlayer 750. The data show that a 3.5 μm support filament 110 coated with a 0.25 μm interlayer 750 (silicon) has a very poor cycle life (<10 cycles).

FIG. 13B shows that the height 114 of the support filament 110 is 17.5 μm and 0.25 μm.
It is an image of the electrode which deposited the silicon | silicone of as an interlayer layer 750. FIG. The data show that the 17.5 μm support filament 110 coated with a 0.25 μm interlayer 750 (silicon) has a very good cycle life (> 30 cycles, <20% capacity reduction). Various embodiments of the present invention include a support filament 110 having a height 114 of at least 17.5 μm (17.5 × 10 −6 m), and at least 0.1 μm, 0.25 μm, 0
. Includes an interlayer of 35 μm, 0.5 μm, or 0.75 μm.

FIG. 14 is a cross section of an electrode in which the height 114 of the supporting filament is 10 μm and the interlayer 750 is not present. This electrode design (linearly measured interlayer material deposition thickness is 0.5μ
m, 1.5 μm, 4.0 μm), and the data shown in FIGS. 9 and 10 are obtained. This result shows enhanced capacity at high temperature and improved cycle life (300 cycles,
40% capacity drop, C / 2 rate, 60 ° C.). Various embodiments of the present invention have at least one
A height 114 of 0 μm (10.0 × 10 −6 m), and at least 0.1 μm, 0.25 μm,
A support filament having an interlayer 750 of 0.35 μm, 0.5 μm, or 0.75 μm is included.

Several embodiments are specifically illustrated and / or described herein. But,
Obviously, modifications and variations are covered by the foregoing teachings and fall within the scope of the appended claims and do not depart from their intended scope. For example, the electrodes described herein can be used in devices other than batteries.

The embodiments described herein are illustrative of the present invention. Since these embodiments of the present invention have been described with reference to illustrative examples, various modifications or adaptations of the described methods and / or specific structures may be apparent to those skilled in the art. All such modifications, adaptations, or variations that rely on the teachings of the invention are considered to be within the scope of the invention. Accordingly, these descriptions and drawings are not to be taken in a limiting sense, and it is clear that the present invention is by no means limited to the illustrated embodiments.

Claims (1)

A substrate;
A support filament bonded to the substrate;
An interlayer comprising a donor-acceptor material configured to receive a reactant of an electrochemical reaction, wherein the donor-acceptor material is disposed along the entire length of the support filament and is eutectoidized silicon and lithium Comprising an interlayer comprising:
The support filament includes a color stop, and the color stop has a larger diameter than a portion of the support filament that is not the color stop, and the region of the interlayer close to the substrate is formed on the substrate of the interlayer layer. causing lower amounts of donor-acceptor material as compared to a region distally against, the amount of interlayer material by weight of per unit area of the support filament before Symbol proximate region, the region of the distal An electrode characterized in that it is less than 10% of the interlayer material.