CN101589230A - Electrochemical actuator - Google Patents

Electrochemical actuator Download PDF

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Publication number
CN101589230A
CN101589230A CNA2007800353514A CN200780035351A CN101589230A CN 101589230 A CN101589230 A CN 101589230A CN A2007800353514 A CNA2007800353514 A CN A2007800353514A CN 200780035351 A CN200780035351 A CN 200780035351A CN 101589230 A CN101589230 A CN 101589230A
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China
Prior art keywords
exciter system
actuator
exciter
displacement
positive electrode
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CNA2007800353514A
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CN101589230B (en
Inventor
姜一民
迈克尔·J·西马
陈利明
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Massachusetts Institute of Technology
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Massachusetts Institute of Technology
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Priority claimed from US11/796,138 external-priority patent/US7994686B2/en
Application filed by Massachusetts Institute of Technology filed Critical Massachusetts Institute of Technology
Priority claimed from PCT/US2007/016849 external-priority patent/WO2008094196A2/en
Publication of CN101589230A publication Critical patent/CN101589230A/en
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Publication of CN101589230B publication Critical patent/CN101589230B/en
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Abstract

The present invention provides systems, devices, and related methods, involving electrochemical actuation. In some cases, application of a voltage or current to a system or device of the invention may generate a volumetric or dimensional change, which may produce mechanical work. For example, at least a portion of the system may be constructed and arranged to be displaced from a first orientation to a second orientation. Systems such as these may be useful in various applications, including pumps (e.g., infusion pumps) and drug delivery devices, for example.

Description

Electrochemical actuator
Statement about federal sponsored research or exploitation
The present invention finishes under the support of the government contract W911W6-05-C-0013 that US military is authorized.Government has some right of the present invention.
Technical field
The invention provides the system, equipment and the method that relate to the electrochemistry excitation.
Background technique
Excitation relate generally to a kind of can mechanical energy be adjusted or the mechanism of the part of movable object or object by energy (for example electric energy, chemical energy etc.) is converted to.Actuator can be classified by the transformation of energy mode.For example, electrostatic actuator converts electrostatic force to mechanical force.
Piezoelectric excitation provides high bandwidth and excitation power (authority) but provide low stress (more much smaller than 1% usually) and require high energizing voltage.But marmem (SMA), magnetostrictor and ferromagnetic shape memory alloys (FSMA) newly developed can have bigger stress produce more slow-response, and this has limited their applicability.(piezoelectricity FSMA) also often has low organism stress to cause the incentive mechanism of moving in the territory based on the field.Above-mentioned motivational techniques are based on the use that the quality factor based on weight is had the high density active material (based on oxide, the metal alloy of lead) of negative effect.Therefore need a kind of technology that high excitation energy density, high excitation power (stress), big free strain can be provided and dedicated bandwidth is arranged.
Before described and used electrochemical some motivational techniques, the excitation material that wherein bears load be in gas phase or liquid phase and can be expected to have low elastic modulus and thereby compare with mode of the present invention, have lower excitation energy density and excitation stress.Although observe displacement, do not confirm mechanical work as yet.
Thereby need improved method and apparatus.
Summary of the invention
The present invention relates to be constructed and arranged to be displaced to the exciter system of second orientation from first orientation, comprise: at least one electrochemical cell that comprises negative electrode and positive electrode, wherein one or two in negative electrode and the positive electrode are actuators and comprise first portion and second portion, and wherein when charging and/or discharge, material embeds with the degree different with second portion, take off embedding, alloyage in, oxidation, the dimensional changes that reduction or plating first portion and experience produce with respect to second portion, cause the differential strain between first portion and second portion and cause the displacement of at least a portion of actuator to actuator thus, the displacement of actuator is done mechanical work and be need not to be coupled to the structure of doing described merit.
The present invention also relates to be constructed and arranged to be displaced to the exciter system of second orientation from first orientation, comprise: at least one electrochemical cell that comprises negative electrode and positive electrode, wherein one or two in negative electrode and the positive electrode are actuators and comprise first portion and second portion, and wherein when charging and/or discharge, material embeds with the degree different with second portion, take off embedding or alloyage in first portion and the dimensional changes that produces with respect to second portion of experience, cause the differential strain between first portion and second portion and cause the displacement of at least a portion of actuator to actuator thus, the displacement of actuator is done mechanical work and be need not to be coupled to the structure of doing described merit.
The present invention also relates to be constructed and arranged to be displaced to the exciter system of second orientation from first orientation, comprise: at least one electrochemical cell that comprises negative electrode and positive electrode, wherein one or two in negative electrode and the positive electrode are actuators and comprise first portion and second portion, and the dimensional changes that wherein first portion's experience produces with respect to second portion when the oxidation of the degree different with second portion of first portion and/or reduction, cause the differential strain between first portion and second portion and cause the displacement of at least a portion of actuator to actuator thus, the displacement of actuator is done mechanical work and be need not to be coupled to the structure of doing described merit.
The present invention also relates to be constructed and arranged to be displaced to the exciter system of second orientation from first orientation, comprise: at least one electrochemical cell that comprises negative electrode and positive electrode, wherein one or two in negative electrode and the positive electrode are actuators and comprise first portion and second portion, and wherein when charging and/or discharge, material with the degree electrochemical deposition different with second portion in first portion and the dimensional changes that produces with respect to second portion of experience, cause the differential strain between first portion and second portion and cause the displacement of at least a portion of actuator to actuator thus, the displacement of actuator is done mechanical work and be need not to be coupled to the structure of doing described merit.
The present invention also relates to actuator equipment, comprise: at least one electrochemical cell, comprise negative electrode, positive electrode and material, material can embed with the degree different with the second portion of electrochemical cell, take off embedding, alloyage in, oxidation, the first portion of reduction or plating electrochemical cell, thereby first portion and/or second portion cause the actuator displacement of doing mechanical work in when discharge experience dimensional changes thus, wherein electrochemical cell be constructed and arranged to charge during fabrication and after using partly discharge or after discharge first not further the charging.
The present invention also relates to infusion pump, comprising: at least one electrochemical cell, comprise negative electrode, positive electrode and embedding material, wherein negative electrode and/positive electrode in charging and/or when discharge experience dimensional changes so that cause fluid to be injected in the health.
The present invention also relates to be constructed and arranged to be used for the actuator of physiology facility (physiological setting), this actuator comprises: the first portion adjacent with second portion, wherein first portion experiences dimensional changes when being exposed to the physiological fluid that comprises material, and wherein because the dimensional changes that electrochemistry embed, material the oxidation/reduction of taking off embedding or first portion from first portion cause actuator of the material that is caused with contacting of material in the first portion.
The present invention also relates to be used for the electrochemical actuator of medicament administration to health, this electrochemical actuator comprises: at least one negative electrode; At least one positive electrode; And material, the voltage or the electric current that are applied of electrochemical actuator wherein, thus voltage or electric current apply or it stops to apply and comprises that thereby the embedding of material at least one electrode of electrochemical actuator causes the volume or the dimensional changes of electrochemical actuator, and wherein volume or dimensional changes cause medicament administration in health.
Description of drawings
Fig. 1 shows (a) example of exciter system according to an embodiment of the invention under the situation that under the situation that does not apply voltage or electric current and (b) is applying voltage or electric current.
Fig. 2 shows (a) is used for allotting at the adjacent fluid container exciter system of fluid according to an embodiment of the invention under the situation that under the situation that does not apply voltage or electric current and (b) is applying voltage or electric current example.
Fig. 3 A-C shows the exciter system of the hardness with the displacement speed that is enough to influence actuator and length of stroke.
Fig. 4 shows the example of exciter system according to an embodiment of the invention.
Fig. 5 shows another example of exciter system according to an embodiment of the invention.
Fig. 6 shows another example of exciter system according to an embodiment of the invention.
Fig. 7 shows another example of exciter system according to an embodiment of the invention.
Fig. 8 A shows and comprises the first portion that formed by different materials and the exciter system of second portion.
The first portion that formed by different materials comprising after Fig. 8 B shows in immersing water and the exciter system of second portion.
Fig. 9 shows and comprises (a) Zn form and (b) convert Zn (OH) at Zn 2Thereby the exciter system of the Zn layer the during excitation of realization exciter system.
Figure 10 shows and comprises (a) Zn form and (b) convert Zn (OH) at Zn 2Thereby another exciter system of the Zn layer the during excitation of realization exciter system.
Figure 11 shows the exciter system that comprises the lithium ion coupling, and wherein actuator (a) was in zero strain and (b) experience excitation after being exposed to electrolyte before being exposed to electrolyte.
Figure 12 shows lithium ion coupling or the coupling of nickel metal-hydrogen thing that (a) assembles during spontaneous discharge after under charged state and (b) coming across in the electrolyte.
Figure 13 shows (a) and is being exposed to before the electrolyte and (b) exciter system that comprises two different pieces when being exposed to electrolyte, wherein this system's experience bending or extruding.
Figure 14 shows (a) and is being exposed to before the electrolyte and (b) exciter system that comprises two different pieces when being exposed to electrolyte, the wherein crooked or unlatching of this system's experience structure.
Figure 15 shows (a) and is being exposed to before the material and (b) exciter system with hinging structure when being exposed to material, wherein this system's experience excitation.
Figure 16 shows the schematic design of confession driving type electrochemical pump.
Figure 17 shows the plotted curve of the displacement reduced time curve of confession driving type deformation (morphing) actuator with built-in strain amplification.
Figure 18 shows the plotted curve by the shifted curve of the electrochemistry deformation actuator of 20% dutycycle control.
Constant current (galvanostatic) discharge that Figure 19 shows piezoelectric bimorph (bimorph) electrochemical actuator that utilizes the thick tinfoil paper of 0.10mm that is adhered to Copper Foil distributes.
The constant-current discharge that Figure 20 shows the electrochemistry piezoelectric bimorph battery that utilizes the thick tinfoil paper of 0.05mm that is adhered to copper distributes.
When taking into consideration with accompanying drawing, others of the present invention, embodiment and feature will become clear from the following specifically describes.Accompanying drawing is schematically and not to plan to draw in proportion.For the sake of clarity, do not have each parts of mark in every width of cloth figure, and each parts of various embodiments of the present invention shown in the figure for understanding the present invention, permission those of ordinary skills are not all to be essential yet.Here all patent applications and the patent quoted are incorporated into this by reference and fully.Be as the criterion with this specification that comprises definition having under the situation of conflict.
Embodiment
The present invention mainly provides system and equipment and the method that relates to the electrochemistry excitation.
In some cases, the invention provides system's (for example exciter system) that can comprise at least one parts, wherein apply volume or the dimensional changes that voltage or electric current can cause these parts to these parts.In some cases, this volume or dimensional changes can produce mechanical work.In certain embodiments, at least a portion of this system can be constructed and arranged to be displaced to another orientation from an orientation.This system also can with another structure connection, thereby the volume of this system or dimensional changes can influence orientation, shape, size, volume or the further feature of this structure.System such as these systems is useful in the various application that for example comprise the pump (for example infusion pump) and the equipment that makes up a prescription.
In certain embodiments, system can comprise in the operating process of this system and the related material of one or more parts (for example electrode).Such as the material of ion can with one or more partial reaction of equipment.Some embodiments of the present invention can relate to the reaction of one or more electrode of material and equipment, and this reaction generates volume or the dimensional changes in the electrode.As used herein, " volume or dimensional changes " is meant expansion, contraction and/or other displacement of system or system's part.Volume or dimensional changes can comprise expansion, contraction, stretching, shortening, distortion, bending, shearing or other displacement of one or more quantity on one or more size.In some cases, volume or dimensional changes can be isotropic.In some cases, volume or dimensional changes can be anisotropic.Such variation can be used for mechanical work and promptly encourage.System can experience the volume or the dimensional changes that can be suitable for concrete any scope of using.For example, thus exciter system can be oriented to contact with fluid container and can expand and the contraction system as coming work in order to the pumping equipment of allotting fluid from fluid container.
In certain embodiments, the invention provides a kind of electrochemical actuator that comprises at least one electrochemical cell, this electrochemical cell comprises anode, negative electrode and material (for example lithium ion), and wherein electrochemical cell experiences volume or dimensional changes when applying voltage or electric current.In certain embodiments, electrochemical actuator also comprises following structure, and this structure comprises and for example is constructed and arranged to volume or dimensional changes by one or more electrochemical cell are displaced to second orientation from first orientation at least one part.When this transposition of partial of this structure, produce mechanical work.As hereinafter more specifically discussing, can encourage various systems by the volume or the dimensional changes of electrochemical cell.
As used herein, " be constructed and arranged to be shifted " exciter system and be meant following exciter system, the orientation that this exciter system can be changed this system i.e. displacement (for example excitation) by this system's at least a portion, this under the predetermined purpose of this system, influence this system or with the performance of the structure of this system relationship.Those skilled in the art will appreciate that the implication of this term.In an example embodiment, exciter system can be positioned near the structure such as fluid container or reservoir, and wherein exciter system is constructed and arranged to make position, shape, size or the further feature of the motion of this system or other shift affects fluid container with from the fluid container pumping or allot fluid.
Advantageously, can by for example crooked, extruding, distortion, stretch and a part that the whole bag of tricks that shrinks come realization system or system from first displacement that is directed to second orientation, as described in hereinafter complete, this can form by the material of change system, configuration, the voltage that applies or electric current, dutycycle or other operating parameter of one or more electrochemical cell of system are changed.Under the situation of system and structure connection, can be for example by changing the location of electrochemical cell for structure to be shifted, structure shape, between battery and structure, form the displacement of the system of change by the material of any material of operative relationship and/or parts.In some cases, this displacement can comprise the linear displacement of the part of system.In some cases, this displacement can comprise the extruding of the part of system.For example, this system can comprise the plate-like part that can have the first plane orientation, and this plate-like part can be displaced to hemispheric second orientation of non-planar surface via extruding when excitation.
In addition, the displacement degree of the part of structure or structure can be at specifically being used for customization.For example in certain embodiments, electrochemical cell of the present invention can cause structure or structure a part for example greater than 5 degree, greater than 10 degree, greater than 20 degree, greater than 30 degree or greater than the displacements of 40 degree.Decide on concrete application, in other embodiments, electrochemical cell for example can cause greater than 1cm, greater than 10cm, greater than 20cm, greater than 50cm or greater than the displacement of 1m.
In some cases, electrochemical cell the volume in charging or when discharge or dimensional shift can be used for carrying out system, system a part or adjacent with system or otherwise with the physical displacement of the structure of system relationship.Volume or dimensional shift (net volume variation) can be in charging and/or discharge process for just, zero or bear.In some cases, can according to the composition or the state of charge of the constituent material of battery, be used for the molecular volume of constituent material table data, easily calculate net volume according to the Volume Changes that occurs at each constituent material and change or on electrochemical cell, directly measure net volume and change.
Can encourage several different structures by electrochemical cell described herein.In certain embodiments, the invention provides the exciter system (for example electrochemical actuator) that is constructed and arranged to when charging or discharge, be displaced to second orientation from first orientation.In some cases, exciter system can be constructed and arranged to be modified to second shape from first shape when charging or discharge.In some cases, the displacement of actuator generation can have the symbol (for example positive and negative) identical with volume that occurs or dimensional changes in electrochemical cell.For example, just be shifted (for example increase of linear dimension) can change (for example expanding) corresponding to the positive net volume of electrochemical cell itself, and negative displacement (minimizing of linear dimension) can change (contraction) corresponding to the negative net volume of electrochemical cell itself.In some cases, the displacement of actuator generation can not have and volume that occurs in electrochemical cell or the identical symbol of dimensional changes.For example, as described in the example, just be shifted and producing by the electrochemical cell of the clean negative Volume Changes of experience.That is to say, the displacement of actuator can with the volume or the dimensional changes decoupling of electrochemical cell.
Exciter system can comprise at least one electrochemical cell, and this electrochemical cell comprises negative electrode and positive electrode.Exciter system also can for example comprise can serial or being greater than or equal to 2, being greater than or equal to 4, being greater than or equal to 10, being greater than or equal to 20 or be greater than or equal to 50 electrochemical cell of parallel operation.In certain embodiments, a plurality of electrochemical cells can engage, still can pile up so that increase integral shift and keep low integral device voltage by electricity in parallel.In certain embodiments, the net volume of electrochemical actuator changes and to be used for carrying out physical displacement, and this physical displacement causes including but not limited to comprising that the pumping of fluid of medicine or allocation or fluid administration are in health.
In certain embodiments, one or two in negative electrode and the positive electrode can be actuators and can change shape and/or be displaced to second orientation from first orientation when the charging of electrochemical cell or discharge.In some cases, exciter system can comprise alternatively the first portion and the second portion of electric connection mutually, and wherein first portion and second portion experience differential volume or dimensional changes or differential displacement when charging or discharge.For example, one or more electrode of experience change in shape or displacement can comprise first portion, and this first portion applies mechanical constraint to the second portion of the displacement that can help one or more electrode.In certain embodiments, first portion and second portion electric connection.In certain embodiments, first portion does not have and the second portion electric connection.
In some instances, first portion and second portion (for example correspond respectively to the positive electrode and the negative electrode of electrochemical cell or vice versa) can be the forms of layer, and it is adjacent or can isolate mutually by other material in other embodiments that these layers can be oriented to be right after mutually ground.In certain embodiments, first portion and second portion are bonding mutually.In certain embodiments, first portion and second portion are systems with the zones of different of a part, and one of them part experiences volume or the dimensional changes that electrochemistry greatly causes than another part.
In certain embodiments, in charging and/or when discharge, material (for example embedding (intercalation) material, electronics or plating material) with the degree different (for example different dynamics, concentration, strain, volume, change in shape or other variation) with second portion embed, take off embedding, alloyage in, oxidation, reduction, plating in or plating first portion.For example, but material can embed, take off embedding or alloyage in, oxidation, reduction or plating first portion second portion not so basically, and perhaps the degree of second portion is less than first portion.Because the differential embedding of first portion, take off embedding or alloyage, oxidation, reduction or plating different with the degree of second portion, so first portion can experience the dimensional changes that is caused, such as the increase of volume or linear dimension or the variation of minimizing or aspect ratio.Because the degree that second portion do not embed, takes off embedding or alloyage, oxidation, reduction or plating material or embedding, take off embedding or alloyage, oxidation, reduction or plating material is less than first portion, changes or can not experience the dimensional changes identical with first portion so second portion can not experience actual size.The result causes differential strain (for example relative strain) between first portion and second portion, this can cause the displacement (for example inner deflection or bending) of actuator at least a portion.The displacement of the actuator that is caused can be done mechanical work and need not to be coupled to the structure of doing described merit.In certain embodiments of the present invention, the excitation of actuator can comprise from the displacement of first expansion that is directed to second orientation, contraction, bending, arc song (bowing), extruding, folding, scrolling or other form.
In some cases, exciter system itself can be that structure is dwindled in strain amplification or strain.For example, exciter system or its part (for example electrode) can be amplified any displacement that for example produces owing to the Volume Changes that occurs in system or system's part.In certain embodiments, exciter system or equipment can amplify the displacement that the volume-variation owing to electrode produces.The displacement of actuator can be used for the power that applies or carry out the displacement of the structure adjacent with actuator.
For any exciter system described herein and equipment (for example pump), although the displacement of exciter system or its part can be used for carrying out mechanical work and need not to be coupled to the structure of doing described merit, exciter system can be coupled to the structure (for example structure is dwindled in strain structure for amplifying, strain) of doing mechanical work in some cases.In some cases, exciter system can be coupled to the structure of doing mechanical work.
The example of exciter system has been shown in the illustrated embodiment in Figure 1A.As shown in this example embodiment, exciter system 110 comprises the negative electrode 112 with positive electrode 114 electric connections.Positive electrode 114 can comprise first portion 116 and second portion 118.In certain embodiments, part 116 and 118 is formed by different materials.Part 116 also can have different electromotive forces with 118.For example, part 116 can comprise the material that can embed, take off embedding, alloyage, oxidation, reduction or plating material with the degree different with part 118.Part 118 can be formed by the material that can not embed, take off embedding or alloyage, oxidation, reduction or plating material basically.In some cases, part 116 can by comprise in aluminium, antimony, bismuth, carbon, gallium, silicon, silver, tin, the zinc one or more material or other material that can when the embedding of lithium or alloyage or chemical combination form, expand form.In a specific embodiment, part 116 is formed by the material that comprises the aluminium that can expand when lithium embeds.Part 118 can be formed by copper, because copper can not embed lithium or and lithium alloyage basically.In some instances, part 118 can be served as the positive electrode current collector and can be extended for example to form joint or current feed beyond electrochemical cell.In other embodiments, part 118 can join joint or the current feed that extends to beyond battery.Negative electrode 112 also can comprise current collector.Exciter system 110 can comprise isolator 122.This isolator can for example be porose isolator film such as glass fiber cloth or the pore polymer isolator is arranged.Also can use the isolator of other type, such as those isolators that in the structure of lithium ion battery, use.Actuator also can comprise it can being the electrolyte 124 of fluid, solid or gel form.This electrolyte can comprise electroactive substance, such as the material that is used for forming negative electrode.Exciter system 110 can be sealed in the cover 126 such as polymer encapsulated.
As shown in the embodiment as shown in Figure 1B, electrochemical cell can have voltage 132, thereby when forming closed circuit between negative electrode and positive electrode, electric current can flow between two electrodes through external circuit.If negative electrode 112 is metal lithium electrodes and electrolyte comprises lithium ion, then the lithium ion electric current can flow to electrode 114 from electrode 112 in inside.The embedding of the lithium of part 116 can cause the dimensional changes such as volumetric expansion.In some instances, this volumetric expansion is compared with initial volume and can be reached at least 25%, at least 50%, at least 75%, at least 100%, at least 150%, at least 200%, at least 250% or at least 300%.High volumetric expansion can for example occur when part 116 is saturated by lithium.Because the embedding of lithium and volume increases, the part 118 that part 116 can be incorporated into may be because minimum or do not have the embedding of lithium and do not expand basically along with part 116.Therefore part 116 provides mechanical constraint.This differential strain between two parts causes positive electrode 114 experience bending or deflections.Because the dimensional changes or the displacement of positive electrode, exciter system 110 can be displaced to second orientation from first orientation.No matter because from negative electrode loss lithium metal and form the volume of the electrochemical cell that compound or lithium alloy caused that embeds lithium or dimensional changes (for example net volume variation) at positive electrode and just be, be zero or negatively this displacement can occur.In some cases, actuator displacement can occurring for positive volume or dimensional changes (for example net volume variation) along with exciter system or its part.What in some cases, actuator displacement can be along with exciter system or its part is that zero volume or dimensional changes (for example net volume variation) occur.In some cases, the actuator displacement can occur along with the volume or the dimensional changes (for example net volume variation) for negative of exciter system or its part.
As used herein, " differential strain " between two parts is meant response (for example excitation) difference of each independent sector when voltage or electric current are applied to two parts.That is to say, system described here can comprise as lower member, these parts comprise the second portion of first portion and related with first portion (for example can contact first portion, can be integrally connected to first portion), wherein substantially under the same terms, first portion can experience volume or dimensional changes and second portion does not experience volume or dimensional changes, and this produces strain between first portion and second portion.Differential strain can cause these parts or its part to be displaced to second orientation from first orientation.The differential embedding of one or more part that in some cases, can be by material and exciter system, take off embedding, alloyage, oxidation, reduction or plating and produce differential strain.
For example, can by some means (Figure 1A) realize part 116 with respect to the differential embedding of part 118, take off embedding, alloyage, oxidation, reduction or plating.In one embodiment, as mentioned above, part 116 can be formed by the material different with part 118, and wherein one of material embeds, takes off embedding, alloyage, oxidation, reduction or plating material basically, and second portion is with littler degree and substance reaction.In another embodiment, part 116 and part 118 can be formed by same material.For example, part 116 and part 118 can be formed and can be intensive basically or porose by same material, such as the powder or the foaming structure of compacting or sintering.In some cases, in order when electrochemical cell is operated, to produce differential strain, part 116 or 118 can have adequate thickness, makes may gradient composition occur owing to limited ion transmits in the operating process of electrochemical cell, and this produces differential strain.In certain embodiments, the zone of a part or a part can preferentially be exposed to material with respect to the zone of second portion or second portion.In other example, to compare with the part of not sheltering or shielding, part is with respect to the shielding of another part or shelter the part that can realize sheltering or shielding still less or bigger embedding, take off embedding or alloyage.This can be for example by the blocking layer of surface treatment or deposition, by the lamination of barrier material or chemistry or heat treatment masked/surface of the part of shielding realizes, thereby help or forbid with the embedding of this part, take off embedding, alloyage, oxidation, reduction or plating.The blocking layer can be formed by any suitable material that can comprise polymer, metal or pottery.In some cases, the effect of another function such as current collector also can be played in the blocking layer in electrochemical cell.The blocking layer can deposit on the surface in certain embodiments equably.In other cases, the blocking layer can form to be formed and/or size gradient, thus have only some part on surface preferentially help or forbid the surface embedding, take off embedding, alloyage, oxidation, reduction or plating.Can be linearity, step, other gradient of exponential sum.In certain embodiments, the porosity in passing part 116 or 118 that comprises preparation dense list surface layer changes and can be used for auxiliary establishing ion concentration gradient and differential strain.The present invention also conceive material with in various degree and other method of first portion reaction so that cause differential strain between first portion and second portion.As hereinafter more specifically as described in, in certain embodiments, the deflection of electrode or the crooked displacement that is used for applying power or realizes useful function.
Here among several embodiments of Miao Shuing, first portion and second portion can be described as being formed by different materials, to realize different characteristic and character.Should be appreciated that for any embodiment described herein, first portion and second portion also can be formed by substantially the same material.Under the situation that first portion and second portion can be formed by same material, first portion and second portion can have at least one different characteristic such as size, thickness, porosity etc. alternatively, and this can produce the differential embedding that causes differential strain, take off embedding, alloyage, oxidation, reduction or plating.For example, first portion and second portion can comprise same material, still can have the different aperture degree, and this realizes the gradient of porosity along first portion and second portion.In some cases, first portion can comprise the porose material (for example powder pressing thing, foam) with first density, and second portion can comprise the porose material with second density different with first density.
As described here, some embodiments of the present invention relate to the reaction of material and one or more electrode.For example, the material embedding can one or more electrode.In certain embodiments, in the operation period of exciter system or equipment, an electrode can obtain the concentration that material spatially changes, thereby this causes the displacement of differential strain generation system or equipment at least a portion.That is to say that the degree that material for example is embedded in the part of electrode can be greater than the degree in the second portion that is embedded into electrode, this has realized differential strain.
Actuator of the present invention or its part (for example electrode), especially at least comprise and to embed, to take off embedding, alloyage those parts with the degree different in the first portion of, oxidation, reduction or plating material with second portion, can have such as any suitable shapes such as plate, sheet, bar, pleated sheet or bar, bundle, cup, bar, pipe, cylinders, as long as it can be displaced to second orientation from first orientation, can be used to realize required function like this.In some cases, at least a portion of actuator can be perforated and/or can have a plurality of " legs " or " arm " or branch road.In some cases, positive electrode and/or negative electricity are very nonplanar.For example, positive electrode and/or negative electrode can be plate or ball or other molded non-planar.In certain embodiments, positive electrode and/or negative electrode can have Any shape and can comprise at least one groove, and one or more groove can help and/or guide the displacement of exciter system or its part.For example, electrode can have groove or projection so that help, guide or guide electrode to move to the mode of second orientation from first orientation.In some cases, electrode can fold along at least one groove when excitation.
Actuator of the present invention can be from the nanometer to the micron and to macroscopic rank on dimensional range.For example in certain embodiments, exciter system 110 can have and is less than or equals 1 meter, be less than or equal 10 centimetres, be less than or equal 1 centimetre, be less than or equal 1 millimeter, be less than or equal 100 microns, be less than or equal 10 microns, be less than or equal 1 micron, be less than or equal 100 nanometers or be less than or equal at least one sizes of 10 nanometers.
The electrode of actuator also can be on dimensional range from the nanometer to the micron order and to macroscopic rank.For example in certain embodiments, electrode 114 can have and is less than or equals 1 meter, be less than or equal 10 centimetres, be less than or equal 1 centimetre, be less than or equal 1 millimeter, be less than or equal 100 microns, be less than or equal 10 microns, be less than or equal 1 micron, be less than or equal 100 nanometers or be less than or equal at least one sizes of 10 nanometers.
The actuator (comprising electrode) that comprises the first portion that can embed, take off embedding, alloyage, oxidation, reduction or plating material with the degree different with second portion can be formed by any suitable material (for example at size active material) of permission with any appropriate format of described substance reaction.In certain embodiments, first portion is formed by varying sized porose material when the ion exchange.As described here, dimensional changes can be volumetric expansion relatively uniformly or contraction, perhaps can be owing to introducing deflection or bending or the extrusion-deformation pattern that differential strain is realized.Porose material can be the fine and close thing of pressed powder or metal foam or at the composite of size active material.Second portion can be by forming in the size non-viable material.First portion and second portion can comprise alternatively such as the additive of tackiness agent or such as the conduction additive of carbon or metal.Can for example comprise in the following material one or more at the size active material: Al, Au, Ag, Ga, Si, Ge, Ti, Sn, Sb, Pb, Zn, carbon, graphite, hard carbon, mesoporous carbon (mesoporous carbon), oxide, embed oxide, layered oxide, clay mineral, sulphide, laminate sulfide, TiS 2, MoS 2And WS 2Be to be understood that actuator of the present invention also can comprise other metal, the compound that comprises metal, inorganic material etc.
In some cases, actuator of the present invention can experience by the dimensional changes that has pore electrod to provide varying sized when the ion exchange.In some cases, there is pore electrod experience when charging or discharge to comprise the dimensional changes of bending, deflection or extruding.In certain embodiments, there is pore electrod can comprise gradient of porosity, wherein has the first portion of pore electrod to have the porosity different with the porosity of the second portion that pore electrod is arranged.In some cases, have pore electrod also to comprise and the surface layer that has pore electrod to contact, wherein surface layer is embedded into, takes off embedding, alloyage, oxidation, reduction or plating so that the bigger degree of pore electrod to be arranged than (lower floor).Surface layer can be partly or is covered or be packaged with the outer surface of pore electrod basically, thereby surface layer can be mainly and/or directly is exposed to other parts of system.In some cases, surface layer can be embedded into or alloyage so that the bigger degree of pore electrod to be arranged than lower floor.In some cases, surface layer can have than lower floor the higher density of pore electrod is arranged.
In some cases, can embed, take off embedding, alloyage can be ionic species in the material of, oxidation, reduction or plating actuator at least a portion (for example part of electrode).The unrestricted example of ion comprises proton, hydroxide ion, sulfate ion, chloranion, phosphate anion and nitrate ion.In other cases, material can comprise alkali metal or alkaline-earth metal.In certain embodiments, material is the electronics that can cause surperficial at least a portion oxidation or reduction.In other embodiments, material is can be with the plating material of the degree different with second portion at first portion's electrochemical deposition.In some cases, material can be selected from proton, alkali metal ion, lithium, Ion complex, hydroxide ion, carbanion, chloranion, sulfate ion, phosphate anion, other multi-atomic ion complex compound etc.In some cases, material is selected from proton, alkali metal ion, Ion complex, hydroxide ion, carbanion, chloranion, sulfate ion and phosphate anion.In some cases, material is a proton.
Material can be originally with such as just being used for forming or the solid form of the material of negative electrode active material is present in the electrochemical cell.In other cases, material can be that lamination is not the solid form of this electrode active material part still to one of electrode.In another embodiment, material can be the form such as the independent solid ion source of solid electrolyte.In another embodiment, material can for example exist with the form as dielectric liquid or gelatin and can be present in the electrochemical cell before the charge/discharge in the first time of battery.In other embodiments, these materials may reside in the material of electrochemical cell outside.For example, material may reside in the environment that uses actuator.In a specific embodiment, actuator is designed to immerse in the fluid that comprises following material, and this material can embed, alloyage is in the part of, oxidation, reduction or plating electrochemical cell electrode.For example, fluid can be a physiological fluid, and material can be the ionic species that is present in the physiological fluid.
In some cases, equipment of the present invention can comprise anode, negative electrode and as the lithium ion of material.When anode applied electric field between negative electrode, this equipment can reversibly charge and discharge.In some cases, in when charging, li-ion electrode can be inserted in the anode, thereby for the negative electrode that volume or size remain unchanged in fact, anode experience volume or dimensional changes.When discharge, lithium ion can be sent to negative electrode from anode, thereby lithium ion can be inserted in the negative electrode.As a result, anode can turn back to its volume/shape before charging, and negative electrode can experience volume or dimensional changes with respect to anode.In some cases, anode and negative electrode can be side by side when charge/discharge cycle or non-volume or the dimensional changes of side by side experiencing.In some cases, have only one can when charge/discharge cycle, experience volume or dimensional changes in anode and the negative electrode.
Actuator of the present invention can be used for various application.For example, actuator can be used for wherein for example can being carried out by actuator the microfluidic device of switching and valve control function.In other cases, can use actuator as in order to the pump that causes in the fluid flow channel or go out from orifice flow, comprise and be used to control the pump that medicine is sent.In other embodiments, actuator can be the part of outside or implantable medical equipment.The material that can embed, take off at least a portion (for example part of electrode) of embedding, oxidation, reduction or plating actuator can be the part of electrochemical cell (for example in the manufacturing before using) in certain embodiments; Yet can be to use the constituent element of the environment of actuator in other embodiments.Actuator also can be the part of the MEMS such as micro mirror array (MEMS) equipment that wherein encourages the addressable minitype actuator independently.In other cases, one or more actuator can be constructed and arranged to be launched into structure when applying electric current or voltage.Such structure can for example be used as tent or scaffold.In other cases, actuator of the present invention can be to come the operation tool of electric expansion or contraction or the parts of medical implant by electricity input.Various application are hereinafter more specifically described.
In certain embodiments, actuator of the present invention can be used for making structure displacement or the distortion adjacent with actuator.For example, as shown in illustrated embodiment among Fig. 2 A, exciter system 150 comprises as the actuator 151 of allotting the pump of fluid 170 from reservoir 172.This pump for example can be allotted greater than 0.01mL, greater than 0.01mL, greater than 1mL, greater than 5mL, greater than 10mL, greater than 100mL, greater than the fluid of the different volumes of 1L.Actuator 151 can use the mode similar to actuator shown in Fig. 1 110 to operate.In brief, material can be with embedding, take off embedding, the alloyage first portion 156 in, oxidation, reduction or electrode plating 154 with respect to part 158 uneven modes, thereby cause differential strain between first and second part.Second portion can be to cause the deflection of electrode 154 or bending and result to cause the deflection or the crooked mechanical constraint of actuator 151.The reservoir 172 adjacent with actuator 151 can be formed by deformable material, thereby the deflection of actuator 151 causes the reservoir pressure inside to increase, and this makes allots fluid 170 from reservoir, as shown in Fig. 2 B.In certain embodiments, can by the displacement speed of actuator from the primary importance to the second place/or degree (for example length of stroke) control the speed of allotting or inject fluid 170 from reservoir.Allotting speed can be controlled so as to constant or variable.Can be by following parameter control excitation speed and/or degree, the amplitude and/or the endurance of all electric currents that applies in this way of these parameters or voltage (for example in charging or discharge process), the material concentration and being used for that will embed, take off the electrode of embedding, alloyage or plating electrochemical cell form the size and the material of the material of electrochemical cell to be formed, such as to form with the actuator first portion of substance reaction and the configuration and the material of second portion in various degree.
One or more electrochemical cell can be arranged to alternatively and the displacement of one or more parts combination with realization system or system's part.In some cases, the electrochemical cell with different fillips can be by patterned arrangement on the surface, and wherein each electrochemical cell is independently controlled.For example can use in the present invention based on U.S. Patent application the 11/150th, No. 477 U.S. Patent Publication No. 2006/0102455 and based on other the configuration of battery, parts and/or equipment described in the international publication number WO2005/124918 of international application PCT/US/2005/020554 number, above-mentioned two applications all are incorporated into this by reference.
Actuator of the present invention can be made to allow the excitation speed and the length of stroke of different range of the material of different hardness.For example, the actuator that length of stroke is long can be formed by one or more material with relative low hardness.In such embodiments, lacking current pulse can cause actuator from the first slow displacement that is directed to second orientation.Contrast, by one or more more the actuator that forms of hard material only when applying electric current, just can be shifted.In such embodiments, actuator can be displaced to the second or the 3rd orientation from first orientation under the situation of not considering load in some instances when the electric current that applies increases progressively at every turn.In certain embodiments, the energy of maximization from the actuator to the mechanical system transmits when the hardness of actuator and mechanical system coupling.Thereby, can carry out the material selection of actuator based on concrete application and/or required incentive mode.
How the hardness that Fig. 3 A-C shows actuator can influence the displacement speed of actuator and the example of length of stroke.In the illustrated embodiment, actuator 180 comprises the first portion that can embed, take off embedding, alloyage, oxidation, reduction or plating material with the degree different with second portion in Fig. 3 A.The end 181 of actuator can be fixed on a certain position at the situation upper/lower positions that actuator is in primary importance a.Actuator can be adjacent with the reservoir 192 that comprises fluid 194 with piston 190.In the non-homogeneous embedding of material (for example for the second portion of actuator and first portion), when taking off embedding, alloyage, oxidation, reduction or plating, actuator 180 can be displaced to position c from position a, as shown in Fig. 3 C.Actuator 180 can be formed to realize long stroke length " ac " by one or more materials with low hardness.This can be for example be applied to actuator and makes actuator be shifted to realize that this displacement that can cause piston 190 is to allot fluid from reservoir by lacking current pulse.Short current pulse can be released fluid lentamente from reservoir and be relaxed to its new equilibrium locations c until actuator.Contrast, Fig. 3 B shows the actuator 182 that is formed by high hardness material in first orientation, and wherein the end of actuator is at position b.When applying the value electric current identical with the electric current that applies to actuator 180 with the endurance, actuator 182 can be displaced to position c from position b, as shown in Fig. 3 C, the length of stroke of actuator 182 " bc " is shorter than the length of stroke " ac " of actuator 180 owing to the different hardness of the material that is used for forming actuator 180 and 182.In certain embodiments, actuator can for example walk abreast or serial is piled up to increase load or the power to structure was applied.
Following example further specifies the difference configuration and the mode that can be used to implement actuator of the present invention.
In Fig. 4 in the illustrated embodiment, exciter system 200 comprises actuator 210, this actuator comprises positive electrode 212, negative electrode 214 and dielectric substrate 216, and this dielectric substrate comprises can embed, take off embedding, alloyage, oxidation, reduction or plating just or the material 218 of negative electrode.Material transmission through dielectric substrate under the voltage 220 that applies can be used for making progress in the direction of arrow 222 and 224 or downward shift driver 210.This displacement can realize for example can being used for opening or the actuator of closed valve, displacement mirror, pump, fluid etc.As discussed above like that, the combination of materials that is used for forming positive electrode and negative electrode can change.For example, suitable material can comprise the active material in lithium ion or the ni-MH battery.As shown in this embodiment, exciter system 210 at one end is fixed in substrate 228.This substrate can serve as mechanical constraint, thereby the part of actuator 230 experience are minimum or not displacement.Because the part 232 of actuator is unfixing, so this part experience realizes crooked displacement.
In another embodiment, can embed, alloyage can be positioned such that the part of actuator preferentially is exposed to material and the different piece of actuator is not exposed to or be exposed to material with degree still less in the material of the part of, oxidation, reduction or plating actuator.For example in Fig. 5 in the illustrated embodiment, exciter system 250 comprises actuator 252, and this actuator comprises part 254 and part 256.Part 256 can be to be exposed to the material 260 that is immersed in the material 262 (for example electrolyte) than part 254 bigger degree.Piston 254 and substrate 264 can conduct and come work as positive electrode and negative electrode.Part 256 can be by insulator 266 and substrate 264 insulation.When applying potential difference between substrate (perhaps at a distance counter electrode) and part 254, material 260 can be with the degree embedding bigger than part 254, take off embedding, alloyage in, oxidation, reduction or plating part 256.Part 254 and/or 256 and the type of action of material 260 for example depend on the particular type of material and be used for forming the material of part 254 and 256.Because the differential strain between part 254 and 256, this effect can cause the deflection of actuator 252.
Can make structure by the several different methods that comprises assembling of MEMS making, various membrane structure deposition process, thick film paint-on technique, electrode deposition process and physics and lamination such as exciter system 200 and 250.Other making method also can be suitable and for known to those of ordinary skills.
Shown in the embodiment, exciter system 270 comprises the electrode 272 with actuator 276 electric connections as illustrated in Figure 6, and actuator 276 can connect (perhaps non-connection integratedly) integratedly to substrate 274.Actuator 276 can be to form uniformly; Yet part 280 can be exposed to material 282 with the part 284 bigger degree than actuator.Exposing (for example different exposed areas) to the difference of material can cause embedding with degree different with part 284 and part 280, take off embedding, alloyage, oxidation, reduction or plating.This can cause for example excitation on the direction of arrow 222 and 224 of actuator.
In certain embodiments, actuator of the present invention can be constructed and arranged to be used in the physiology facility, such as in the health.For example, some embodiments of the present invention are provided for the electrochemical actuator of medicament administration in the health, as described here, these actuators comprise at least one negative electrode, at least one positive electrode and material, the electrochemical actuator voltage or the electric current that can be applied wherein, thus voltage or electric current apply or it stops to comprise the embedding of material at least one electrode of electrochemical actuator, this realizes the volume or the dimensional changes of electrochemical actuator.In some cases, volume or dimensional changes can for example via distribution or method for implanting as described herein and other method with medicament administration in health or the fluid administration that will comprise medicine be useful in health the time.
In some instances, actuator is dipped into the physiological fluid (for example blood, urine, sweat etc.) of the material that comprises the part that can embed actuator electrode.When embedding, electrode can experience the displacement that is directed to second orientation from first.In other embodiments, material can be when being exposed to physiological fluid takes off from the part of electrode and is embedded into the health.Perhaps in other embodiments, material can be when being exposed to physiological fluid the part of oxidation or reducing electrode, this can realize displacement.In other example, can beyond health, use actuator, for example actuator can be exposed to the physiological fluid of removing from health.
Fig. 7 is the example ion of the actuator that can use in the physiology facility.Actuator 290 comprises positive electrode 292, negative electrode and is positioned two insulators 296 between the electrode.Actuator 290 can immerse in the physiological fluid 298 that comprises material 299, and this material can be for example be embedded in the electrode or from an electrode with the degree bigger than another electrode when applying voltage or electric current and takes off embedding.This can cause actuator from first displacement that is directed to second orientation.Can realize the different shift modes of actuator according to the Machine Design of actuator.For example, actuator can be the shape of bundle shape, Zhe shape, support (stent), dish or multiple-level stack structure.Also can cause that structure is from first expansion that is directed to second orientation, contraction, folding, distortion, bending, scrolling etc. with other actuator shape and design.In certain embodiments, actuator can be the form of medical implant or all implant components, as support, sensor, prosthese (prosthetic) etc.
In another embodiment of the present invention, exciter system comprises at least one electrochemical cell, and this electrochemical cell comprises negative electrode, positive electrode and can embed, take off embedding, the alloyage material in the first portion of, oxidation, reduction or plating electrochemical cell with the degree different with the second portion of electrochemical cell.Because material and first and/or one of the above-mentioned effect of second portion, first and/or second portion can be when discharge the experience dimensional changes, this causes the actuator of doing mechanical work to be shifted.In certain embodiments, electrochemical cell is constructed and arranged to charge during fabrication and discharge in use.In certain embodiments, electrochemical cell is constructed and arranged to charge during fabrication and partly discharge or not further charging after discharge first after using.Exciter system can be constructed and arranged to spontaneously discharge.In some cases, actuator can be encouraged to cause repeatedly by the discharge of one or many ground constantly in difference.Can the disposable actuator when discharge (for example partial discharge, discharge fully).Such configuration can be useful for the portable equipment such as some pump, sensor, implant and medical equipment.
One embodiment of the present of invention comprise and being used for the infusion pump of fluid infusion to health.This infusion pump comprises at least one electrochemical cell, and this electrochemical cell comprises negative electrode, positive electrode and material, and wherein negative electrode and/or positive electrode experience dimensional changes when charging and/or discharge makes fluid infusion in health.Alternatively, infusion pump can not comprise material during fabrication, but in use when being exposed to material infusion pump can carry out excitation and inject fluid.In some were arranged, infusion pump was constructed and arranged to spontaneously discharge.Such equipment is confession power, this means the electrochemical cell of making equipment under charged state.This equipment can comprise and is selected as making electrochemical cell to expand when discharge or the positive electrode material and the negative electrode material of distortion.For example, can use the material (for example expand and reach 300%) that by lithiumation the time, expands as the lower cost materials conduct of silicon and tin.
Comprise the volume value of allocation and allot the pumping rate of endurance and can depend on cell expansion or rate of deformation, this cell expansion or rate of deformation can be controlled by the discharge rate of electrochemical cell again.Can carry out discharge control by the whole bag of tricks, such as be used for the resistance of external circuit of battery discharge by variation.External control can for example comprise resistor, and this resistor comprises thin metal or the wiring that also comes work as fus.This can be used for by the controlled self discharge of resistor or external circuit permission electrochemical cell.In a specific embodiment, variable resistor is implemented in the external circuit that comprises solid-state circuit so that control discharge rate and pumping rate.By changing the non-essential resistance of battery, can control spark speed and excitation speed.
In another embodiment, the dutycycle of equipment can change so that control the limit or the degree of displacement or pumping.In this embodiment, the external circuit that is used for equipment discharge or charging can repeatedly switch between disconnection and closed circuit or " connect and turn-off ".That is to say, can control dutycycle by the external circuit of disconnection and/or closed and actuator device association.The frequency of connection/shutoff pulse and endurance can provide the control of displacement speed and total shifting.For example, if externally the equipment under the short-circuit condition is in time t performance discharge fully, this realizes total strain ε, thereby switches between disconnection and closed circuit condition, the feasible cumulative time that is in closed circuit cost is the t/10 corresponding with 10% dutycycle, and wherein clean strain is ε/10.In the endurance of closed circuit pulse constant embodiment, can come controlled deformation speed by the change pulse frequency.Pulse frequency and endurance also can change independently with the inherent nonlinearity in displacement that adapts to equipment and the time response relation, so that realize the relation of displacement with the time distribution of the actuator wanted or pump.
In other embodiments, discharge rate can be designed in the battery and (for example can design self-discharge rate).In a specific embodiment, use the method known to the skilled in electrochemical apparatus or the field of batteries to design the internal driving of battery so that produce required discharge rate.Externally the resistance between the outside lead of short-circuit condition or battery is lower than under those conditions of internal battery impedance basically, discharge rate and therefore encourage speed mainly to depend on the internal driving of battery.For example, the a certain maximum discharge rate that can introduce at using controlling method described herein and more low rate design battery, have the high relatively internal driving that safe low discharge speed still is provided even perhaps can design cells under the accidental short circuit condition.
Equipment rate of deformation and/or quantity the corresponding pumping rate and/or the quantity of the pump of such Equipment Control (and by) can be building up in the equipment, thereby for example disposable discardable equipment is in predetermined set speed and time and/or volume pumping.Alternatively or in addition, can utilize control to come structure equipment to make in the using process of equipment, to change or among one of several different settings, discharge/pumping rate and/or degree are being set before the use equipment.In some instances, in the time can repeatedly using equipment, can be between using, in use wait and change discharge/pumping rate and/or quantity.By numeral or analog circut or combination, those skilled in the art can design the system in the equipment of any of these feature.
By these and/or other means, can change pumping rate widely by the discharge rate of control electrochemical cell.In certain embodiments, the transmission signal that can remotely control, for example send by the control circuit to control dutycycle or external loading resistance is wirelessly controlled discharge rate.Then pump for example can be allotted greater than 0.01mL, greater than 0.1mL, greater than 1mL, greater than 5mL, greater than 10mL or greater than the fluid of the different volumes of 50mL if desired.
The application of the actuator of the present invention of pump form can be used for following application, and these application include but not limited to subcutaneous delivery, intravenous injection, intrathecal injection, other common method to health delivering drugs and fluid, air freshener or the perfume sprinkler and the implantable drug delivery device of medicine or fluid.
For example, as everyone knows when bimetal coupling is immersed in the electrolyte, bimetal to one of be anode and preferentially do not have oxidation that and another is preferentially oxidized.An example is the anodic protection of zinc to iron and steel.In an example embodiment, Fig. 8 A shows first portion 302 and second portion 304, and first portion and second portion are formed by different materials.Same structure after Fig. 8 B shows in immersing water.This structure comprises layer 306 now.If first portion comprises Fe, second portion and comprises Zn that then formation comprises Zn (OH) when being exposed to water 2Part 306.Reaction in part 302 is 2H ++ 2e=H 2(g), and in the reaction of part 306 are Zn+2 (OH -)=Zn (OH) 2+ 2e.
As shown in Fig. 9 A-B, actuator 310 comprises first portion 312 and second portion 314.If first portion is formed by Fe and second portion is formed by Zn in thin layer, then convert Zn (OH) at Zn 2The time, at Zn (OH) 2(Zn+2 (OH for example during the formation -)=Zn (OH) 2+ 2e) volumetric expansion will cause spontaneous excitation, and this causes the displacement of curve form, as shown in Fig. 9 B.This spontaneous being activated at is used for carrying out mechanical work in the actuator of the present invention.
As shown in Figure 10 A-B, second portion 322 is formed by Fe if first portion 320 is formed by Zn, then (Zn+2 (OH for example when Zn changes -)=Zn (OH) 2+ 2e), structure 318 will be opened, as shown in Figure 10 B.The excitation of this class will be used for such as support, expansion dish or the such structure of other structure in order to alleviate compressive stress between the vertebra.Can use the material of expanding simply by preferential absorption ion or molecular substance from fluid to realize the excitation of similar type.
Related domain ordinary person can select other bimetal of being suitable for using in the present invention right.
In health, wish to avoid tangible gas to develop.Use also hope at some and have the material that the lasting plastic deformation of experience still has obdurability.In certain embodiments, it can be favourable using following actuator, this actuator spontaneously discharges at positive electrode and the mutual electric short circuit of negative material and when immersing in the following electrolyte, and this electrolyte comprises can embed, take off embedding, the alloyage material at least a portion of, oxidation, reduction or plating actuator.
Figure 11 A-B shows the lithium ion coupling of assembling and coming across in the electrolyte spontaneous discharge of time experience under charged state (for example a part comprises Li 0.5CoO 2And another part comprises Li xTi 5O 12, x>4 wherein).(as the alternative scheme of lithium ion coupling, actuator can be that under charged state, assemble and nickel metal-hydrogen thing coupling experience spontaneous discharge when coming across in the electrolyte (for example a part comprises Ni 3+OOH and another part comprises MH x, wherein M is a metal)).Figure 11 A shows the actuator that was in zero strain before being exposed to electrolyte, and Figure 11 B shows the actuator after being exposed to electrolyte.When discharge, the first portion of actuator expand into the volume bigger than the second portion of actuator, causes the bending (contraction) of actuator thus.Therefore, the spontaneous discharge when actuator is exposed to electrolyte can cause decay.
Coupling of the lithium ion of experience spontaneous discharge (Figure 12 B) or the coupling of nickel metal-hydrogen thing when Figure 12 A-B shows (Figure 12 A) that assembles and coming across in the electrolyte under charged state.The shape of actuator causes it to expand when spontaneous discharge.
Can in actuator of the present invention, use numerous types of materials.For example, when material can use Ti metal as electrode material during for hydrogen, because Ti metal is good hydrogen absorbing medium.Other suitable hydrogen absorbing medium comprises precious metal.Pt, Rh, Ir and Au also are can be as the toughness and the robust metallic of electrode material.In a specific embodiment, can by will be for example hydrated metal join the non-hydrated metal to and make from the support of opening (perhaps other actuator design), thereby hydrogen causes the displacement of actuator to the transmission of another metal from a metal in being exposed to electrolyte the time.As widely used in the semiconductor device art, as shown in Figure 13-14, this concrete mode also can be benefited from introducing the diffusion impervious layer between two metals, thereby avoids causing the hydrogen that encouraged before being exposed to electrolyte to spread between two metals.Figure 13 shows (a) and is being exposed to before the electrolyte and (b) comprising two different pieces and comprising the exciter system that is positioned the diffusion impervious layer between the each several part alternatively when being exposed to electrolyte, the wherein crooked or extruding of this system's experience, and each part comprises different materials (for example metal).Similarly, Figure 14 shows (a) and is being exposed to before the electrolyte and (b) comprising two different pieces (comprising different materials (for example metal) separately) and comprising the exciter system that is positioned the diffusion impervious layer between the each several part alternatively when being exposed to electrolyte, the wherein crooked or unlatching of this system's experience structure, and each part comprises different materials (for example metal).In certain embodiments, iridium is because its biocompatibility and the attractive metal that is used as being used to form at least a portion of actuator.
In another embodiment, for example as shown in Figure 15 A-B, actuator of the present invention can comprise hinging structure.Actuator can comprise can preferentially embed, take off embedding, alloyage in the first portion 342 of, oxidation, reduction or plating material with preferentially do not embed, take off the second portion 344 of embedding, alloyage, oxidation, reduction or plating material.In some instances, second portion 346 and third part 348 are formed by same material.When actuator is exposed to first material, first portion can embed, take off embedding, alloyage, oxidation, reduction or plating material with the degree different with first and/or the degree of third part, this causes the displacement (for example expanding) of actuator, as shown in Figure 15 B.Alternatively, second portion 346 and third part 348 are formed by different materials, and when being exposed to second material, actuator can be displaced to second orientation from first orientation.
Can in various the setting, use the actuator of the present invention that comprises first portion and second portion, this actuator charging and/or when discharge material embed, take off embedding, alloyage in, oxidation, reduction or plating first portion with the degree different with second portion, first portion's experience is with respect to the gained dimensional changes of second portion.Thereby actuator of the present invention can have configuration, shape and/or the design except above-mentioned configuration, shape and/or design.The example of such configuration, shape and/or design is included in U.S. Patent number 6,545, and 384,5,907,211,5,954,079,5,866,971,5,671, configuration, shape and/or the design described in 905 and 5,747,915, these patents all are incorporated into this by reference.
Consideration at low voltage, long lifetime electrochemical actuator design is described now.In certain embodiments, the design of low voltage, long lifetime electrochemical actuator comprises some operation standard.In one embodiment, provide a kind of method of operating following electrochemical cell, this electrochemical cell comprises negative electrode, positive electrode, nonaqueous electrolyte and as the lithium of material (for example embedding material).Can operate electrochemical cell makes positive electrode have the average isostatic electromotive force (perhaps off load voltage (OCV)) that is less than pact+4V with respect to lithium metal in its use charged state.Negative electrode has average potential greater than pact+0.2V with respect to lithium metal in its use charged state.Electrochemical cell can with can operative relationship be arranged from the parts that first orientation is displaced to second orientation.The operation of electrochemical cell can cause the volume or the dimensional changes of electrochemical cell.When applying the voltage that is less than about 10V to electrochemical cell, these parts can be displaced to second orientation from first orientation according to the volume or the dimensional changes of electrochemical cell.
As hereinafter more specifically as described in, crossing high potential and may cause electrochemical corrosion at positive electrode at the current collector and/or the active material of positive electrode.In some cases, high potential also may cause the degraded of nonaqueous electrolyte or salt, and this may cause the loss and/or the interior undesirable side effect of battery of electrolyte conductivity.Like this, some electrochemical cell of the present invention can be manipulated into to have in the charged state of battery and be less than about 4V, is less than pact+3.5V, is less than pact+3.0V or is less than the average isostatic electromotive force of pact+2.5V.
Hereinafter also described (for example in its use charged state with respect to lithium metal) and crossed the balanced electromotive force of harmonic average and may cause negative effect, such as the electrochemical corrosion of negative electrode current collector or the deposition of lithium metal.Thereby, can operate electrochemical cell and make negative electrode have greater than pact+0.2V, greater than pact+0.5V, greater than pact+1.0V or greater than the average isostatic electromotive force of pact+1.5V.Depend on concrete electrochemical cell, can select the maximum value and the minimum value scope of the average isostatic electromotive force of positive electrode and negative electrode respectively.For example, in one embodiment, positive electrode has the average isostatic electromotive force that is less than pact+3.5V, and negative electrode has the average isostatic electromotive force greater than pact+0.5V.In another embodiment, positive electrode has the average isostatic electromotive force that is less than pact+3.5V, and negative electrode has the average isostatic electromotive force greater than pact+1.0V.In another embodiment, positive electrode has the average isostatic electromotive force that is less than pact+3.5V, and negative electrode has the average isostatic electromotive force greater than pact+1.5V.In another embodiment, positive electrode has the average isostatic electromotive force that is less than pact+3.0V, and negative electrode has the average isostatic electromotive force greater than pact+0.5V.Certainly, can select to be used for other average isostatic potential range of positive electrode and negative electrode.
In certain embodiments, the operation electrochemical cell can relate to the voltage that will be less than about 10V and is applied to electrochemical cell and according to the volume or the dimensional changes of electrochemical cell parts is displaced to second orientation from first orientation.As hereinafter more specifically discussing, the voltage that applies (being operating voltage) is generally low so that increase the cycle life of electrochemical actuator.Thereby the operation electrochemical cell can comprise applying and be less than about 10V, is less than about 8V, is less than about 7.5V, is less than about 6V, is less than about 5V or is less than the voltage of about 4V.Yet should be appreciated that the voltage that applies can be higher than the steady state voltage that applies for some period that requires high power excitation in the endurance of blink.Thereby, can be less than about 10V, be less than about 8V, be less than about 7.5V, be less than about 6V, be less than about 5V or be less than about 4V apply voltage operate electrochemical cell greater than 95% operation lifetime.In other example, can so voltage-operated electrochemical cell greater than 90%, greater than 80%, greater than 70%, greater than 60% or greater than 50% operation lifetime.
Below at the design of nonaqueous electrolyte lithium electrochemical cells consideration at the electrochemical actuator design of low voltage, long lifetime is described particularly.Yet be to be understood that these principles also can be applied to any electrochemical cell as actuator.
Be used for to be overpotential (in charging process) or to owe electromotive force (in discharge process) overpotential and owe electromotive force and be respectively when a certain state of charge at the balanced or static of battery or more than the off load voltage (OCV) or the following value that applies voltage in the driving force that transmits the material that comprises ionic species as the electrochemical cell of actuator.If electromotive force and each compound x (concentration) if relation be known and be known that then those of ordinary skills can easily determine OCV according to state of charge such as the ratio and the such battery parameter of the irreversible loss degree of ionic species in cyclic process of negative electrode and anode material.For example, LiCoO 2-graphite battery can have along with state of charge the OCV that changes continuously between about 3.9V and about 3V, and LiFePO 4-graphite battery has the approaching constant voltage of about 3.3V in big state of charge.
For asking high excitation speed, may wish in the charged state process, to have big overpotential and in discharge process, have the big electromotive force of owing.On the other hand, also recognizing here may be because some former thereby especially influence the performance and the life-span of battery in many charged circulations to the scope of the electromotive force that electrochemical cell applies.High-end at operating voltage range recognized that high potential can cause current collector (such as aluminium) or the electrochemical corrosion of active material or the degraded of nonaqueous electrolyte or salt at positive electrode.This may cause undesirable side effect in the loss of electrolyte conductivity or the battery, such as forming gas.At the low side of operating voltage, cross low potential and can cause the electrochemical corrosion of negative electrode current collector (such as copper) or the deposition of lithium metal, if the electromotive force when the electromotive force of negative electrode reaches lithium metal and a stablize then situation afterwards occurs.Therefore, for asking high excitation speed and, may wish to have low relatively OCV and make and in charging process, to apply high overpotential and do not reach the stable restriction of electrolyte system or positive current collector for asking the stability and the long lifetime of the non-water lithium electrochemical cells that is used for encouraging.Yet low OCV should be not low excessively; Otherwise, the high electromotive force when owing electromotive force and may reach anode collector (such as copper) dissolving that in discharge process, applies, perhaps this can cause the lithium metal may be by plating.Selection to the active material of the positive electrode that is used to satisfy these standards and negative electrode is important, because may wish to provide high excitation energy and power in electrochemical cell of the present invention.
In certain embodiments, wish to have following positive electrode material, the OCV that is less than about 4V that this positive electrode material has two-forty and high strain and measures with respect to lithium metal.In other embodiments, the OCV with respect to lithium measurement is less than about 3.5V, is less than about 3V or is less than about 2.5V.The unrestricted ion of such positive electrode material comprises with LiFePO 4, TiS 2, TaS 2And alloy and the electric polarization compound of the form of modification for the basis arranged on forming.In some cases, electrochemical cell comprises following negative electrode material, these negative electrode materials have high power and in used compositing range with respect to lithium metal at least+OCV of 0.1V.In other cases, OCV at least+0.5V or more.For example, graphite can be that suitable material makes clean strain exist when using with positive electrode material.Another suitable material has when being included in lithiumation in big lithium compositing range and to be about the nearly constant potential of 1.57V with respect to lithium metal and to have the Li that zero volume almost changes xTiO 2Spinel, for example Li of starting ingredient 4Ti 5O 12Thereby this can allow to be used for excitation in the Volume Changes of positive electrode.In certain embodiments, this type of electrochemical cell that is combined as the basis with positive electrode material and negative electrode material has the battery OCV that is less than about 3.5V usually.Certainly, might have when the charging of battery or discharge on the occasion of and negative value between the cell voltage that changes and keep all the time with respect to lithium metal and do not have too high positive electrode electromotive force and do not have the above-mentioned condition of low negative electrode electromotive force.
When such battery is used for electrochemistry when excitation, the overpotential that applies and owe electromotive force and can be implemented in charging voltage and the discharge voltage under battery OCV on the battery OCV.Yet the absolute value of the operating voltage of battery generally remains low.For example, the absolute value of operating voltage can be less than about 10V, is less than about 7.5V, is less than about 5V or is less than about 3.5V.Should be noted that to asking the high power excitation in the endurance blink voltage that applies can be pulse character and can be safely apparently higher than the steady state voltage that will cause electrochemistry to damage usually to such battery.Yet in order to keep operation electrochemical cell under the condition of cell voltage obtaining the long lifetime, the voltage that applies can be realized being less than about 5V, being less than about 4.5V or being less than the electromotive force at positive electrode of 4V with respect to lithium metal.Can be by using based on such as LiFePO 4, LiTiS 2And LiTaS 2The positive electrode material of such compound is realized this point.
The choice criteria that is used for high mechanical energy metric density, high-power electrochemical excitation compound is described now.The theoretical mechanical energy density of excitation compound is by equation 1/2E ε 2Given, wherein E is a Young's modulus and ε is the strain that can cause under the specific operation condition.Therefore, the material of high strain and high elastic modulus has the electromotive force that is used for providing at electrochemical cell of the present invention high-energy-density.
About electrochemical actuator, the strain of recognizing acquisition here is not to be linear along with the concentration of embedding in the electrochemical cell or alloying substances.As described in No. the 11st, 796,138, the U.S. Patent application that is incorporated into this by reference, for example embedding compound L i xTiS 2The plotted curve of strain contrast Li concentration x in, slope of a curve is at low Li concentration steepest.Thereby, if wish to operate the given electric energy acquisition maximum machine energy of actuator and/or obtain the highest mechanical output, then using Li from actuator for being used for xTiS 2Wish during as electrochemistry excitation compound in x is about 0 to 0.4 scope, to operate.The latter is according to following consideration: embedding amount of material x is the product of electric current and time, thereby for the specific operation electric current, has the faster excitation of compound acquisition of higher strain for given x value.
Recognize that also the mechanical output of electrochemical actuator can decide on the rate capacity of electrochemical cell (for example charging or discharge rate).Can make ion or electron diffusion length be the short two-forty ability that obtains by electrolyte and/or the design battery of selecting the macroion conductivity.For example, can wish the fine particle size so that reduce diffusion length and correspondingly reduce diffusion time for electrode based on particle.
Therefore the transmission character of material also can be the important choice criteria that is used to design electrochemical actuator.For example, the chemical diffusion coefficient of the ionic species of responsible Volume Changes can be selected as height.One embodiment of the present of invention have shown the ε by equation 1/2E 2" power factor " that can be used as the quality factor that are used for the comparison different materials that D is given, wherein D is the chemical diffusion coefficient of the ionic species in the interested material.Fig. 4 compares the power factor of different materials and their proportion.The material of noting high power factor and low-gravity ρ can provide more high power factor as electrochemical actuator when all other conditions equate.For example, as TiS 2And TaS 2Stratiform two chalcogenides can be useful especially electrochemistry excitation compound according to these standards.
The inventor has realized that interested quality factor in the excitation field also comprise can be with the specific power of mechanical output and can be with the power factor of mechanical output as per unit mass as per unit volume.In using, the majority excitation wish to make two values maximum.The characteristic diffusion length that ionic species transmits is considered in the specific power requirement that it should be noted that electrochemical actuator in the operating process of electrochemical actuator.Although transmit length comprise between the electrode, through the electrode hole with stride across the length of isolator, encourage speed to surpass diffusion and be sent to the middle time necessary of material itself.Therefore, particle size (for the actuator based on particle) and chemical diffusion coefficient are key factor.For comparative material on equal basis, suppose that material can be processed into and has similar particle size, specific power can be defined as quantity 1/2 (E ε 2D Li/ x 2) and power factor is defined as 1/2 (E ε 2x 2ρ/D Li), wherein x is particle size (for example radius or a diameter).Fig. 4 is the specific power and the proportion thereof of different materials relatively, and Fig. 6 compares the specific power and the power factor thereof of different materials.Can select to be used for the suitable material of electrochemical actuator according to these choice criteria.For example as TiS 2And TaS 2Stratiform disulfide can be useful especially electrochemistry excitation compound.
In one embodiment, the electrochemical actuator of at least two of electrochemical actuator utilizations of the present invention (for example first and second) collaborative work makes when an electrochemical actuator charging (for example in order to produce useful mechanical work) another electrochemical actuator discharge or vice versa.For example, system or equipment can be included in about first electrochemical cell that disposes in the positioned opposite each other and second electrochemical cell, and the discharge that makes the battery of winning realizes the charging of second battery and the discharge of second battery realizes the charging of first battery.This paper also comprises and is constructed and arranged to be displaced to the parts of second orientation by charging and/or the discharge of at least one in first electrochemical cell and second electrochemical cell from first orientation.Certainly, be included in structure about the electrochemical cell that disposes in the positioned opposite each other can be included in many groups of such electrochemical cells disposing in the positioned opposite, for example greater than 2, greater than 5, greater than 10, greater than 20 or greater than 50 pairs of electrochemical cells.Such battery is serial or parallel operation relative to each other.Though before in active structure, used paired relative actuator (because the ratio work when compression when stretching of most actuators is better or vice versa), and in electrochemical actuator of the present invention, used such design that additional benefit is still arranged.Electrochemical actuator is storage or release electric energy when they carry out mechanical work, and if such electric energy dissipation (for example hot form by resistor electric energy is dissipated), then the energy consumption of actuator or exciter system may be height.Yet, by making that at round electric energy between the actuator another actuator discharges saving power in large quantities when an actuator charges.Being located such that each electrochemical actuator can be another benefit that another electrochemical actuator applies the relative electrochemical actuator of power can be by charging in the relative actuator one or two or discharging and control the stress that is provided with on the actuator.For example, this layout can allow to control prestressing force on the actuator to optimize exciting force, creep (creep) and/or the compliance of actuator.Another benefit is when the accurate positioning that can charge independently or improve actuator when discharging relative actuator.
The typical electrochemical battery comprises following electrode (for example anode), and this electrode expands and another electrode (for example negative electrode) shrinks or vice versa in discharge process so that reduce volume change in the battery in charging process.This may be favourable for some application, because little Volume Changes can for example reduce the layering of some layer in the battery.Yet in some embodiments of the invention, two electrodes in charging or discharge process, all expand or electrode do not shrink and another electrode to expand be favourable.Advantageously, such configuration allows ceiling capacity to be used for encouraging rather than slatterning when offsetting another electrode.
Thereby another embodiment comprises following electrochemical cell, and this electrochemical cell comprises anode and negative electrode, and this anode and negative electrode are constructed and arranged to make that another electrode does not shrink basically in the cyclic process of one of electrode volumetric expansion at least 1%.In other embodiments, one of electrode volumetric expansion at least 0.5%, at least 2% or at least 4% and another electrode does not shrink basically.For example, when one of anode or negative electrode expanded, another volume can expand or can be constant.Parts can have operative relationship with such electrochemical cell, and these parts can be displaced to second orientation from first orientation by the charging and/or the discharge of electrochemical cell.Can be by this expand simultaneously or electrode expands and another electrode does not shrink that suitable material is used for anode and negative electrode implement anode and negative electrode.
In some cases, electrode is h substance (for example lithium) spontaneously, and this causes the expansion of electrode or one or more parts of contraction and/or equipment to be directed to moving of second orientation from first.The electrode material of performance spontaneous discharge be well known in the art and wish under concrete " acquiescence " state status of equipment, for example electrochemical cell intentionally or can be favourable under the accidental short circuit situation.
Be suitable for that material as electrode comprises such as metal, metallic oxide, metal sulfide, metal nitride, metal alloy, intermetallic compounds, other comprises compound, other inorganic material electric activating materials such as (for example carbon) of metal.In some cases, electrode can advantageously comprise the material with high elastic modulus.In some cases, material can be as the variation of experiencing volume or other size with substance reaction time the described here.In certain embodiments, electrode can comprise such as monocrystal or the multicrystal material that comprises crystalline structure.In certain embodiments, electrode can comprise amorphous or disordered structure.
In some cases, the material of formation anode comprises one or more in aluminium, silver, gold, boron, bismuth, gallium, germanium, indium, lead, antimony, silicon, the tin.In certain embodiments, the material of formation anode can comprise Li 4Ti 5O 12Perhaps its any alloy or doping are formed.The examples of material that can form negative electrode comprises LiCoO 2, LiFePO 4, LiNiO 2, LiMnO 2, LiMn 2O 4, Li 4Ti 5O 12, TiSi 2, MoSi 2, WSi 2, TiS 2Perhaps TaS 2Perhaps its any alloy or doping are formed.In some cases, the material of formation negative electrode can comprise TiS 2Perhaps TaS 2In other embodiments, the material of formation negative electrode can comprise LiMPO 4, wherein M is one or more first trip transition metal (for example Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn) or its any alloy or mixes and form.In some cases, negative electrode comprises carbon, and wherein carbon can be the form of graphite, carbon fiber structural, vitreous carbon structure, highly oriented pyrolytic graphite, disordered carbon structure or its combination.Comprise that electrochemical cell that such material forms can be for example with respect to the above-mentioned cathode potential operation less than+4V of the electromotive force of lithium metal.Anode potential for example can be selected from respect to the electromotive force of the lithium metal above-mentioned electromotive force greater than+0.5V.
In some cases, the material of formation electrode can comprise the material that intersperses among in the material.For example, electrode can comprise the material of some, thereby the substance source that electrode can be used as in the equipment comes work.In certain embodiments, substrate or other blocking materials can with substance reaction to cause volume or dimensional changes.For example, silicon wafer or other metal or the substrate that comprises metal can be made by lithiumation and occur volume or dimensional changes when the charged of electrochemical cell.
Be used for can be selected to and with substance reaction (for example lithiumation and take off lithium) time, show some character at the material that electrode of the present invention uses.Material shows the volume or the dimensional changes (for example excitation) of a certain type or quantity when for example, can be selected in being used in as electrochemical cell described here.Those of ordinary skills can use simple and easy filler test to select such material.In some cases, the character of material and/or behavior can be known, and those of ordinary skills can for example select material to be fit to concrete the application based on required volume-variation amount.As people such as A.Yamada at J.Electrochem, Soc., 148, described in the A224 (2001), for example known phosphorus-olivine Li (Fe, Mn) PO 4Reversible lithium embed the Volume Changes that produces 7.4-10% based on the ratio of Fe/Mn.In some cases, can the behavior when the charging of battery and the discharge comes screening material as the material of electrode and observation material by incorporating in electrochemical cell.
In some cases, can select electrode material based on the ability of material and substance reaction.For example, when lithium is material, can select material based on the ability that material promptly and/or reversibly receives lithium particle (for example lithiumation) when the charge/discharge and/or emits lithium ion (for example taking off lithium).Also can determine the corresponding strain that material is related with the reversible reaction of material by the speed that the understanding ion is sent in the material.Can test experimentally or use such as the tabulation or the estimated value of the such character of ionic diffusion coefficient, ion and electron conductivity and surface reaction velocity coefficient and carry out such determining in theory.Those skilled in the art can use this information to select to be used as the suitable material of electrode.
Can make electrode by method as known in the art.In one embodiment, can be from comprising polymer adhesive and/or as the suspension casting electrode material based on powder of the conduction additive of carbon.The intensive layer that compacts that can roll extrusion (for example roll off) suspension has required active material percent by volume with formation under high pressure (for example every linear inch number ton).
Be suitable for comprising and to play the material that is used to store and transmit the medium of ion and plays the effect of spacer between anode and the negative electrode in some cases as electrolytical material.Can use any liquid, solid or the gel material that to store and to transmit ion, as long as material does not have electrochemistry and chemism and material to help to transmit ion (for example lithium ion) between anode and negative electrode with respect to anode and negative electrode.Electrolyte can be non-conductive to prevent short circuit between anode and the negative electrode.
Electrolyte can comprise in order to one or more ionic electrolytes that ionic conductance is provided and comprise one or more liquid electrolyte solvents, gelatin polymer material or polymer material.In some cases, electrolyte can be nonaqueous electrolyte.Suitable nonaqueous electrolyte can comprise organic bath, and these organic baths comprise liquid electrolyte, gelatin electrolyte and solid electrolyte.For example Dorniney is at Lithium Batteries (New Materials, Developmentsand Perspectives, the 4th chapter 137-165 page or leaf, Elsevier, Amsterdam (1994)) in and people such as Alamgir at Lithium Batteries (New Materials, Developmentsand Perspectives, the 3rd chapter 93-136 page or leaf, the example of nonaqueous electrolyte has been described Elsevier, Amsterdam (1994)).The example of non-aqueous electrolyte solvent includes but not limited to non-aqueous organic solvent, as for example N-methylacetamide, acetonitrile, acetal, ketal, ester, carbonite, sulfone, sulphite, sulfolane, aliphatic ether, cyclic ethers, glyme, polyethers, phosphate ester, siloxane, dioxolanes, N-alkyl pyrrolidone, its substitutive derivative (for example its halide derivative) and combination thereof.
In certain embodiments, electrochemical cell can also comprise in the system of being positioned or the equipment, for example be positioned blocking layer or spacer material (for example layer) between negative electrode and the anode.Thereby spacer can be the material of anode and negative electrode being isolated mutually or insulating and preventing short circuit and allow to transmit ion between anode and negative electrode.Being suitable for material as spacer material comprises the material of material with high elastic modulus and/or high hardness (for example rigidity), electrical insulation and/or has and be enough to stand high pressure, weight and/or strain (for example load) and the material of not loss of function.In some cases, partition layer can be porose.The example of spacer material comprises glass, pottery, silicate ceramics, steinheilite, aluminium oxide, aluminosilicate or other mixed-metal oxides or the nitride or the carbide of electrical insulation.In some cases, partition layer can comprise polymeric material.The partition layer that for example comprises elastic material can be useful when the shearing motion that allows between one or more parts.
In one embodiment, can use pottery handle or the paint-on technique field in the known following method of those of ordinary skill on the surface at one or two electrodes before the assembled layers, porose spacer material is cast into particle or slurry layer, all spray deposited in this way, the scraper coatings of these methods, silk-screen printing, net apply, counter-rotating (comma-reverse) applies or channel mould (slot-die) applies at interval.
Equipment of the present invention can also comprise in order to be fit to the concrete optional feature of using.For example, equipment of the present invention can comprise power supply, current collector (such as the current collector that comprises conductive material), outer enclosure layer, partition layer etc.Encapsulated layer can comprise electrochemistry insulating material or other protective material.
As pretreatment or handle this system or equipment alternatively before the actuator.The pretreatment of equipment can strengthen mechanical property, hardness, excitation energy density, excitation strain, reversibility and/or the life-span of equipment and/or can reduce creep strain and the strain sluggishness.In some cases, equipment or its one or more parts can be subjected to hydrostatic pressure and/or uniaxial stress with the material and/or the parts of ruggedized equipment and/or reduce the free volume amount.In certain embodiments, applied pressure can be 10,000psi, 20,000psi, 30,000psi, 45,000psi or bigger.Be to be understood that thereby any amount of exerting pressure can be used for pre-processing device and prevent the internal fault of equipment and/or can realize the improvement of equipment performance.
Following example be intended to illustrate some embodiment of the present invention, but will be not understood to limit the scope of the invention and also not have illustration complete scope of the present invention.
Example 1
Confession driving type electrochemical pump
In this indication example, can use actuator of the present invention as the confession driving type electrochemical pump that is used for insulinization.
The 1st paradiabetes clinical treatment is insulinization normally, wherein is used in combination long-acting and injection short-acting insulin according to regular blood glucose measurement.Treatment can comprise the insulin infusion pumps therapy that comprises continuous subcutaneous infusion of insulin (CSII), and this therapy is allotted the insulin of rapid onset from the pump of microprocessor control by microcatheter.Some existing pumps can be allotted rapid onset insulin continuously and ascending-dose can be provided before the meal or after the meal.Infusion is provided with change in per three days, thereby for multiple injection every day (MDI) therapy of routine, effectively frequency injection reduces significantly.The exclusive use of onset insulin has obtained improved greatly dosage predictability rapidly, as long as the long-acting form of insulin works by form the storage storehouse below skin.Yet the speed that insulin discharges from such storage storehouse may be looked such as the such factor of physical activity and be changed significantly.Confession driving type electrochemical pump can solve the problem that effective frequency injection reduces and the insulin rate of release changes.
Confession driving type electrochemical pump can be designed to send the 2.0mL useful load in 72 hours period.Figure 16 shows the schematic design that is used to confess driving type electrochemical pump 350.Negative electrode 355 provides the lithium source, and positive electrode 360 is expansion elements.Battery is an electrochemical equilibrium, thereby the available lithium in the negative electrode can make positive electrode expand.Can design 300% volumetric expansion that pump is used for positive electrode, this same vertical shift that power is delivered to excitation plate that produces with piston, this excitation plate is applied to pressure the reservoir 365 that comprises insulin solutions again.The vertical displacement of positive electrode can be depended on its width/aspect ratio (being assumed to be 2: 1 here) and Volume Changes.Electrolyte can be the non-water lithium cell electrolyte of standard.Encapsulation can be and the current encapsulation similar polymerization thing encapsulation that is used for rechargable lithium ion cell.
Advantageously, can control the rate of release of insulin solutions by the suitable material of selecting to be used for to form positive electrode.For example, for the electrochemical pump with the low relatively positive electrode material of hardness, positive motor can be displaced to its new equilibrium locations lentamente when discharge.This can realize slowly applying power to reservoir, thus insulin slowly is infused in the health.
Pump can have the volume of 8.6mL, and this volume will allow<total equipment volume of 15mL.14.5g the pump quality should allow total equipment quality of about 20g.Utilization is to material and electrolytical suitable selection, and this pump design can be by required basic speed insulin delivery during 72 hours.For asking the corresponding pill speed of battery discharge speed with about C/5 (all told that is battery discharges 5 hours), can incorporate extra design improvement into.In addition and/or replace, pump can have and be used for the existing similar specification of continuous infusion pump size.For example, such as the Lilly product
Figure A20078003535100431
Rapid onset insulin be packaged into the solution that concentration is every milliliter 100 unit.The representative basis insulin level can per hour regulated between 0.5 to 1.5 unit.The meal bolus quantities of taking medicine can comprise that consuming every 10g carbohydrate is 1 unit, thereby may wish maximum 10 units of meal clothes.The pharmacodynamics of rapid onset insulin shows sent this dosage in 15 minutes.Any more of a specified duration sending can be seen some differences with the subcutaneous injection of same quantity.Therefore, sending peak rate is 0.1mL volume in 15 minutes.Cross-section area is 6.5cm 2The linear compression of reservoir require the maximum shift speed of 0.167 micron of 0.015cm in 15 minutes or per second.Gross payload every day of insulin solutions must be about 50 units or 0.5mL.Therefore, to need volume be the useful load of 1.5mL to three day of supplys.
Example 2
Electrochemical actuator
In this indication example, electrochemical actuator comprises the piezoelectric bimorph chip architecture, this structure comprise be adhered to the copper layer at size active lithium storage material layer.The copper layer and is not stable on electrochemistry at the operation electromotive force copper layer of electrochemical cell basically and lithium alloyage or embedding.This piezoelectric bimorph chip architecture forms the positive electrode of battery.The copper layer also can serve as the positive electrode current collector and can extend beyond final sealed cell to form joint or current feed or can join joint or the current feed that extends to beyond battery.Negative electrode is the lithium metal layer that is adhered to or is deposited on the copper layer that is used as negative current collector.Being positioned between two electrodes is porose spacer film, for example such as glass fiber cloth that uses in the structure of lithium ion battery or porose polymer spacers.Perfusion is such as electrolytical non-water lithium conductive liquid electrolyte or non-water power double layer capacitor commonly used in lithium primary cell or rechargeable battery technology in the stratiform battery.Example comprises following solvent, and this solvent comprises that ethylene carbonate and carbonic acid two ethyl volume ratios are 1: 1 mixture, and the concentration that has wherein inserted as lithium conduction salt is the LiPF of 1M 6, perhaps inserted identical LiPF 6The acetonitrile as solvent of salt.
Electrochemical actuator is sealed in the polymer encapsulated.Battery is in charged state when assembling, and wherein the tin positive electrode has the lithiumation electromotive force lower than lithium metal negative electrode.Thereby when connecting positive current collector and negative current collector electric current and flow between two electrodes, the lithium ion electric current flows to tin in inside from lithium.The alloyage of tin and lithium is implemented in the saturated volumetric expansion that can reach near 300% of tin when lithium.When volume increased when the tin layer because with lithium alloyage, the copper layer that it is adhered to provided mechanical constraint, and piezoelectric bimorph experience displacement (for example crooked).At negative electrode, the loss of lithium also may cause little stress, but because lithium has high tenacity near room temperature, the stress of this stress ratio positive electrode is much smaller.Therefore, entire cell is owing to the tin layer Volume Changes on the electrochemical actuator that comprises positive electrode experiences deflection.The deflection of battery is applied to pressure again and is positioned to the medicine reservoir adjacent with actuator.The medicine reservoir comprises the fluid that comprises medicine and is centered on by the deformable device such as bladder.Applied pressure causes from reservoir and allots medicine.
Example 3
The deflection of electrochemistry piezoelectric bimorph
In this indication example, the piezoelectric bimorph chip architecture of example 2 is made into the shape of as shown in Fig. 3 A-C semicircle or the deflection of " U " shape.One end of this deflection anchors to the support or the shell of allocation equipment, and the other end freely is shifted when the deflection of piezoelectric bimorph experience.When electrochemical cell discharged, this deflection stretched out, thereby and the free end of this deflection power is applied to the bladder that comprises medicine and allots medicine from bladder through via hole or valve.
Example 4
Confession driving type deformation actuator with built-in amplification
In this example, make electrochemical cell and study the ability that it encourages when applying voltage or electric current.Be to push porose ball by-325 netted tin powder (99.8%[metal basis], Alfa Aesar) in 1/2 inch the mould at diameter under the 750lbf.Ball weight is the thickness that 0.625g and measured one-tenth have 0.89mm.By 180 ℃ in the air smelting furnace with assembly heating 30 minutes, to use BiSnAg scolder (Indium Corporation of America) and flux #5RMA (Indium Corporation of America) that ball is welded to thickness be 15 microns Copper Foil.Use this electrode assemblie as the positive electrode in the electrochemical cell, (~0.8mm thickness is Aldrich) as negative electrode and use the lithium paper tinsel.
Two-layer Celgard 2400 spacers are used for isolating tin positive electrode and lithium paper tinsel negative electrode.The lithium foil electrode is attached to the current collector of also being made by the Copper Foil of 15 micron thickness.Use is by (volume ratio is 4: 1: 3: the 1.33M LiPF that dissolves in the mixed solvent 2) at ethylene carbonate, propylene carbonate, dimethyl carbonate and methyl ethyl carbonate 6The liquid electrolyte of forming.Use the heat sealing thing with cell sealing in the big envelope of making by polyethylene pack material.The off load voltage of battery is 2.8-2.9V when assembling, and this shows that it is in charged state.Cell voltage promptly drops to relative steady state value 0.5-0.4V when discharge, and this is the feature of Sn-Li electrochemistry coupling.
Battery discharges by 1 ohmic resistor that connects positive current collector and negative current collector.With the plane vertical measurement displacement of tin dish and lithium paper tinsel, measure the battery of discharge from the linear variable differential transformation device (LVDT) of Micro-Epsilon and use.Come survey measurements by National Instrument NI-USB 6009 data acquisition equipments with LabView (National Instruments) interface.Figure 17 shows the plotted curve from the displacement of the gained of this experiment according to the time.
After the initial small amount of compression that is caused by lithium and spacer that applying on a small quantity of LVDT produces under the power, actuator extends 1.8mm along with its discharge in 11 hours period.This absolute displacement surpasses the original depth of Sn ball according to the factor that is about two.After test, the check of the actuator that decomposes shown discharge to occur, wherein lithium from negative electrode corrode and with tin ball alloyage from a side.The displacement that easily observes actuator is deformed into " cup-shaped " shape owing to cylindrical tin ball, and its convex face is the side towards spacer and lithium electrode.The shape deformation of therefore visible tin ball is owing to the differential strain that produces on the ball, and wherein the side experience towards lithium electrode expands.After distortion, show the load that to support under the situation that the ball that is being out of shape do not break more than 1kg at the mechanical load on the direction of displacement vertical with the plane of ball.Therefore, actuator has hardness basically, and with the same in the drug delivery applications that can allot fluid through one or more pin or microneedle, this will be for will being useful such as the allocation of the bladder of fill fluid or the application of pumping.Near actuator by placing this example the bladder of such fill fluid and integral body packed in the rigid container can be implemented drug delivery device.
Such medication injection device is for example sent and will be fit to for (72 hours) on the 3rd of insulin.Such as the Lilly product
Figure A20078003535100461
Rapid onset insulin generally be packaged into the solution that concentration is every milliliter 100 unit.Total load every day of insulin solutions can be about 50 units or 0.5mL.Therefore, the pump with three day of supplys can hold~total volume of 2.0mL.For example, the actuator of describing in this example produces the displacement more than 1.5mm, and this displacement is 13cm acting on area 2Reservoir the time can easily obtain required 2.0mL volume.The representative basis insulin level can per hour regulated between 0.5 to 1.5 unit.The meal bolus quantities of taking medicine can comprise that consuming every 10gm carbohydrate is 1 unit, thereby may wish maximum 10 units of meal clothes.The drug effect of onset insulin hint can be sent this dosage in 15 minutes rapidly.Therefore, sending peak rate can be corresponding to 5% of total volume in 15 minutes.Carry out complete send of the displacement of 1.5mm corresponding to 2mL insulin load, the actuator in this example can easily satisfy the pill rate requirement.In order to slow down speed, can implement as hereinafter in the increase of external loading resistance described in the example 7 or dutycycle control to satisfy basic rate requirement.
Owing to produce electrochemistry excitation due to the differential strain on the electrode, this example can confirm electrochemical actuator and the drug delivery device in the certain embodiments of the invention by confirming.The consideration that the net volume of actuator in the discharge process of battery changes shows that the gained displacement does not change net volume variation not relevant and in fact symbol and battery on the contrary with net volume.More various Li xThe part molecular volume of lithium and the molecular volume of pure lithium in the Sn alloy observe pure lithium and have bigger molecular volume, and therefore wherein lithium is the discharge realization net volume minimizing of the battery of negative electrode.For example, the compound L i that the Li/Sn stoichiometry is low relatively 2.5Sn has 38.73cm 3Mol -1Molecular volume.Because pure Sn metal has 16.24cm 3Mol -1Molecular volume, so with the difference 22.49cm of compound 3Mol -1Be by Li 2.5The volume that 2.5Li among the Sn occupies.Comparatively speaking, the molecular volume of pure Li is 13.10cm 3Mol -1Thereby 2.5 mole of lithium metals will have 32.75cm 3Volume.Therefore, battery discharges fully to form Li on positive electrode side 2.5Sn will realize that 2.5 mole of lithium are sent to Sn from the Li electrode, and this realizes the clean minimizing of equipment volume.Similarly, the compound L i that stoichiometry is high relatively 4.4The molecular volume of Li is 42.01cm among the Sn 3Mol -1, and 4.4 moles pure Li metal has 57.62cm 3Mol -1Volume.The discharge of equally, such battery realizes that net volume reduces.Although the time negative Volume Changes is arranged, still appear at outwards or just being shifted of observing in the actuator of this example in discharge.The distortion of the deflection of actuator or " extruding " pattern is amplified because the distortion due to the differential strain on the ball.
Example 5
The constant-current discharge of electrochemical actuator
The constant-current discharge of research electrochemical cell in following example.Utilization is made electrochemical cell described in example 4 as contacting the conduction copper self adhesive tape rather than the scolder that use between porose tin ball and copper collector.Use Maccor 4300 cell testers (Maccor) that battery is carried out constant-current discharge (constant discharge current).Tin ball weight is 0.628g and is measured as the thickness with 1.06mm.Suppose that all tin are become compound L i by lithiumation 4.4Sn, the theoretical capacity of ball are 624mAh.The off load voltage of battery is 2.8-2.9V when assembling, and this shows that it is in charged state.Battery is discharged to 0.01V at 0.88mA.Discharge capacity is 56.22mAh, this show battery in 63.6 hours discharge time, be discharged to it theoretical capacity only 9%.Yet, observe the tin ball and be squeezed into approximately uniform distortion in the mode identical with actuator in the example 1.If this example confirms closed just going between and negative lead-in wire then the current limited of the electrochemical actuator that can spontaneously discharge and encourage are controlled in the circuit externally.
Example 6
Electrochemistry piezoelectric bimorph actuator
By shelter with the Kapton self adhesive tape thickness be 50 microns and area be 40mm * 5mm Copper Foil a side and paper tinsel be dipped in the molten tin make the piezoelectric bimorph plate electrode to apply a side with the tin layer.The constraint that is expected to be provided by Copper Foil when the electrochemistry lithiumation of tin will realize crooked or " curling " of piezoelectric bimorph chip architecture, and wherein convex side is a lithiumation tin.Use this piezoelectric bimorph as positive electrode assemble to example 4 and example 5 in the similar electrochemical cell of electrochemical cell, and utilize and assemble towards the tin layer and the lithium paper tinsel negative electrode of spacer.The off load voltage of battery is 2.8-2.9V when assembling, and this shows that battery is in charged state.Battery with the electric current of 0.089mA by constant-current discharge to 0.01V.Discharge capacity is 7.7mAh, and this representative is about 50% discharge condition and hypothesis Li with regard to about 10 microns tin thickness 4.4The complete lithiumation of Sn is formed.Divide electrolytic cell and tin-copper piezoelectric bimorph plate electrode to show bending basically at all free edges of piezoelectric bimorph after discharge, this has confirmed shape deformation.
In other experiment, thickness be 0.05mm (99.999%[metal basis], Alfa Aesar) and 0.10mm (99.99%[metal basis], Alfa Aesar) tin metal paper tinsel sample joins the Copper Foil of 15 micron thickness separately to, and this forms area is the smooth piezoelectric bimorph plate electrode of 20mm * 5mm.Use two-layer Celgard 2400 spacers to construct electrochemical cell to isolate tin/copper piezoelectric bimorph positive electrode and thick lithium paper tinsel (Aldrich) negative electrode of 0.4mm.For each battery, it also is the current collector of being made by the Copper Foil of 15 micron thickness that the lithium foil electrode is attached to, and uses by (volume ratio is 4: 1: 3: the 1.33M LiPF that dissolves in the mixed solvent 2) at ethylene carbonate, propylene carbonate, dimethyl carbonate and methyl ethyl carbonate 6The electrolyte of forming.Use the heat sealing thing with each cell sealing in the big envelope of making by polyethylene pack material.
Use Maccor 4300 cell testers (Maccor) that battery is carried out constant-current discharge.The battery that uses the thick tinfoil paper of 0.10mm to make is discharged to 0.01V at 0.4178mA.Discharge capacity is 1.65mAh (a theoretical discharge capacity 4%).Figure 19 illustrates the discharge that is used for this device distributes.Observe the piezoelectric bimorph plate electrode and " curl " at all free edges when dismounting, this confirms serious deformation.
Use battery that 0.05mm tinfoil paper makes to be 1.65mAh (theoretical capacity 4%) until discharge capacity in the 0.4076mA discharge.Figure 20 illustrates the discharge that is used for this equipment distributes.Similar to 0.10mm tinfoil paper piezoelectric bimorph, also all the free edge performances at piezoelectric bimorph are crooked when decomposing for this equipment.
These examples confirm various electrochemistry piezoelectric bimorph actuator of the present invention.These results also show and can need not electrochemical cell of the present invention is fully discharged so that obtain obvious deformation, and the differential strain that the discharge of the only small percentage of theoretical battery capacity is realized may be enough to realize required excitation
Example 7
The dutycycle control of electrochemical actuator
The design electrochemical actuator similar to design described in the example 1 carries out the dutycycle controlled discharge so that obtain slow rate of deformation.Dutycycle is by electronic relay (Radio Shack) control, this relay be turn on and off by Current Control from Maccor 4300 cell testers (Maccor) and be connected with 1 ohm of external loading resistor in series at the terminal of electrochemical cell.Relay is closed in the cell tester received current and disconnect during in current interruptions.The dutycycle of configuration 20% is wherein connected in the 50ms of electric current among total period of 200ms.Figure 18 shows the plotted curve of the shifted curve that is used for the electrochemistry deformation actuator recently controlled by 20% duty.The gained displacement of equipment shown in Figure 18 confirms the distortion of actuator at low controllable rate.As described here, a kind of optional method that obtains controlled low rate of deformation can be by more high-resistance external loading the actuator among Figure 18 to be discharged.
Example 8
Confession driving type electrochemical actuator with bigger driving voltage
Under some circumstances,,, may wish the average discharge volt higher average discharge volt of Billy with the first preceding example of tin and lithium metal such as when the sufficient driving voltage of needs even there is obvious battery polarization.Since antimony than the relative higher off load voltage of lithium metal (~0.95V), antimony can be the useful deformation electrode material that is used for such application.Use-325 netted antimony powder ends (99.5%[metal basis], Alfa Aesar) rather than tin powder as in the example 1, to prepare electrochemical apparatus.In being 1/2 inch mould, diameter pushes tin powder at 2250lbf.The gained ball is that 0.687g and 1.31mm are thick, and this theoretical capacity with 454mAh is corresponding.Sample at the electric current constant-current discharge of 3.025mA to 0.01V.Discharge capacity is 49.98mAh (theoretical capacity 11%) and the gross distortion of realizing the tin ball.
Although described and illustrated several embodiments of the present invention here, but those of ordinary skills will easily imagine various other means and/or the structure that is used to carry out function described herein and/or obtains result described herein and/or one or more advantage, and various such variation and/or modification are considered as within the scope of the invention.More generally, those skilled in the art will readily appreciate that all parameters described herein, size, material and configuration be for example and actual parameter, size, material and/or configuration will depend on one or more concrete application of being quoted of instruction of the present invention.Those skilled in the art will recognize that or can only use normal experiment to establish the many equivalent embodiment of the specific embodiment of the invention described herein.Therefore will understand previous embodiment and be only present by example and can be in the scope of claims and equivalents thereof with specifically describing and claimed mode mode in addition be implemented the present invention.The present invention relates to each independent characteristic described herein, system, product, material, kit and/or method.In addition, if it is internally inconsistent that such feature, system, product, material, kit and/or method do not have, then any combination of two or how such feature, system, product, material, kit and/or method is included in the scope of the present invention.
In specification and in claims during inapplicable numeral-classifier compound, unless clearly opposite specified otherwise should be understood to mean " at least one/a kind of ".
In specification and the phrase that in claims, uses " and/or " should be understood to mean " any or two " in the element of such combination, promptly jointly exist in some cases and the element that exists dividually in other cases.Unless clearly indicate on the contrary, except by " and/or " can have other element relevant with those elements of concrete sign or that have nothing to do alternatively the element of the concrete sign of clause.Therefore as unrestricted example, can refer to A in one embodiment and do not have B (comprising the element except B alternatively), refer to B in another embodiment and do not have A (comprising the element except A alternatively), refer to A and B (comprising other element alternatively) etc. in another embodiment when referring to " A and/or B " when being used in combination as " comprising " with open language.
As in the specification and using in claims, " perhaps " should be understood to have with definition as mentioned " and/or " identical implication.For example, when item in separation is enumerated, " perhaps " or " and/or " should be interpreted as comprising, comprise that promptly at least one in enumerating of a plurality of elements or element also comprises a plurality of and comprise the item of additionally not enumerating alternatively.Only such as " ... in only one " or " ... in accurate one " or when using in the claims " by ... form " such term that clearly indicates on the contrary just will refer to and comprise a plurality of elements or the element accurate element in enumerating.Generally speaking, term used herein " perhaps " should only be interpreted as representing the option (" or another but be not two ") of exclusiveness in time before the exclusiveness term such such as " any ", one of " ... ", " ... in only " or " ... in accurate "." basically by ... form " should have its ordinary meaning that it uses in being used in claims the time in the Patent Law field.
As in the specification and using in claims, phrase " at least one " when referring to the enumerating of one or more element, should be understood to mean at least one element of selecting in any one or a plurality of element from element is enumerated, but and not necessarily be included in each element that element specifically enumerates in enumerating at least one, do not get rid of any combination of the element of element in enumerating yet.This definition also allows can have relevant with those elements of concrete sign or irrelevant element alternatively the concrete element that identifies in the element that phrase " at least one " refers to is enumerated.Therefore, as unrestricted example, " at least one among A and the B " (perhaps equivalence for " at least one among A or the B " or equivalence for " at least one among A and/or the B ") can refer at least one in one embodiment, comprises a plurality of A alternatively and do not have B (and comprise alternatively except B element); Refer at least one in another embodiment, comprise a plurality of B alternatively and do not have A (and comprise alternatively except A element); Refer at least one in another embodiment, comprise that alternatively a plurality of A and at least one promptly comprise a plurality of B (and comprising other element alternatively) etc. alternatively.
In claims and in above-mentioned specification, such as " comprising ", " carrying ", " having ", " comprising ", " relating to ", " maintenance " wait all transition phrases be interpreted as open, promptly mean and include but not limited to.As in United States Patent Office's patent examination handbook the 2111.03rd joint, setting forth like that, have only the transition phrase " by ... form " and " basically by ... composition " should be respectively closure or semi-closed phrase.

Claims (151)

1. exciter system, it is constructed and arranged to be displaced to second orientation from first orientation, and described exciter system comprises:
At least one electrochemical cell that comprises negative electrode and positive electrode,
In wherein said negative electrode and the positive electrode one or two are actuators and comprise first portion and second portion, and
Wherein when charging and/or discharge, material embeds, takes off the dimensional changes that embedding, alloyage produce with respect to described second portion in, oxidation, reduction or the described first portion of plating and experience with the degree different with described second portion, give thus described actuator between described first portion and described second portion differential strain and cause the displacement of at least a portion of described actuator
The displacement of described actuator is done mechanical work and be need not to be coupled to the structure of doing described merit.
2. exciter system according to claim 1, wherein said first portion and described second portion electric connection.
3. exciter system according to claim 1, wherein said material are to embed material.
4. exciter system according to claim 1, wherein said material is a proton.
5. exciter system according to claim 1, wherein said material are the plating materials.
6. exciter system according to claim 1, wherein said first portion and second portion are formed by different materials.
7. exciter system according to claim 1, wherein said first portion and second portion are formed by substantially the same material.
8. exciter system according to claim 1, wherein said first portion has different electromotive forces with second portion.
9. exciter system according to claim 1, wherein said first portion and second portion are to be exposed to described material in various degree.
10. exciter system according to claim 1 also comprises following structure, and described structure comprises at least one part that is constructed and arranged to be displaced to from described first orientation by the displacement of described actuator second orientation.
11. exciter system according to claim 1, wherein said material embed, take off embedding basically or alloyage does not still embed, takes off embedding or alloyage in described second portion in described first portion.
12. exciter system according to claim 1, wherein said first portion embeds described material so that cause differential strain between described first portion and described second portion with the degree different with described second portion.
13. exciter system according to claim 1, wherein said first portion with the degree different and described material alloyage with described second portion so that between described first portion and described second portion, cause differential strain.
14. exciter system according to claim 1, wherein said first portion and described second portion are conductive.
15. exciter system according to claim 1 wherein when charging or discharge, causes the volume displacement of fluid from described reservoir thereby the displacement of at least a portion of described actuator applies power on reservoir.
16. exciter system according to claim 15, wherein said fluid comprises medicine.
17. exciter system according to claim 16, wherein said medicine is an insulin.
18. exciter system according to claim 1, wherein said positive electrode and/or negative electrode are the shapes of bar, plate, sheet, cup, pleated sheet or band.
19. exciter system according to claim 1, wherein said positive electrode and/or negative electricity are very nonplanar.
20. exciter system according to claim 1, wherein said positive electrode and/or negative electrode are plate or ball shape.
21. exciter system according to claim 1, wherein said positive electrode and/or negative electrode comprise at least one groove.
22. exciter system according to claim 1, wherein said positive electrode and/or negative electrode have a plurality of " legs " or " arm " or branch road.
23. exciter system according to claim 1, wherein said electrochemical cell is constructed and arranged to spontaneously discharge.
24. exciter system according to claim 1, wherein said exciter system is coupled to the structure of doing mechanical work.
25. exciter system according to claim 1, wherein said exciter system is not coupled to the structure of doing mechanical work.
26. exciter system according to claim 1, wherein said actuator displacement is generated by the positive volume or the dimensional changes of described exciter system.
27. exciter system according to claim 1, wherein said actuator displacement is generated by the zero volume or the dimensional changes of described exciter system.
28. exciter system according to claim 1, wherein said actuator displacement is generated by the negative volume or the dimensional changes of described exciter system.
29. an exciter system, it is constructed and arranged to be displaced to second orientation from first orientation, and described exciter system comprises:
At least one electrochemical cell that comprises negative electrode and positive electrode,
In wherein said negative electrode and the positive electrode one or two are actuators and comprise first portion and second portion, and
Wherein when charging and/or discharge, material embeds, takes off the dimensional changes that embedding or alloyage produce with respect to described second portion in described first portion and experience with the degree different with described second portion, give thus described actuator between described first portion and described second portion differential strain and cause the displacement of at least a portion of described actuator
The displacement of described actuator is done mechanical work and be need not to be coupled to the structure of doing described merit.
30. exciter system according to claim 1, wherein said first portion and described second portion electric connection.
31. exciter system according to claim 29, wherein said material are to embed material.
32. exciter system according to claim 29, wherein said material is a proton.
33. exciter system according to claim 29, wherein said material are the plating materials.
34. exciter system according to claim 29, wherein said first portion and second portion are formed by different materials.
35. exciter system according to claim 29, wherein said first portion and second portion are formed by substantially the same material.
36. exciter system according to claim 29, wherein said first portion has different electromotive forces with second portion.
37. exciter system according to claim 29, wherein said first portion and second portion are to be exposed to described material in various degree.
38. exciter system according to claim 29 also comprises following structure, described structure comprises at least one part that is constructed and arranged to be displaced to from described first orientation by the displacement of described actuator second orientation.
39. exciter system according to claim 29, wherein said material embed, take off embedding basically or alloyage does not still embed, takes off embedding or alloyage in described second portion in described first portion.
40. exciter system according to claim 29, wherein said first portion embeds described material so that cause differential strain between described first portion and described second portion with the degree different with described second portion.
41. exciter system according to claim 29, wherein said first portion with the degree different and described material alloyage with described second portion so that between described first portion and described second portion, cause differential strain.
42. exciter system according to claim 29, wherein said first portion and described second portion are conductive.
43. exciter system according to claim 29 wherein when charging or discharge, causes the volume displacement of fluid from described reservoir thereby the displacement of at least a portion of described actuator applies power on reservoir.
44. according to the described exciter system of claim 43, wherein said fluid comprises medicine.
45. according to the described exciter system of claim 44, wherein said medicine is an insulin.
46. exciter system according to claim 29, wherein said positive electrode and/or negative electrode are the shapes of bar, plate, sheet, cup, pleated sheet or band.
47. exciter system according to claim 29, wherein said positive electrode and/or negative electricity are very nonplanar.
48. exciter system according to claim 29, wherein said positive electrode and/or negative electrode are plate or ball shape.
49. exciter system according to claim 29, wherein said positive electrode and/or negative electrode comprise at least one groove.
50. exciter system according to claim 29, wherein said positive electrode and/or negative electrode have a plurality of " legs " or " arm " or branch road.
51. exciter system according to claim 29, wherein said electrochemical cell is constructed and arranged to spontaneously discharge.
52. exciter system according to claim 29, wherein said exciter system is coupled to the structure of doing mechanical work.
53. exciter system according to claim 29, wherein said exciter system is not coupled to the structure of doing mechanical work.
54. exciter system according to claim 29, wherein said actuator displacement is generated by the positive volume or the dimensional changes of described exciter system.
55. exciter system according to claim 29, wherein said actuator displacement is generated by the zero volume or the dimensional changes of described exciter system.
56. exciter system according to claim 29, wherein said actuator displacement is generated by the negative volume or the dimensional changes of described exciter system.
57. an exciter system, it is constructed and arranged to be displaced to second orientation from first orientation, and described exciter system comprises:
At least one electrochemical cell that comprises negative electrode and positive electrode,
In wherein said negative electrode and the positive electrode one or two are actuators and comprise first portion and second portion, and
Wherein described first portion with the degree oxidation different with described second portion and/or when reduction the dimensional changes that produces with respect to described second portion of described first portion experience, give thus described actuator between described first portion and described second portion differential strain and cause the displacement of at least a portion of described actuator
The displacement of described actuator is done mechanical work and be need not to be coupled to the structure of doing described merit.
58. exciter system according to claim 1, wherein said first portion and described second portion electric connection.
59. exciter system as claimed in claim 57 also is included in the oxidation of described first portion and/or when reduction to embed, take off embedding or alloyage in the material of described first portion with the degree different with described second portion.
60. according to the described exciter system of claim 59, wherein said material is to embed material.
61. according to the described exciter system of claim 59, wherein said material is a proton.
62. according to the described exciter system of claim 59, wherein said material is the plating material.
63. according to the described exciter system of claim 57, wherein said first portion and second portion are formed by different materials.
64. according to the described exciter system of claim 57, wherein said first portion and second portion are formed by substantially the same material.
65. according to the described exciter system of claim 57, wherein said first portion has different electromotive forces with second portion.
66. according to the described exciter system of claim 59, wherein said first portion and second portion are to be exposed to described material in various degree.
67. according to the described exciter system of claim 57, also comprise following structure, described structure comprises at least one part that is constructed and arranged to be displaced to from described first orientation by the displacement of described actuator second orientation.
68. according to the described exciter system of claim 59, wherein said material embeds, takes off embedding basically or alloyage does not still embed, takes off embedding or alloyage in described second portion in described first portion.
69. according to the described exciter system of claim 59, wherein said first portion embeds described material so that cause differential strain between described first portion and described second portion with the degree different with described second portion.
70. according to the described exciter system of claim 59, wherein said first portion with the degree different and described material alloyage with described second portion so that between described first portion and described second portion, cause differential strain.
71. according to the described exciter system of claim 57, wherein said first portion and described second portion are conductive.
72., wherein when charging or discharge, cause the volume displacement of fluid from described reservoir thereby the displacement of at least a portion of described actuator applies power on reservoir according to the described exciter system of claim 57.
73. according to the described exciter system of claim 72, wherein said fluid comprises medicine.
74. according to the described exciter system of claim 73, wherein said medicine is an insulin.
75. according to the described exciter system of claim 57, wherein said positive electrode and/or negative electrode are the shapes of bar, plate, sheet, cup, pleated sheet or band.
76. according to the described exciter system of claim 57, wherein said positive electrode and/or negative electricity are very nonplanar.
77. according to the described exciter system of claim 57, wherein said positive electrode and/or negative electrode are plate or ball shape.
78. according to the described exciter system of claim 57, wherein said positive electrode and/or negative electrode comprise at least one groove.
79. according to the described exciter system of claim 57, wherein said positive electrode and/or negative electrode have a plurality of " legs " or " arm " or branch road.
80. according to the described exciter system of claim 57, wherein said electrochemical cell is constructed and arranged to spontaneously discharge.
81. according to the described exciter system of claim 57, wherein said exciter system is coupled to the structure of doing mechanical work.
82. according to the described exciter system of claim 57, wherein said exciter system is not coupled to the structure of doing mechanical work.
83. according to the described exciter system of claim 57, wherein said actuator displacement is generated by the positive volume or the dimensional changes of described exciter system.
84. according to the described exciter system of claim 57, wherein said actuator displacement is generated by the zero volume or the dimensional changes of described exciter system.
85. according to the described exciter system of claim 57, wherein said actuator displacement is generated by the negative volume or the dimensional changes of described exciter system.
86. an exciter system, it is constructed and arranged to be displaced to second orientation from first orientation, and described exciter system comprises:
At least one electrochemical cell that comprises negative electrode and positive electrode,
In wherein said negative electrode and the positive electrode one or two are actuators and comprise first portion and second portion, and
Wherein when charging and/or discharge, material with the degree electrochemical deposition different with described second portion in described first portion and the dimensional changes that produces with respect to described second portion of experience, give thus described actuator between described first portion and described second portion differential strain and cause the displacement of at least a portion of described actuator
The displacement of described actuator is done mechanical work and be need not to be coupled to the structure of doing described merit.
87. exciter system according to claim 1, wherein said first portion and described second portion electric connection.
88. 6 described exciter systems according to Claim 8, wherein said material are to embed material.
89. 6 described exciter systems according to Claim 8, wherein said material is a proton.
90. 6 described exciter systems according to Claim 8, wherein said material is the plating material.
91. 6 described exciter systems according to Claim 8, wherein said first portion and second portion are formed by different materials.
92. 6 described exciter systems according to Claim 8, wherein said first portion and second portion are formed by substantially the same material.
93. 6 described exciter systems according to Claim 8, wherein said first portion has different electromotive forces with second portion.
94. 6 described exciter systems according to Claim 8, wherein said first portion and second portion are to be exposed to described material in various degree.
95. 6 described exciter systems also comprise following structure according to Claim 8, described structure comprises at least one part that is constructed and arranged to be displaced to from described first orientation by the displacement of described actuator second orientation.
96. 6 described exciter systems according to Claim 8, wherein said material embed basically, take off embedding or alloyage in described first portion but do not embed, take off embedding or alloyage in described second portion.
97. 6 described exciter systems according to Claim 8, wherein said first portion embeds described material so that cause differential strain between described first portion and described second portion with the degree different with described second portion.
98. 6 described exciter systems according to Claim 8, wherein said first portion with the degree different and described material alloyage with described second portion so that between described first portion and described second portion, cause differential strain.
99. 6 described exciter systems according to Claim 8, wherein said first portion and described second portion are conductive.
100. 6 described exciter systems wherein when charging or discharge, cause the volume displacement of fluid from described reservoir thereby the displacement of at least a portion of described actuator applies power on reservoir according to Claim 8.
101. according to the described exciter system of claim 100, wherein said fluid comprises medicine.
102. according to the described exciter system of claim 101, wherein said medicine is an insulin.
103. 6 described exciter systems according to Claim 8, wherein said positive electrode and/or negative electrode are the shapes of bar, plate, sheet, cup, pleated sheet or band.
104. 6 described exciter systems according to Claim 8, wherein said positive electrode and/or negative electricity are very nonplanar.
105. 6 described exciter systems according to Claim 8, wherein said positive electrode and/or negative electrode are plate or ball shape.
106. 6 described exciter systems according to Claim 8, wherein said positive electrode and/or negative electrode comprise at least one groove.
107. 6 described exciter systems according to Claim 8, wherein said positive electrode and/or negative electrode have a plurality of " legs " or " arm " or branch road.
108. 6 described exciter systems according to Claim 8, wherein said electrochemical cell is constructed and arranged to spontaneously discharge.
109. 6 described exciter systems according to Claim 8, wherein said exciter system is coupled to the structure of doing mechanical work.
110. 6 described exciter systems according to Claim 8, wherein said exciter system is not coupled to the structure of doing mechanical work.
111. 6 described exciter systems according to Claim 8, wherein said actuator displacement is generated by the positive volume or the dimensional changes of described exciter system.
112. 6 described exciter systems according to Claim 8, wherein said actuator displacement is generated by the zero volume or the dimensional changes of described exciter system.
113. 6 described exciter systems according to Claim 8, wherein said actuator displacement is generated by the negative volume or the dimensional changes of described exciter system.
114. an actuator equipment comprises:
At least one electrochemical cell, comprise negative electrode, positive electrode and following material, described material can embed, take off embedding, the alloyage first portion in, oxidation, reduction or the described electrochemical cell of plating with the degree different with the second portion of described electrochemical cell, thereby described first portion and/or second portion cause the actuator displacement of doing mechanical work in when discharge experience dimensional changes thus, wherein said electrochemical cell be constructed and arranged to charge during fabrication and after using partly discharge or after discharge first not further the charging.
115. exciter system according to claim 1, wherein said first portion and described second portion electric connection.
But 116. the time be disposable in discharge according to the described actuator equipment of claim 114.
117. according to the described actuator equipment of claim 114, wherein said equipment is fluid pump.
118. according to the described actuator equipment of claim 114, wherein said equipment is the infused fluid pump that is used for fluid is delivered to health.
119., cause the volume displacement of fluid from described reservoir thereby wherein on reservoir, apply power in the described actuator displacement of when discharge according to the described actuator equipment of claim 114.
120. according to the described actuator equipment of claim 119, wherein said fluid comprises medicine.
121. according to the described actuator equipment of claim 120, wherein said medicine is an insulin.
122. according to the described actuator equipment of claim 119, the constant rate of wherein said volume displacement or variable.
123., wherein control described volume displacement by the discharge rate of controlling described battery according to the described actuator equipment of claim 119.
124. according to the described actuator equipment of claim 119, wherein the resistance of the circuit by changing described battery discharge is controlled described volume displacement.
125. according to the described actuator equipment of claim 119, described actuator equipment has dutycycle, wherein said dutycycle is controlled by the external circuit of disconnection and/or closed and described actuator device association.
126. according to the described actuator equipment of claim 114, wherein said dimensional changes is provided by the varying sized pore electrod that has when the ion exchange.
127. according to the described actuator equipment of claim 126, wherein said pore electrod is arranged is the fine and close thing of pressed powder or metal foam or at the size active material with at the composite of size non-viable material, described electrode comprises additive alternatively.
128. according to the described actuator equipment of claim 126, the wherein said dimensional changes that has pore electrod experience when charging or discharge to comprise bending, deflection or extruding.
129. according to the described actuator equipment of claim 128, wherein said have pore electrod to comprise gradient of porosity.
130. according to the described actuator equipment of claim 128, wherein said have pore electrod also to comprise surface layer.
131. according to the described actuator equipment of claim 130, wherein said surface layer is to have the bigger degree of pore electrod to be embedded into, to take off embedding, alloyage, oxidation, reduction or plating than described.
132. according to the described actuator equipment of claim 114, the embedding with the material of from proton, alkali metal ion, Ion complex, hydroxide ion, carbanion, chloranion, sulfate ion and phosphate anion, selecting or expanding during alloyage of wherein said electrochemical cell at the size active material.
133. according to the described actuator equipment of claim 114, wherein said electrochemical cell at the size active material and lithium embeds or alloyage and comprise Al, Au, Ag, Ga, Si, Ge, Ti, Sn, Sb, Pb, Zn, carbon, graphite, hard carbon, mesoporous carbon, oxide, embed oxide, layered oxide, clay mineral, sulphide, laminate sulfide, TiS 2, MoS 2And WS 2In one or more.
134. according to the described actuator equipment of claim 114, wherein said electrochemical cell is constructed and arranged to spontaneously discharge.
135. an infusion pump comprises:
At least one electrochemical cell comprises negative electrode, positive electrode and embedding material, wherein said negative electrode and/positive electrode in charging and/or when discharge experience dimensional changes so that make fluid infusion in health.
136. according to the described infusion pump of claim 135, wherein said electrochemical cell is constructed and arranged to spontaneously discharge.
137. according to the described infusion pump of claim 135, wherein said fluid comprises liquid, solid-liquid mixture, slurry or gelatin.
138. according to the described infusion pump of claim 135, wherein said fluid comprises medicine.
139. according to the described infusion pump of claim 135, wherein said medicine is an insulin.
140. according to the described infusion pump of claim 135, the constant rate of wherein said infusion or variable.
141., wherein control the speed of described infusion by the discharge rate of controlling described battery according to the described exciter system of claim 114.
142. according to the described exciter system of claim 114, wherein the resistance of the circuit by changing described battery discharge is controlled the speed of described infusion.
143. according to the described exciter system of claim 119, described exciter system has dutycycle, wherein said dutycycle is controlled by the external circuit of disconnection and/or closed and described actuator device association.
144. an actuator, it is constructed and arranged to be used for the physiology facility, and described actuator comprises:
The first portion adjacent with second portion, wherein said first portion experiences dimensional changes when being exposed to the physiological fluid that comprises material, and wherein because the dimensional changes that electrochemistry embed, described material the oxidation/reduction of taking off embedding or described first portion from described first portion cause described actuator of the described material that is caused with contacting of described material in the described first portion.
145. exciter system according to claim 1, wherein said first portion and described second portion electric connection.
146. according to the described actuator of claim 144, wherein said first portion has different electromotive forces with described second portion.
147. according to the described actuator of claim 144, wherein said physiological fluid is a blood.
148. according to the described actuator of claim 144, wherein said material is a proton.
149. according to the described actuator of claim 144, in its implanted health.
150. according to the described actuator of claim 144, wherein said actuator is constructed and arranged to spontaneously discharge.
151. one kind is used for the electrochemical actuator of medicament administration to health comprised:
At least one negative electrode;
At least one positive electrode; And
Material,
Voltage that wherein said electrochemical actuator is applied or electric current, described thus voltage or electric current apply or it stops to apply and comprises that thereby the embedding of described material at least one electrode of described electrochemical actuator causes the volume or the dimensional changes of described electrochemical actuator, and
Wherein said volume or dimensional changes cause medicament administration in health.
CN2007800353514A 2006-07-26 2007-07-26 Electrochemical actuator Expired - Fee Related CN101589230B (en)

Applications Claiming Priority (5)

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CN102792476A (en) * 2009-12-11 2012-11-21 保尔·萨巴梯埃-图卢兹第三大学 Piezoelectric and/or pyroelectric composite solid material, method for obtaining same and use of such a material
CN103975236A (en) * 2011-09-29 2014-08-06 杨百翰大学 Lead-free oxygen sensor
CN107394296A (en) * 2016-05-03 2017-11-24 福特全球技术公司 Sensitively battery unit state-of-charge and health status monitoring based on strain
WO2018072677A1 (en) * 2016-10-17 2018-04-26 MicroMED Co., Ltd. Micro delivery device
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US10750987B2 (en) 2005-07-21 2020-08-25 Steadymed Ltd. Drug delivery device with electrically controlled volume changing means
CN113573453A (en) * 2021-08-19 2021-10-29 大连理工大学 Device for measuring surface charge of surface dielectric barrier discharge plasma exciter

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CN1231988C (en) * 2001-07-04 2005-12-14 上海神力科技有限公司 Deionizing system for fuel battery
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Cited By (10)

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Publication number Priority date Publication date Assignee Title
US10750987B2 (en) 2005-07-21 2020-08-25 Steadymed Ltd. Drug delivery device with electrically controlled volume changing means
CN102792476A (en) * 2009-12-11 2012-11-21 保尔·萨巴梯埃-图卢兹第三大学 Piezoelectric and/or pyroelectric composite solid material, method for obtaining same and use of such a material
CN102792476B (en) * 2009-12-11 2015-11-25 保尔·萨巴梯埃-图卢兹第三大学 Piezoelectricity and/or thermoelectricity solid synthetic material and its preparation method and application
CN103975236A (en) * 2011-09-29 2014-08-06 杨百翰大学 Lead-free oxygen sensor
CN107394296A (en) * 2016-05-03 2017-11-24 福特全球技术公司 Sensitively battery unit state-of-charge and health status monitoring based on strain
WO2018072677A1 (en) * 2016-10-17 2018-04-26 MicroMED Co., Ltd. Micro delivery device
CN108214466A (en) * 2018-02-26 2018-06-29 孟金来 Machine caterpillar
CN110202611A (en) * 2018-02-28 2019-09-06 精工爱普生株式会社 Robot
CN110202611B (en) * 2018-02-28 2023-07-11 精工爱普生株式会社 Robot
CN113573453A (en) * 2021-08-19 2021-10-29 大连理工大学 Device for measuring surface charge of surface dielectric barrier discharge plasma exciter

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