CN101427415A - 3-D microbatteries based on interlaced micro-container structures - Google Patents
3-D microbatteries based on interlaced micro-container structures Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
An electrical energy storage device (20,70) includes a substrate (22), which is formed so as to define a multiplicity of micro-containers separated by electrically-insulating and ion-conducting walls (32). A first plurality of anodes (A) is disposed in a first subset (24) of the micro-containers, and a second plurality of cathodes (C) is disposed in a second subset (26) of the micro-containers. The anodes and cathodes are arranged in an interlaced pattern.
Description
Cross reference to related application
The rights and interests that the application requires to be filed in the U.S. Provisional Patent Application 60/566,205 on April 27th, 2004 and is filed in the U.S. Provisional Patent Application 60/590,833 on July 22nd, 2004.It is relevant with the PCT patent application PCT/IL2004/000945 that is filed on October 14th, 2004.These related applications are transferred to the assignee of present patent application, and their disclosure is incorporated herein by reference.
Technical field
The present invention relates generally to electric energy, particularly three-dimensional (3D) micro cell.
Background technology
The small two-dimension thin-film microbattery is known in the art.For example, its disclosure United States Patent (USP) 5,338,625 and 5,567,210 incorporated herein by reference has been described the thin-film microbattery as the standby or main integrated power source of electronic equipment.Described battery comprises the electrolyte and the vanadium oxide negative electrode of lithium anode, electrochemical stability.Described battery directly is manufactured on the semiconductor chip, on the semiconductor element or on the part of chip carrier.
Its disclosure United States Patent (USP) 6,610,440 incorporated herein by reference described can with microelectromechanicpositioning (MEMS) system or the integrated or integrated microcosmic battery of other microscopic circuits with it.The inventor has described and has been used to use the intermittent reaction thing electricity to be carried out the closed system microcosmic battery of storage inside.Described battery comprises microscopic electrode, electrolyte and electrolytical container.
In its disclosure United States Patent (USP) 6,197,450 incorporated herein by reference, three-dimensional thin-film microbattery has been described.The little electrochemical energy memory cell of film (MEESC) has been described as micro cell and double layer capacitor (DLC).This energy storage units comprises two thin layer electrodes, solid electrolyte thin intermediate and the 4th optional current collector thin layer.Described layer is deposited on the surface of substrate successively.Substrate comprises a plurality of cavities of the arbitrary shape with high aspect ratio, and these a plurality of cavities have increased total electrode area of every volume ratio.
In addition, people such as Long are at " Three-Dimensional Battery Architectures ", Chemical Review, and the 10th volume, No. 104, in October, 2004 the 3D micro cell has been described in the 4463-4492 page or leaf, the document is incorporated herein by reference.
People such as Hart are at " 3-D Microbatteries ", ElectrochemistryCommunications, and the 5th volume, 2003, the geometric configuration of 3D micro cell has been described in the 120-123 page or leaf, the document is incorporated herein by reference.This paper provides the electric current that several K-A array configurations are shown and the finite element modelling of Potential Distributing.
People such as Kleimann are at " Formation of Wide and Deep Pores in Silicon byElectrochemical Etching ", Materials Science and Engineering B, the 69-70 volume, 2000, described a kind of method that is used for producing at silicon the chamber array in the 29-33 page or leaf, the document is incorporated herein by reference.People such as Li are at " Microfabrication of ThermoelectricMaterials by Silicon Molding Process ", Sensors and Actuators A, the 108th volume, 2003, described another in the 97-102 page or leaf and be used to produce the technology of microcavity array, the document is incorporated herein by reference.This author has described a kind of technology that is used to make the thermoelectric micromodule of fine scale with intensive aligning and high aspect ratio unit.
Summary of the invention
Embodiments of the invention provide improved 3D micro cell, and it is compared with micro cell as known in the art, and good energy density and capacity is provided.
Disclosed micro cell is included in two groups of little containers of high aspect ratio that form in the substrate.Little container is filled with suitable anode and cathode material and is used as the electrode of micro cell.The pattern that anode and negative electrode are arranged to interlock and separate by the wall of backing material.
Processed ionic conductivity and the electric insulation of substrate wall of separating little container to strengthen them.In certain embodiments, a plurality of microcosmic hole forms in partition wall, so that strengthen the ionic conductivity between anode and the negative electrode.Will be described below a kind of method of using the porose silicon substrate of metal assistant chemical etching formation.In certain embodiments, there is hole wall also oxidized to increase their electric insulation.There is pore structure to be filled, as liquid electrolyte, composite polymer electrolyte (CPE) or hybridized polymer electrolyte (HPE) with ionic conduction and material electric insulation.
In certain embodiments, the little container of anode and negative electrode forms in the apparent surface of substrate.This configuration has been simplified the technology of filling little container and has been prevented the mixing of anode and cathode material.
In other embodiments, all little containers form in single of substrate.In this configuration, custom-designed mask and/or interim fill process have prevented the mixing of different electrode materials.
But in an alternative embodiment, print in the depression in the backing material by that will approach and little molding of porose separator film mechanically stable or minute-pressure and to form little container.
In certain embodiments, disclosed 3D micro cell is used for to the microelectronic circuit power supply that is integrated in this micro cell on the same substrate.
Compare with other 3D micro cell as known in the art, micro cell described herein provides good energy density.The manufacturing process that describes below is relatively easily implemented.In addition, as will be illustrated below, disclosed configuration makes it possible to use many kinds of anodes and cathode material.Similarly, disclosed configuration makes it possible to use the various electrolytes that comprise liquid electrolyte.
Principle of the present invention can be used to use the staggered electrode group by porose divider separates to make other small-sized energy storage device such as capacitor.
Therefore, provide a kind of electric energy storage device according to one embodiment of present invention, having comprised:
Substrate, it is formed so that limit a large amount of little container of being separated by wall electric insulation and ionic conduction; And
Be arranged on more than first anode in first sub little container of organizing, and be arranged on more than second negative electrode in second sub little container of organizing, the pattern that described anode and negative electrode are arranged to interlock.
In a disclosed embodiment, wall has break-through itself and the hole that forms.Additionally or alternatively, wall comprises the porose separator film that puts on substrate.Further additionally or alternatively, at least some holes are filled with electrolyte.In certain embodiments, electrolyte comprises at least a in liquid electrolyte, hybridized polymer electrolyte (HPE) and the composite polymer electrolyte (CPE).
In another embodiment, at least a hole that forms in use electrochemical etching process and the chemical etching process.
In another embodiment again, substrate comprises at least a in metal, sodium ion conductor and the lithium ion conductor of silicon, GaAs, carborundum, ceramic material, thermoelasticity polymer, thermoplastic polymer, surface oxidation.
In another embodiment again, electric energy storage device comprises one of lithium micro cell and lithium ion micro battery.
In another disclosed embodiment, little container of the first and second son groups forms in the single surface of substrate.But in an alternative embodiment, little container of the first and second son groups forms in the corresponding apparent surface of substrate.Additionally or alternatively, substrate comprises the middle wafer of the little containers that wherein are formed with the first and second son groups and is coupled to the surface of middle wafer so that form at least one face wafer of bottom surface of little container of at least one height group.
In a disclosed embodiment, wall is oxidized at least in part.
In another embodiment, this device comprises at least one at least one current collector that is coupled in a plurality of anodes and a plurality of negative electrode.Additionally, this at least one current collector comprises one of metal forming and depositing metal layers.
In another embodiment again, use bonding (pasting) technology, vacuum-assisted to embed at least a in technology and the thick film depositing operation and come deposition anode and negative electrode.
In another embodiment again, that little container has is square, at least a in triangle, hexagon and the circle.In another embodiment, little container has the degree of depth diameter ratio greater than 1.In another embodiment again, at least a in a large amount of little container arrangement squarelys, triangle and the hexagon lattice.In another embodiment, use at least a in etch process and the lithographic printing etch process to form a large amount of little containers.
In a disclosed embodiment, anode comprises lithiated intercalation compound, and it comprises at least a in carbon, graphite, lithium alloy and the lithium.In another embodiment, negative electrode comprises MoS
2, FeS
2, WS
2, LiCoO
2, LiNiO
2And Li
1+xMn
2-yO
4At least a in the material.
A kind of microelectronic component also is provided according to one embodiment of present invention, has comprised:
Substrate;
Be arranged on the microcircuit on the substrate; And
Be arranged in the substrate and be coupled so that the electric energy storage device of electrical power to be provided to microcircuit, this memory device comprises:
Be formed on the little container of a large amount of three-dimensionals in the substrate, separate by wall electric insulation and ionic conduction; And
Be arranged on a plurality of anodes in first sub little container of organizing, and be arranged on a plurality of negative electrodes in second sub little container of organizing, the pattern that described anode and negative electrode are arranged to interlock.
A kind of method that is used to construct electric energy storage device also is provided according to one embodiment of present invention, has comprised:
In substrate, form a large amount of three-dimensional little containers, make little container separate by wall electric insulation and ionic conduction; And
More than first anode is arranged in little container of the first son group, and more than second negative electrode is arranged in little container of the second son group pattern that described anode and negative electrode are arranged to interlock.
Description of drawings
According to below in conjunction with the detailed description of accompanying drawing to embodiments of the invention, will more fully understand the present invention, in the accompanying drawings:
Fig. 1 is the schematic diagram of the visualization of micro cell according to an embodiment of the invention;
Fig. 2 is the schematic sectional view of micro cell according to an embodiment of the invention;
Fig. 3 schematically illustrates the flow chart that is used to make the method for micro cell according to an embodiment of the invention;
Fig. 4 is the schematic diagram of the visualization of micro cell according to another embodiment of the present invention;
Fig. 5 is the schematic top view of the mask that uses in the manufacturing of micro cell according to an embodiment of the invention;
Fig. 6 schematically illustrates the flow chart that is used to make the method for micro cell according to an embodiment of the invention;
Fig. 7 A is the schematic sectional view of microelectronic component according to an embodiment of the invention; And
Fig. 7 B is the schematic top view of microelectronic component according to another embodiment of the present invention.
Embodiment
Two-sided microbattery configurations
Fig. 1 is the schematic diagram of the visualization of micro cell 20 according to an embodiment of the invention.Micro cell 20 forms in substrate 22.Substrate is semiconductor wafer typically.Although the method that describes below can be used to make micro cell in the wafer of any thickness, the typical thickness of silicon wafer is in the scope of 100-800 micron.In one embodiment, substrate 22 comprises silicon.Alternatively, can use other backing material, comprise: semi-conducting material such as GaAs (GaAs) and carborundum (SiC); Ceramic material such as aluminium oxide; Glass; Plastics such as various thermoelasticity and thermoplastic polymer; The metal substrate of surface oxidation; And other suitable material.In other embodiments, substrate can comprise solid ion conductor such as sodium ion conductor or lithium ion conductor.(for example, Owen in " Ionically Conducting Glasses " and Armand the purposes of such material has been described in " Ionically conductivePolymers ".These two pieces of documents all appear at " Solid StateBatteries ", Sequeira and Hooper (editors), and Nato Science Series E, Springer, October 1985, and it is incorporated herein by reference.) in certain embodiments, micro cell comprises lithium battery or lithium ion battery.
The electrode of micro cell 20 is arranged on two groups and is formed in the substrate 22, is called here in the chamber of " little container ".First group of little container 24 forms in first of substrate 22.Second group of little container 26 forms in the opposite face of this substrate.As will be described below, little container 24 is as a plurality of anodes of micro cell.Little container 26 is as a plurality of negative electrodes.(the little container of anode and negative electrode is represented with " A " and " C " respectively in the drawings.Anode and negative electrode are referred to as " electrode ".)
These two groups of little containers typically with periodic, staggered patterned arrangement in substrate 22.(staggered pattern is sometimes referred to as " crossing one another " pattern).In the example of Fig. 1, anode and negative electrode with staggered patterned arrangement on square net, wherein each electrode have opposite polarity four nearest-neighbors (be each negative electrode four anodes as nearest-neighbors, and vice versa).Most of electrochemical reaction occurs between the nearest-neighbors of such opposite polarity.In other embodiments, anode and negative electrode can be arranged to other pattern, as the configuration described in the paper of above-cited Hart.But the paper of Hart has been described several alternatives of little container and has been arranged, comprises square, triangle and hexagon grid.Every kind of layout is shown as at the specific performance demand of micro cell such as electric current uniformity, energy capacity and power between the electrode and optimizes.Generally speaking, the number of negative electrode does not need to equal the number of anode.In addition, each electrode can be the negative electrode of the anode of any number and any number as nearest-neighbors.
The shape of the little container in the example of Fig. 1 is square.But in alternative embodiment, can use other suitable little container shapes such as triangle, rectangle, hexagon or circular little container.The characteristic width of little container or the typical range of diameter are that several microns are until tens microns.Depend on the electrical specification of little container width, wall thickness and battery, the total number of the little container in the typical micro cell can change to several ten thousand from hundreds of.Typically, little container has high aspect ratio, and promptly their degree of depth is significantly greater than their width or diameter.Generally speaking, little container need not all have identical size.
Can use any two groups of little containers 24 and 26 of making in several technology as known in the art.For example, the paper of above-cited Kleimann has been described a kind of electrochemical etching method that is used for forming at silicon substrate the chamber.Above-cited United States Patent (USP) 6,197, but 450 several alternative methods that are used at the backing material etched cavity have been described.Another example that is called " dry ecthing " method is by Robert Bosch, GmbH (Stuttgart, Germany) Kai Fa inductively coupled plasma (ICP) technology.ICP technology is for example at United States Patent (USP) 6,720, describes in 273, and the disclosure of this patent is incorporated herein by reference.Any other suitable method such as etching and/or lithographic process can be used to form these two groups little containers 24 and 26 equally.Typically, the wall of separating between little container is etched to several microns thickness.Penetrate in the chamber and stop little container before the apparent surface of substrate and form technology, typically keep in the 1-100 micrometer range, be preferably the base thickness degree in the 10-50 micrometer range.In certain embodiments, as will be explained below, the feasible wall of separating the substrate 22 of little container is porose.Depend on the relation of thickness and the thickness of the partition wall between little container at the end of little container of each son group, can make the end of little container of each son group for integral body or only part is porose.
But in an alternative embodiment, make the cross structure of little container group by using two or more wafers.For example, available three wafers are made cross structure.Middle wafer is etched or otherwise be processed into and comprise two groups of little containers, allows these two groups of little containers to penetrate the whole thickness of middle wafer in this configuration.Make two face wafers.First wafer comprises the hole of mating with little container group 24.Second wafer comprises the hole of mating with little container group 26.First wafer is that little container group 26 forms the solid end, and second wafer is that little container group 24 forms the solid end.These three wafers are joined together to form the two-sided micro-container structures of 3D shown in Fig. 1.
In certain embodiments, after little vessel filling electrode material, all anodes all are connected electrically to positive electrode current collector 28.Similarly, all negative electrodes all are connected to cathode current collector 30.These two current collectors comprise the metal level on the surface that puts on substrate 22.Current collector can comprise thin metal film or thin metal foil such as the Copper Foil that is deposited on the substrate 22. Current collector 28 and 30 comprises the voltage terminal of micro cell 20, and uses suitable wiring to be connected to the circuit of being powered by micro cell.
In other embodiments, can omit one or whole two current collectors.Typically, when male or female fully conducts electricity, can omit corresponding current collector.As the part of electrode fill process, be to allow electrode material to overflow little container and form conductive layer on the substrate surface as a kind of possible method of current collector with electrode.This conductive layer is with electrode interconnection and play the effect of current collector.
Fig. 2 is the schematic sectional view of micro cell 20 according to an embodiment of the invention.View shown in Fig. 2 is the vertical section of this micro cell on the plane located of the mark " II " of the Fig. 1 on be arranged in.This sectional view shows the substrate 22 that the little container 26 of little container 24 of anode and negative electrode is separated.After chamber 24 is filled with anode material, can see that anode and current collector 28 have to electrically contact.Anode is by backing material and current collector 30 electric insulations.Similarly, negative electrode and current collector 30 have and electrically contact, and isolate by backing material and current collector 28.
In certain embodiments, the part of substrate is further processed ionic conductivity and/or the electric insulation to strengthen them.Certainly, the ionic conductivity between anode and the negative electrode is the pith that produces the electrochemical reaction of the electric current in the micro cell 20.In one embodiment, make that the wall of separating 32 is porose so that ion can flow through it between little container.Will be described below and be used for producing the exemplary process in hole at substrate 22.
There is hole wall typically to comprise nano-pore (typically, diameter is that tens nanometers are to the hundreds of nanometer).Wall is filled with ionic conduction and material electric insulation then.In certain embodiments, this material comprises the liquid electrolyte that is injected with pore structure and filler opening.In other embodiments, this material comprises hybridized polymer electrolyte (HPE) or composite polymer electrolyte (CPE).To demonstration electrolyte and the demonstration methods that some are used to prepare such material be described in the micro cell example below.Fill electrolytical wall and comprise the anode of micro cell and the porose spacer layer between the negative electrode.In particular, the whole thickness of wall 32 is run through in some holes, connects anode and the little container of negative electrode.As the part of the electrochemical reaction in the micro cell, such through hole makes ion can flow through it.Therefore, porose separator provides electric insulation (electronics stops) in the ionic conduction that allows between the electrode.In certain embodiments, the part of substrate 22 is oxidized before embedding electrolyte, so that strengthen their electric insulation.
Two-sided micro cell manufacture method
Fig. 3 schematically illustrates the flow chart that is used to make the method for micro cell 20 according to an embodiment of the invention.This method is by forming step 40 at the first little container, forms first group of little container 24 and begin in a face of substrate 22.As mentioned above, step 40 typically comprises suitable etching and/or imprint lithography.The degree of depth of control chamber makes little container not penetrate the apparent surface of substrate.Similarly, form step 42, in the apparent surface of substrate, form second group of little container at second little container.Little container is separated by the thin-walled that typically is several micron thickness.
Form step 44 in the hole, make that wall 32 is porose.In one embodiment, step 44 comprises metal assistant chemical etch process.In a kind of exemplary process, substrate 22 is dipped into PdCl
2In the acid solution (typically being 0.564mM) five seconds.Then, substrate is dipped into the freshly prepd H of comprising
2O
2: in the etching mixture of ethanol: HF (1:2:4) 40-60 minute.This technology is typically at room temperature carried out.In other embodiments, use electrochemical etching process.Electrochemical etching process typically comprises substrate is immersed suitable etching solution and apply electric field between substrate and solution.The exemplary process of this kind has been described in the U.S. Provisional Patent Application of quoting in the above 60/566,205.Alternatively, any other suitable method that is used for producing pore structure as known in the art is used in substrate 22 and produces the hole.
The result of step 40-44 is cross structures that form, two groups of little containers in two apparent surfaces of substrate 22.Little container is separated by the thin hole wall that has.
But (use therein among the above-mentioned alternative embodiment of the staggered micro-container structures of the wafer manufacturing of three joints, step 40-44 replaces with a technology, this technology comprises: form in middle wafer in through hole, the little wall of a container in separating middle wafer and form the hole, in two face wafers, form the hole of alternate group, and two face wafers are joined to the apparent surface of middle wafer.)
Be filled with suitable electrode material at 46, two groups of little containers of electrode filling step.At separator filling step 48, there is hole wall 32 to be filled then with electrolyte.At last, if necessary, apply step 50 at gatherer, current collector 28 and 30 is applied in the surface of substrate 22.
In certain embodiments, can put upside down the order of step 46 and 48, before filling the little container of electrode, introduce electrolyte.
The single face microbattery configurations
Fig. 4 is the schematic diagram of the visualization of micro cell 70 according to another embodiment of the present invention.Although above-mentioned micro cell 20 forms, in some cases, go up formation 3D micro cell for single that is desirably in substrate on two surfaces of substrate 22.For example, in some cases, micro cell is used for to one that is formed on substrate 22 lip-deep microcircuit power supply.Under such situation, expectation makes microbattery configurations be suitable for relative, the untapped surface of substrate.Under other situation, the thickness of substrate is too big so that can not realize bilateral structure, the structure as shown in top Fig. 1 and 2.
Fig. 4 shows the grid of the little container that forms in a face of substrate 22.Little container is divided into two staggered groups 24 and 26, is used separately as the anode and the negative electrode of micro cell 70.Any suitable arrangement of being discussed in the description that little container 24 and 26 shape, yardstick and pattern can use as Fig. 1 for how much.
Can use aforesaid any suitable manufacture method to form little container.In certain embodiments, can use two wafers to make the single face micro-container structures.First wafer comprises two groups of little containers of the whole thickness that allows to penetrate wafer.Second wafer that joins first wafer to serves as the solid end of little container.
But in other alternative embodiment, other structure can be used as the electrode of micro cell 70 as staggered comb shape, volute or helical structure.
Little container is separated by the wall 32 that typically is several micron thickness.Use comprises that as known in the art any suitable method of previously described method makes wall porose.As in the two-sided micro cell 20, by making the hole wall ionic conduction to there being hole wall to fill suitable electrolyte.In certain embodiments, also make wall 32 electric insulations by oxidation.
Fig. 5 is the schematic top view of the mask that uses in the manufacturing of micro cell 70 72 according to an embodiment of the invention.Because little container group 24 and 26 all is filled with corresponding anode and cathode material from the same one side of substrate, so need to be used in filling to stop when another organizes little container the mask of one group of little container.The use of mask 72 has prevented the mixing of different electrode materials.Mask 72 comprises the alternately grid of opening 74 and blocking unit 76.The opening of mask 72 and the pattern of blocking unit are designed to the pattern match with the anode and the little container of negative electrode of micro cell 70.
When little container 24 is filled anode material, mask 72 is placed on the surface of substrate 22, makes opening 74 overlap with little container 24.Blocking unit overlaps with little container 26, thereby prevents that anode material from entering this container slightly.Similarly, when when little container 26 is filled cathode material, this mask is placed and makes opening 74 overlap with little container 26, and the little container 24 of blocking unit 76 protections.After placing this mask, use aforesaid any suitable method, to little vessel filling electrode material.
In one embodiment, use two different masks, every group of little container is with a mask.Alternatively, by changing the position of mask, single mask can be used for filling two groups of little containers.In the art, can be well-known with the mechanical translation and the registration arrangement of enough accuracy (typically being 1 micron the order of magnitude) location mask 72.As mentioned above such, the grid of little container can be taked different shapes and configuration.Mask 72 is generated as and employed little container grid coupling.Additionally or alternatively, before filling one group of little container, another is organized little container and is filled with interim material such as polymer.This filling prevents that wrong electrode material from entering little container.This interim filling is removed subsequently.
After anode and negative electrode are filled suitable electrode material, if necessary then can apply one or two current collector (not shown).
Single face micro cell manufacture method
Fig. 6 schematically illustrates the flow chart that is used to make the method for micro cell 70 according to an embodiment of the invention.Form step 80 in the single face chamber, in the single surface of substrate 22, form the pattern of little container.Grid comprises two groups of little containers 24 and 26.Form step 82 in the single face hole, make that wall 32 is porose.In certain embodiments, wall 32 is also oxidized so that their electric insulations.
At anode filling step 84, little container 24 is filled with suitable anode material.As mentioned above, mask 72 is placed on the substrate to prevent that anode material from entering little container 26.Randomly, at cleaning 86, the surface of substrate 22 is cleaned to remove remaining anode material.At negative electrode filling step 88, little container 26 is filled with suitable cathode material then.Mask 72 is placed on the substrate and enters little container 24 so that prevent cathode material.( step 84 and 88 order can be put upside down, and fill negative electrode earlier and recharge anode.) randomly, in planarisation step 90, the surface of substrate 22 is cleaned and is flattened.
Randomly, form step 92, apply or form one or two current collector at current collector.At last, at electrolyte filling step 94, wall 32 is filled with the material of ionic conduction such as above-mentioned demonstration material.In certain embodiments, step 94 can be in step 84 and 88 any or the two before, before the intercalation electrode material, fill electrolyte to porose layer.
Porose separator molding or impression
But in an alternative embodiment (not shown), thin and porose separator film mechanically stable is by in " little molding " or " micro-embossing " suitable depression in the substrate 22.Little molding and micro-embossing are the known technologies that uses in the manufacturing of MEMS device.This technology generations has been replaced little container etch process.But in this alternative technology, perforated film is divided into loculus with depression, to produce little container.Then, to little vessel filling anode material and cathode material.Form where necessary after the current collector, fill the electrolyte of ionic conduction to perforated film.In the art, have pore polymer and the plastic material that can be used to implement pore membrane is known.For example, Heckele and Schomburg are at " Review on Micromolding of Thermoplastic Polymers ", Journal ofMicromechanics and Microengineering, the 14th volume, 2004, described such material in the R1-R14 page or leaf, the document is incorporated herein by reference.Described author has described several thermoplastic polymers that are used for little molding.People such as Song are at " Review of Gel-Type PolymerElectrolytes for Lithium-Ion Batteries ", Journal of Power Sources, the 77th volume, 1999, described in the 183-197 page or leaf based on two kinds in these polymer be the electrolyte of polymethyl methacrylate (PMMA) and polyvinylidene fluoride (PVDF), the document is incorporated herein by reference.
Integrated micro cell and microcircuit
One of application of micro cell is to use micro cell to power to microelectronic circuit, and micro cell and microcircuit are manufactured on the same substrate.
Fig. 7 A is the schematic sectional view of microelectronic component according to an embodiment of the invention.This device comprises the microcircuit 100 that is manufactured on the substrate 22.This microcircuit is by being manufactured on micro cell 20 power supplies of describing among two-sided 3D micro cell on the same substrate such as top Fig. 1 and 2.
Fig. 7 B is the schematic top view of microelectronic component according to another embodiment of the present invention.As among top Fig. 7 A, microcircuit 100 is manufactured on the substrate 22.This microcircuit is by being manufactured on micro cell 70 power supplies of describing among single face micro cell on the same substrate such as top Fig. 4.Fig. 7 B shows a configuration, and wherein this battery and this microcircuit are placed on the same surface of substrate side by side.Alternatively, this micro cell and this microcircuit can be manufactured on the apparent surface of substrate 22, have reduced the gross area of tube core.
The demonstration micro cell
Following example has illustrated and can use the several possible 3D micro cell of disclosed structure and method to implement.
Example 1
Can in silicon substrate, make and comprise lithium-ion anode, hybridized polymer electrolyte and MoS
2The 3D micro cell of negative electrode.Can use technology described in the paper of above-cited Li in the silicon wafer of 500 micron thickness, to form the two-sided cross structure of 50 microns little containers of square 50 x of separating by the wall of 10 micron thickness.This bilateral structure is similar to the structure shown in top Fig. 1.Can be by this structure be immersed the freshly prepd H that comprises
2O
2: made wall porose in 40-60 minute in the etching mixture of ethanol: HF (1:2:4).
Use the traditional casting process that for example comprises that vacuum is filled, fill hybridized polymer electrolyte (HPE) film to porose two-sided cross structure.PVDF-2801 copolymer (Kynar) can be used as adhesive.Pyrogenic silica can be used as the filler of polymer film.The PVDF powder (Aldrich) or among the DMSO dissolves in high-purity cyclopentanone (cyclopentatone).Interpolation pyrogenic silica 130 (Degussa) and propylene carbonate (PC, Merck).At room temperature stir this mixture 24 hours to produce equal chylema.This slurry is used for filling the anode that connects in the silicon substrate and the through hole of the little container of negative electrode.After solvent evaporates fully, the MoS that combines with polystyrene to the little vessel filling of negative electrode
2Powder.Cathode material can be embedded by centrifuge.
Active anode material in this example can comprise lithia graphite or passive metal lithium powder.In order to produce lithia graphite, naphthalene and some lithium paper tinsels of 2.5mmol are placed in the 1-methyl butyl ether of 10mL.Under 25 ℃, dried argon environment, stirred this mixture about 24 hours, to produce lithium-naphthalene-1-methyl butyl ether (Li-NM) complex compound.The formation of Li-NM complex compound can be changed into dark purple solution and confirms from limpid by color.After forming this complex compound, embed the flake graphite and the intercalation that wrap in the gram of 0.2 in the stainless net and begin.Can stir an about week of this solution.
The solid of filtration residue is also used hexane wash.Lentamente distilled water is added in this solution.LiOH with the known volume under the HCl titration liquid phase.From the initial molal quantity of Li-NM, deduct the molal quantity of the LiOH that calculates, with the actual molal quantity of the lithium that provides intercalation.For example by using and being used for embedding the identical method of top cathode material, lithia graphite is mixed with polystyrene and embed in the little container of anode.
In this stage, can connect current collector.Then, to perforated film filling liquid imines lithium (LiImide)-ethylene carbonate (EC): dimethyl carbonate (DMC) 1:1 (v/v) electrolyte.When to polymer film filling liquid electrolyte, produce gel polymer electrolyte.
The expection cut-ff voltage of this battery is the 1.3-2.4 volt.Charge/discharge current density is expected at 10-100 μ A/cm
2In the scope.
Example 2
Can in silicon substrate, make and comprise lithium-ion anode, hybridized polymer electrolyte and MoS
2The single face 3D micro cell of negative electrode.For example, can use technology described in the paper of above-cited Kleimann in the silicon wafer of 400 micron thickness, to form the single face cross structure of the little container of separating by the wall of 10 micron thickness of square 50x50 micron.This single-sided structure is similar to the structure shown in top Fig. 4.As in the top example 1, can be by this structure be immersed the freshly prepd H that comprises
2O
2: made wall porose in 40-60 minute in the etching mixture of ethanol: HF (1:2:4).Filling the negative electrode of alternate group can carry out by shelter relative group when inserting the corresponding electrode material with the little container of anode.
Example 3
Can in silicon substrate, make and comprise lithium-ion anode, hybridized polymer electrolyte and FeS
2The 3D micro cell of negative electrode.Can carry out the preparation substrate and fill HPE in the mode that is similar to top example 1 to porose silicon.Can be by using imines lithium P (EO)
20Polymer dielectric is with FeS
2Powder is dispersed in the acetonitrile (acetonytrile) and prepares based on pyritous cathode material.These components fully can be mixed several hours to produce the slurry of homogeneous.For example use traditional spin coating proceeding, to the little vessel filling cathode material of negative electrode.Anode material can comprise as the lithia graphite described in the top example 1.
The cut-ff voltage of this micro cell is expected in the 1.1-2.1 volt scope.Charge/discharge current density is contemplated to about 40 μ A/cm
2
Example 4
The micro cell of this example is similar to example 1.Yet, in this example, at first cathode material and anode material are embedded in little container.Just for example use vacuum that liquid electrolyte is embedded into having in the hole wall of silicon substrate then.Can carry out embedding from two surfaces of substrate by use pore structure that has along the wall extension between two surfaces of substrate.The cut-ff voltage of micro cell is expected in the 1.3-2.4 volt scope.Charge/discharge current density is contemplated to about 50 μ A/cm
2
Example 5
Can utilize WS as cathode material
2Manufacturing is similar to the micro cell of example 1.
Example 6
Can in silicon substrate, make and comprise lithium-ion anode, liquid or HPE electrolyte and LiCoO
2The micro cell of negative electrode.Dissimilar graphite such as carbonaceous mesophase spherules (MCMB), natural, synthetic or expanded graphite can be used as lithium intercalation material of main part.In one embodiment, making micro cell under the discharge condition fully.The filling of little container is typically according to the method described in the top example 1.The expection cut-ff voltage is in 3.0-4.2 volt scope, and expection charge/discharge current density is at 0.1-10 μ A/cm
2In the scope.
Example 7
Can utilize and comprise Li
1+xMn
2-yO
4The cathode material manufacturing be similar to the micro cell of example 5.
The expection cut-ff voltage of this battery is in 3.5-5.3 volt scope, and charge/discharge current density is expected at 0.1-10 μ A/cm
2In the scope.
Example 8
Can in silicon substrate, make and comprise lithium-ion anode, composite polymer electrolyte (CPE) and MoS
2The 3D micro cell of negative electrode.Can prepare cathode material in the mode that is similar to top example 1.With the EC of P (EO), the 30mg of the imines lithium of 45mg, 300mg and the Al of 100mg
2O
3Preparation comprises the imines lithium
1P (EO)
20EC
19% (v/v) Al
2O
3The 10-20 micron thick film composite polymer electrolyte (CPE) of compound.To have 5 * 10
6The polyethylene P (EO) of mean molecule quantity (Aldrich) about 24 hours of 45-50 ℃ of following vacuumize.Can be by P (EO), imines lithium and the ethylene carbonate (EC) of known quantity is about with having of aequum
The inorganic filler such as the Al of average diameter
2O
3(Buehler) be dispersed in together in the AG acetonitrile and prepare polymer syrup.For guaranteeing to form the suspension of homogeneous, can use the high speed homogenization device.Can stir this suspension about 24 hours.Then the CPE film is cast on the 3D substrate.Can use vacuum and spin coating proceeding to come to through hole filled polymer electrolyte.
The current density of this battery is contemplated to about 50 μ A/cm
2The cut-ff voltage of discharge is contemplated to about 1.1 volts.The cut-ff voltage of charging is contemplated to about 2.2 volts.
Example 9
Can make and comprise lithium anode, liquid or compound HPE and MoS
2The 3D micro cell of negative electrode.Atomic vessel filling molten lithium faces south under about 185 ℃.Can prepare negative electrode and HPE in the mode that is similar to top example 1.The faradic efficiency expection of micro cell is near 100%.
Although method described herein and device are primarily aimed at the manufacturing of 3D micro cell, principle of the present invention also can be used for using little container of interleaved set and porose separator to make other energy storage device such as capacitor.
Therefore it should be understood that the foregoing description is quoted from as example, and the present invention is not limited to the content that specifically illustrates hereinbefore and describe.On the contrary, scope of the present invention comprises above that each combination of features of describing and sub-portfolio the two and those skilled in the art can expect when reading preamble and the not variation of disclosed each feature and modification in the prior art.
Claims (62)
1. electric energy storage device comprises:
Substrate, it is formed so that limit a large amount of little container of being separated by wall electric insulation and ionic conduction; And
Be arranged on more than first anode in first sub described little container of organizing, and be arranged on more than second negative electrode in second sub described little container of organizing, the pattern that described anode and negative electrode are arranged to interlock.
2. according to the device of claim 1, wherein said wall has break-through itself and the hole that forms.
3. according to the device of claim 2, wherein said wall comprises at least a porose separator film that puts on described substrate that uses in little moulding technology and the micro-embossing technology.
4. according to the device of claim 2, at least some in the wherein said hole are filled with electrolyte.
5. according to the device of claim 4, wherein said electrolyte comprises at least a in liquid electrolyte, hybridized polymer electrolyte (HPE) and the composite polymer electrolyte (CPE).
6. according to the device of claim 2, at least a formation in electrochemical etching process and the chemical etching process used in wherein said hole.
7. according to each the device among the claim 1-6, wherein said substrate comprises at least a in metal, sodium ion conductor and the lithium ion conductor of silicon, GaAs, carborundum, ceramic material, thermoelasticity polymer, thermoplastic polymer, surface oxidation.
8. according to each the device among the claim 1-6, wherein said electric energy storage device comprises one of lithium micro cell and lithium ion micro battery.
9. according to each the device among the claim 1-6, described little containers of the wherein said first and second son groups form in the single surface of described substrate.
10. according to each the device among the claim 1-6, little containers of the wherein said first and second son groups form in the corresponding apparent surface of described substrate.
11. according to each the device among the claim 1-6, wherein said substrate comprises the middle wafer of the little containers that wherein are formed with the described first and second son groups and is coupled to the surface of described middle wafer so that form at least one face wafer of bottom surface of little container of at least one described son group.
12. according to each the device among the claim 1-6, wherein said wall is oxidized at least in part.
13. each the device according among the claim 1-6 comprises at least one at least a current collector that is coupled in described a plurality of anode and the described a plurality of negative electrode.
14. according to the device of claim 13, wherein said at least one current collector comprises one of metal forming and depositing metal layers.
15. according to each the device among the claim 1-6, wherein said anode and negative electrode use adhesion technique, vacuum-assisted to embed at least a deposition the in technology and the thick film depositing operation.
16. according to each the device among the claim 1-6, that wherein said little container has is square, at least a in triangle, hexagon and the circle.
17. according to each the device among the claim 1-6, wherein said little container has the degree of depth diameter ratio greater than 1.
18. according to each the device among the claim 1-6, at least a in wherein said a large amount of little container arrangement squarelys, triangle and the hexagon lattice.
19. according to each the device among the claim 1-6, wherein said a large amount of little containers use etch processs to form.
20. according to each the device among the claim 1-6, wherein said anode comprises lithiated intercalation compound, described lithiated intercalation compound comprises at least a in carbon, graphite, lithium alloy and the lithium.
21. according to each the device among the claim 1-6, wherein said negative electrode comprises MoS
2, FeS
2, WS
2, LiCoO
2, LiNiO
2And Li
1+xMn
2-yO
4At least a in the material.
22. a microelectronic component comprises:
Substrate;
Be arranged on the microcircuit on the described substrate; And
Be arranged in the described substrate and be coupled so that the electric energy storage device of electrical power to be provided to described microcircuit, described memory device comprises:
Be formed on the little container of a large amount of three-dimensionals in the described substrate, separate by wall electric insulation and ionic conduction; And
Be arranged on a plurality of anodes in first sub described little container of organizing, and be arranged on a plurality of negative electrodes in second sub described little container of organizing, the pattern that described anode and negative electrode are arranged to interlock.
23. according to the device of claim 22, wherein said wall has break-through itself and the hole that forms.
24. according to the device of claim 23, wherein said wall comprises at least a porose separator film that puts on described substrate that uses in little moulding technology and the micro-embossing technology.
25. according to the device of claim 23, at least some in the wherein said hole are filled with electrolyte.
26. according to the device of claim 25, wherein said electrolyte comprises at least a in liquid electrolyte, hybridized polymer electrolyte (HPE) and the composite polymer electrolyte (CPE).
27. according to the device of claim 23, at least a formation in electrochemical etching process and the chemical etching process used in wherein said hole.
28. according to each the device among the claim 22-27, wherein said substrate comprises at least a in metal, sodium ion conductor and the lithium ion conductor of silicon, GaAs, carborundum, ceramic material, thermoelasticity polymer, thermoplastic polymer, surface oxidation.
29. according to each the device among the claim 22-27, wherein said electric energy storage device comprises one of lithium micro cell and lithium ion micro battery.
30. according to each the device among the claim 22-27, described little containers of the wherein said first and second son groups form in the single surface of described substrate.
31. according to each the device among the claim 22-27, little containers of the wherein said first and second son groups form in the corresponding apparent surface of described substrate.
32. according to each the device among the claim 22-27, wherein said substrate comprises the middle wafer of the little containers that wherein are formed with the described first and second son groups and is coupled to the surface of described middle wafer so that form at least one face wafer of bottom surface of little container of at least one described son group.
33. according to each the device among the claim 22-27, wherein said wall is oxidized at least in part.
34. each the device according among the claim 22-27 comprises at least one at least a current collector that is coupled in described a plurality of anode and the described a plurality of negative electrode.
35. according to the device of claim 34, wherein said at least one current collector comprises at least a in metal forming and the depositing metal layers.
36. according to each the device among the claim 22-27, wherein said anode and negative electrode use adhesion technique, vacuum-assisted to embed at least a deposition the in technology and the thick film depositing operation.
37. according to each the device among the claim 22-27, that wherein said little container has is square, at least a in triangle, hexagon and the circle.
38. according to each the device among the claim 22-27, wherein said little container has the degree of depth diameter ratio greater than 1.
39. according to each the device among the claim 22-27, at least a in wherein said a large amount of little container arrangement squarelys, triangle and the hexagon lattice.
40. according to each the device among the claim 22-27, wherein said a large amount of little containers use etch processs to form.
41. according to each the device among the claim 22-27, wherein said anode comprises lithiated intercalation compound, described lithiated intercalation compound comprises at least a in carbon, graphite, lithium alloy and the lithium.
42. according to each the device among the claim 22-27, wherein said negative electrode comprises MoS
2, FeS
2, WS
2, LiCoO
2, LiNiO
2And Li
1+xMn
2-yO
4At least a in the material.
43. a method that is used to construct electric energy storage device comprises:
In substrate, form a large amount of three-dimensional little containers, make described little container separate by wall electric insulation and ionic conduction; And
More than first anode is arranged in described little container of the first son group, and more than second negative electrode is arranged in described little container of the second son group pattern that described anode and negative electrode are arranged to interlock.
44., wherein form described a large amount of little container and comprise the hole that forms the described partition wall of break-through according to the method for claim 43.
45. according to the method for claim 44, wherein form described a large amount of little container and comprise following at least a: the porose separator film of little molding and micro-embossing in described substrate.
46., wherein form described a large amount of little container and comprise that in described hole at least some fill electrolyte according to the method for claim 44.
47. according to the method for claim 46, wherein said electrolyte comprises at least a in liquid electrolyte, hybridized polymer electrolyte (HPE) and the composite polymer electrolyte (CPE).
48., wherein form described hole and comprise and use at least a in electrochemical etching process and the chemical etching process to come the described hole of etching according to the method for claim 44.
49. according to each the method among the claim 43-48, wherein said substrate comprises at least a in metal, sodium ion conductor and the lithium ion conductor of silicon, GaAs, carborundum, ceramic material, thermoelasticity polymer, thermoplastic polymer, surface oxidation.
50. according to each the method among the claim 43-48, wherein said electric energy storage device comprises one of lithium micro cell and lithium ion micro battery.
51., wherein form the described little containers that form the described first and second son groups in the single surface that described a large amount of little container is included in described substrate according to each the method among the claim 43-48.
52., wherein form the described little containers that form the described first and second son groups among the corresponding apparent surface that described a large amount of little container is included in described substrate according to each the method among the claim 43-48.
53. according to each the method among the claim 43-48, wherein form described a large amount of little container and be included in the described little container of formation in the middle wafer, and at least one face wafer is coupled to the surface of described middle wafer so that form the bottom surface of little container of at least one described son group.
54. each the method according among the claim 43-48 wherein forms at least a portion that described a large amount of little container comprises the described wall of oxidation.
55., comprise at least one current collector be coupled at least a in described a plurality of anode and the described a plurality of negative electrode according to each the method among the claim 43-48.
56. according to the method for claim 55, described at least one current collector that wherein is coupled comprises and applies at least a in metal forming and the depositing metal layers.
57., wherein deposit described anode and negative electrode and comprise that applying adhesion technique, vacuum-assisted embeds at least a in technology, thin film deposition processes and the thick film depositing operation according to each the method among the claim 43-48.
58., wherein form described a large amount of described little container and comprise and form at least a in square, triangle, hexagon and the circular little container according to each the method among the claim 43-48.
59., wherein form described a large amount of little container and comprise and form the little container that has greater than 1 degree of depth diameter ratio according to each the method among the claim 43-48.
60., wherein form described a large amount of little container and comprise at least a with in described little container arrangement squarely, triangle and the hexagon lattice according to each the method among the claim 43-48.
61., wherein form described a large amount of little container and comprise and apply etch process according to each the method among the claim 43-48.
62., described anode and negative electrode wherein are set are included in and stop described more than first and second another kinds in little containers when a kind of in described more than first and second little containers fills electrode material according to each the method among the claim 43-48.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US56620504P | 2004-04-27 | 2004-04-27 | |
| US60/566,205 | 2004-04-27 | ||
| US60/590,833 | 2004-07-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101427415A true CN101427415A (en) | 2009-05-06 |
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| CN104584159A (en) * | 2012-09-28 | 2015-04-29 | 英特尔公司 | Nanomachined structures for porous electrochemical capacitors |
| CN104662714A (en) * | 2012-08-16 | 2015-05-27 | 艾诺维克斯公司 | Electrode structures for three-dimensional batteries |
| US9136794B2 (en) | 2011-06-22 | 2015-09-15 | Research Triangle Institute, International | Bipolar microelectronic device |
| CN105308772A (en) * | 2013-03-15 | 2016-02-03 | 艾诺维克斯公司 | Separators for three-dimensional batteries |
| CN105390661A (en) * | 2014-08-21 | 2016-03-09 | 庄臣及庄臣视力保护公司 | methods for manufacturing biocompatible cathode slurry for use in biocompatible batteries |
| CN105393396A (en) * | 2013-07-03 | 2016-03-09 | 加州理工学院 | Carbon nanotubes - graphene hybrid structures for separator free silicon - sulfur batteries |
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| CN106920918A (en) * | 2015-10-12 | 2017-07-04 | 三星电子株式会社 | Three-diemsnional electrode structure and the battery with electrode structure |
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| CN109638272A (en) * | 2011-11-21 | 2019-04-16 | 英飞凌科技股份有限公司 | Lithium battery, the method for manufacturing lithium battery, integrated circuit and the method for manufacturing integrated circuit |
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| CN105308772A (en) * | 2013-03-15 | 2016-02-03 | 艾诺维克斯公司 | Separators for three-dimensional batteries |
| CN105308772B (en) * | 2013-03-15 | 2018-11-16 | 艾诺维克斯公司 | Diaphragm for three-dimensional batteries |
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| CN106794985B (en) * | 2014-06-11 | 2019-03-12 | 韩国标准科学研究院 | The large area manufacturing method of the GaAs conductor nano tube/linear array of vertical alignment |
| CN106794985A (en) * | 2014-06-11 | 2017-05-31 | 韩国标准科学研究院 | The large area manufacture method of the GaAs conductor nano tube/linear arrays of vertical alignment |
| CN105390661A (en) * | 2014-08-21 | 2016-03-09 | 庄臣及庄臣视力保护公司 | methods for manufacturing biocompatible cathode slurry for use in biocompatible batteries |
| CN107851831A (en) * | 2015-08-07 | 2018-03-27 | 国际商业机器公司 | For narrow, low profile micro cell total silicon it is hermetically sealed and processing |
| CN106920918A (en) * | 2015-10-12 | 2017-07-04 | 三星电子株式会社 | Three-diemsnional electrode structure and the battery with electrode structure |
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