WO2010032159A1 - Dispositif électrochimique 2d ou 3d employant des électrodes actives composites - Google Patents

Dispositif électrochimique 2d ou 3d employant des électrodes actives composites Download PDF

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Publication number
WO2010032159A1
WO2010032159A1 PCT/IB2009/053920 IB2009053920W WO2010032159A1 WO 2010032159 A1 WO2010032159 A1 WO 2010032159A1 IB 2009053920 W IB2009053920 W IB 2009053920W WO 2010032159 A1 WO2010032159 A1 WO 2010032159A1
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Prior art keywords
electrochemical device
nano
electrolyte
cathode
active material
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PCT/IB2009/053920
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English (en)
Inventor
Willem Frederik Adrianus Besling
Rogier Adrianus Henrica Niessen
Johan Hendrik Klootwijk
Nynke Verhaegh
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Nxp B.V.
Koninklijke Philips Electronics N.V.
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Publication of WO2010032159A1 publication Critical patent/WO2010032159A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0436—Small-sized flat cells or batteries for portable equipment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/40—Printed batteries, e.g. thin film batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a modified electrochemical device such as a rechargeable Li-ion solid-state battery design that is preferably integrated in 3D silicon.
  • EP 1463071 A2 discloses a layered ruthenic acid compound, which is converted to a protonic layered ruthenic acid hydrate, which is then converted to a layered alkylammonium-ruthenic acid intercalation compound to obtain a colloid containing ruthenic acid nanosheets having a thickness of 1 nm or smaller. Thereby, a ruthenic acid nanosheet is obtained.
  • the material may be used in high power capacitors.
  • nanoscale ion storage materials that exhibit unique properties measurably distinct from their larger scale counterparts.
  • the nanoscale materials can exhibit increased electronic conductivity, improved electromechanical stability, increased rate of intercalation, and/or an extended range of solid solution.
  • Useful nanoscale materials include alkaline transition metal phosphates, such as LiMPO 4 , where M is one or more transition metals.
  • the nanoscale ion storage materials are useful for producing devices such as high energy and high power storage batteries, battery-capacitor hybrid devices, and high rate electrochromic devices.
  • US2007/292763 Al discloses a method of manufacture an article of a cathode (positive electrode) material for lithium batteries.
  • the cathode material is a lithium molybdenum composite transition metal oxide material and is prepared by mixing in a solid state an intermediate molybdenum composite transition metal oxide and a lithium source. The mixture is thermally treated to obtain the lithium molybdenum composite transition metal oxide cathode material. It is noted that this patent deals with bulk powder electrodes and not with thin film processed energy storage electrodes for (integrated) Li- ion batteries. This is regarded as a completely different class of elements.
  • the present invention is aimed at solving the above problems.
  • the present invention relates to a 2D or 3D electrochemical device, comprising an anode, a cathode, an electrolyte comprising one or more components, wherein the cathode and/or anode comprise two or more materials selected from the group consisting of (nano) laminates, (nano) clusters, and (nano) cluster composites, and mixtures thereof, wherein at least one first material functions as an storage material for one or more components of the electrolyte, and wherein at least one second material is an electrochemically non-active material, wherein said first material has a different composition from said second material, a method of making the same, and use of said electrochemical device in an application.
  • the present electrochemical device reduces the overall volume expansion/contraction of a composite such as thin film electrode for a micro power source. This is highly beneficial as, especially in a 3D integrated power source, extreme care has to be taken that expansion/contraction within the power source, such as a battery stack, does not lead to deterioration of performance.
  • the present invention relates to a 2D or 3D electrochemical device, comprising an anode, a cathode, an electrolyte comprising one or more components, wherein the cathode and/or anode comprise two or more materials selected from the group consisting of (nano) laminates, (nano) clusters, and (nano) cluster composites, and mixtures thereof, wherein at least one first material functions as an storage material for one or more components of the electrolyte, and wherein at least one second material is an electrochemically non-active material, wherein said first material has a different composition from said second material.
  • the invention discloses a novel and improved way to mitigate and/or control the volume expansion occurring in electrochemical devices, such as solid-state (3D and 2D) battery stacks. In this way, the mechanical stability and lifetime of said in electrochemical devices can be maintained or vastly improved without sacrificing in performance.
  • the present invention discloses a electrochemical device, such as a modified rechargeable solid-state battery design, that is either 2D or integrated in a 3D etched substrate such as silicon, porous alumina, germanium, metal (foil), Cu, Ta, etc.
  • This modified design uses composite active battery electrodes, which comprise a mixture of (nano)laminate and/or (nano)clusters of two different materials, one being the storage (e.g. intercalation) material and one being a non-active material.
  • the storage material functions as a - A - volume for one or more electrolyte species (components).
  • the species may be stored in interstitial space, in interlayer space, in crystal structure in general, may form dislocations, or combinations thereof.
  • the present storage capacity is somewhat deteriorated compared to a device with only one material.
  • the performance and integrity and stability over time are greatly improved, as is the reliability.
  • the storage material comprises 20-99% of the anode and/or cathode volume available, preferably from 30-80%, more preferably from 40-75, such as from 50-70%.
  • the storage capacity should not be too small and should be readily accessible for electrolyte species. Therefore the volume of storage material should be as large as possible.
  • the non-active material functions to keep the volume of the electrochemical device as constant as possible. Therefore, the volume of the non-active material should also be as large as possible.
  • the function of the storage material prevails over the function of the non-active material.
  • a battery is also meant to comprise one or more cells, each cell being formed according to any of the present claims.
  • the structure of the present device relates to an active and passive (non-active) material.
  • the composition and structure of the anode and cathode e.g. clusters, laminates, etc., are functionally interchangeable.
  • the anode may comprise the active and passive material, or the cathode may comprise both, or both the cathode and anode may comprise the active and passive (non-active) material.
  • the cathode comprises the active and passive material, in view of storage properties of the active material.
  • the anode comprises silicon, or a mixture of silicon and germanium.
  • the electrochemically inert (non-active) material such as a passive oxide
  • a passive oxide i.e. an electrochemically stable material that is a non convertible material in a voltage region of operation
  • an electrochemically active material i.e. intercalation compound
  • nano refers to a size in the order of 1-1000 nm, and in the present invention is also meant to encompass sizes in the order of 1 ⁇ m to 1000 ⁇ m, and even 1 mm to 100 mm. It preferably refers to sizes in the order of 1-1000 nm, as these sizes offer the best ratio of surface/volume of the materials in question.
  • the storage material expands/contracts during device operation like an ordinary anode/cathode, but its expansion/contraction is being 'absorbed'/mitigated by an inert, volume-constant non active material.
  • the overall effect of the composite electrode is a reduction in volume change, resulting in a more mechanically stable system.
  • the ratio between the materials, as well as the type of nano-structure of the composite i.e. nano-clusters, core-shell clusters, nano- laminate, etc.
  • the volume change can be controlled accordingly. It id extremely difficult to arrive as such designs, as most materials or combinations thereof do not form any of the present structures. Extensive research has been carried out to arrive at the present structures.
  • an electrochemical energy source is present, characterized in that one or both the anode and the cathode of the battery are adapted for storage of species of the solid state electrolyte.
  • species are selected from at least one of following elements: H, Li, Be, Mg, Cu, Ag, Na and K, and preferably Li.
  • a suited electrolyte is LIPON.
  • the electrochemically non-active material preferably conducts these species well, as well as other electrolytes, and preferably also electrons. As such, the performance of the matrix in terms of storage capacity and conductivity of an optionally generated current is further improved.
  • the at least one second material functions as a non-active material for the aforementioned species within the electrochemical potential range in which the intercalation/storage material is electrochemically active.
  • Such second material is typically not an alloy.
  • the present invention relates to use of a nanolaminate or nanoclustering or combination thereof to distinguish a passive matrix and an active electrode material. It is noted that this does not resemble a structure identical to any of those described in the prior art found. It is noted that the use of nano materials in intercalation cells is known, but is generally used to: - enhance active surface area of the electrode by means of self- assembly of storage materials onto bio-materials (WO2006/045076)
  • the invention relates to a 2D or 3D electrochemical device according to claim 1, selected from the group consisting of integrated battery, energy storage device and power source, preferably an integrated battery, and/or wherein the electrolyte is an inorganic solid state electrolyte.
  • the invention relates to a 2D or 3D electrochemical device, wherein the electrochemically non-active material is chosen from the group of compounds comprising one or more of a Group VIII metal.
  • the electrochemically non-active material is chosen from the group of compounds comprising one or more of a Group VIII metal oxides, such as RuO 2 , RhO 2 , PdO 2 , FeO 2 , CoO 2 , NiO 2 , OsO 2 , IrO 2 , PtO 2 , preferably RuO 2 , Group VIII metal nitrides, Group VIII metal sulfides, Group VIII metal halides, and combinations thereof. It is found that specifically Group VIII metals, and compositions thereof, are suited, as these materials are stable, non-active, etc. in the range of operation.
  • the present embodiment is structurally firmer, and consists of relatively more electrochemically non-active material.
  • RuO 2 is used, as it is a stable material, capable of withstanding volume changes, and providing a good mechanical stability over time.
  • both the cathode and anode material may be a matrix with RuO 2 particles embedded in it. Such an embodiment further provides a larger capacity per volume.
  • the invention relates to a 2D or 3D electrochemical device, wherein the electrochemically non-active material forms (nano) clusters around the storage material, or wherein the storage material forms (nano) clusters around the electrochemically non-active material, or wherein layers of storage material are alternated with layers of electrochemically non-active material, or wherein (nano) clusters of storage material and (nano) clusters of electrochemically non-active material are randomly mixed, and combination hereof.
  • the structures can be obtained by depositing layers, forming a laminate, or by co-deposition of materials under well defined conditions, thereby forming clusters of various forms, depending on conditions.
  • the above structures are specifically related to the use of the materials according to the invention, e.g. a combination of a non-active material such as a Group VIII oxide and e.g. LiCoO 2 .
  • the formation of clusters, or laminates, occurs further at specific ratios between materials used.
  • the invention relates to a 2D or
  • the size of the (nano) clusters is from 1-5000 nm, preferably from 2-250 nm, and/or wherein the layers have a thickness of 1-2000 nm, preferably 2-1000 nm, such as from 20-500 nm.
  • the invention relates to a 2D or 3D electrochemical device, having an electrolyte causing a volume change, wherein the electrolyte is preferably a material comprising Lithium, wherein the volume change is less than 3% upon storage (intercalation) or di-intercalation of electrolyte ions, preferably less than 2.5%, such as less than 2%.
  • the invention relates to a 2D or 3D electrochemical device, wherein the electrochemically non-active material conducts charge carriers such as Li and/or electrons well, preferably both.
  • the non- active material contributes to properties of the present device, such as an improved conductivity.
  • the invention relates to a 2D or 3D electrochemical device, wherein the device further comprises one or more high aspect ratio structures, selected from trenches, pillar, holes and combinations thereof.
  • An advantage of these 3D structures is that they increase the battery area.
  • the 3D structures do preferably not act as electrodes or "active" part of the battery layer stack. Further, these 3D structures are mechanically and in operation stable, have a large surface to volume ratio, have improved power characteristics and improved lifetime, etc.
  • the invention in a second aspect relates to a method of forming a 2D or 3D electrochemical device according to the invention, comprising the steps of: providing a substrate; and applying an electrolyte by a technique such as co-deposition by physical vapor deposition, or co-evaporation, or alternating deposition by LPCVD or ALD, or by ink-jetting, or by sol-gel processing of mixed solutions, or spraying, or combinations thereof.
  • a technique such as co-deposition by physical vapor deposition, or co-evaporation, or alternating deposition by LPCVD or ALD, or by ink-jetting, or by sol-gel processing of mixed solutions, or spraying, or combinations thereof.
  • the invention relates to a device, such as long-lifetime autonomous applications such as lighting control unit, a presence and motion detection device, a building (energy) control unit, an autonomous light source, green house sensor platform, wireless add-on sensors, medical implantable devices, OLED devices, presence detection, implantables, smart cards and hearing aids, comprising a 2D or 3D electrochemical device according to the invention.
  • a device such as long-lifetime autonomous applications such as lighting control unit, a presence and motion detection device, a building (energy) control unit, an autonomous light source, green house sensor platform, wireless add-on sensors, medical implantable devices, OLED devices, presence detection, implantables, smart cards and hearing aids, comprising a 2D or 3D electrochemical device according to the invention.
  • Fig. 1 shows a schematic part of a prior art solid state battery.
  • Fig. 2 shows a schematic part of the present solid state battery.
  • Fig. 3 shows a schematic part of the present solid state battery.
  • Fig. 4 shows a schematic of the present solid state battery.
  • Fig. 1 shows a schematic part of a prior art solid state battery.
  • a substrate (100) and a cathode (110) are shown.
  • the cross-section of a common active electrode in this case a well-known LiCoO 2 cathode is used
  • a volume change (170) of 6 vol. % is expected between these two states.
  • Such a volume change is undesired, in view of operating performance, e.g. charging, de charging, power delivery, and life time of the battery.
  • the electrochemically non-active material conducts both lithium ions and electrons well.
  • RuO 2 is chosen. This material is a good electronic conductor and known to show lithium ion conductivity, but is, however, not able to intercalate lithium ions at the electrochemical potential at which
  • LiCoO 2 stores/releases the bulk part of its lithium.
  • Fig. 2 shows a schematic part of the present solid state battery.
  • a substrate (200) at least one first material functions as an storage material (211) for one or more components of the electrolyte, and wherein at least one second material functions as a non-active matrix (210), wherein said first material has a different composition from said second material.
  • This composite cathode system can be realized in several different ways, these being: 1. A nanocluster system in which nanoclusters/nanoparticles of the active
  • LiCoO 2 material and the inactive RuO 2 material are randomly mixed on a nano-scale (figure 2a).
  • a nano-scale Depending on the ratio of active and inactive material, more clusters of the active or more of the inactive material will be formed.
  • figure 2a is not limited to the ratio between clusters of active and inactive material.
  • the ratio of clusters active/inactive material may vary between 1 :10 and 10:1. Further, it is noted that clusters may vary in size, e.g. due to a natural process (such as statistics), due to the ratio mentioned, due to material properties etc.
  • a core-shell system in which nanoclusters/nanoparticles comprise an active LiCoO 2 core and an inactive RuO 2 shell, or vise versa.
  • a typical size of said core-shell clusters is from 5-500 nm, preferably from 10-250 nm.
  • the size of the clusters may be varied and controlled by changing the above ratio, the materials used etc. (see fig. 2c).
  • the core shell clusters can have as a core an active material, and as a shell an inactive material, or vice versa.
  • Fig. 2c shows a schematic drawing, however, in reality the clusters may have any form, e.g. substantially spherical, multigonal, etc. 3.
  • the thickness of the films is from 5-500 nm, preferably from 10-250 nm (see fig. 2b). All these examples are shown in Fig.2.
  • the volume expansion of the whole electrode (assembly) can be mitigated or, at least, controlled in order to reduce stress in the complete battery system.
  • Fig.3. which as indicated above, may equally well be the nano laminate solution as well as the given core-shell solution.
  • the introduction of the RuO 2 'matrix' material is able to reduce the volume change which is a value a lot lower that the sole cathode.
  • Fig. 3 shows a schematic part of the present solid-state battery.
  • a substrate 300
  • a storage material 311
  • a non-active matrix 310) are shown.
  • the cross-section of a nanocluster composite cathode system comprising a LiCoO 2 active material (311) and a RuO 2 inactive material (310), in its lithiated (left) and de- lithiated state (right).
  • a volume change (370) of less than 4 vol.% is expected between these two states.
  • Another aspect of the invention is related to stress relaxation: if volume expansion due to lithiation or de-lithiation would result in local fracture of the composite material, the fracture energy of the tip will easily get absorbed within the composite material. In monolithic cathode and anode materials the fracture tip will continue through the whole film resulting in complete fracture.
  • Fig. 4 shows a schematic of the present solid-state battery, specifically a concept of a 3D solid-state micro battery.
  • a substrate typically silicon is shown.
  • a first current collector typically forming part of the silicon substrate is shown.
  • a patterned 3D or 2D layer is formed, preferably a silicon layer.
  • a barrier layer 420 is deposited on the pattern formed before.
  • a cathode layer 430 is formed on top of the barrier layer.
  • Fig. 4e a solid state electrolyte is deposited.
  • an anode is deposited.
  • a second current collector is provided.
  • the cathode material is typically deposited on top of the bottom current collector (basic metallic component typically Pt or Ru metal deposited by PVD or by ALD) with an underlying adhesion layers consisting of TiO 2 , Ti and or TiN. All these materials can be deposited by PVD, CVD or ALD methods. Although feasible in 2D the alternating deposition of different cathode materials by PVD becomes even more complicated in 3D due to line of sight limitation in physical vapor deposition methods. This will result in films with poor step coverage and most probably also different film stoichio merries as function of depth.
  • a nanolaminated structure is advantageously deposited by Low Pressure Chemical Vapor Deposition (LPCVD) or Atomic Layer Deposition (ALD) which techniques are known to have much better step conformality and good control of stoichiometry on surfaces that have large topography.
  • LPCVD Low Pressure Chemical Vapor Deposition
  • ALD Atomic Layer Deposition
  • the entire stack can be deposited inside, for example, a single CVD reactor chamber.
  • the growth of the active, Li-intercalating cathode material is carried out by Low-pressure CVD.
  • the material comprises of e.g., LiMO 2 where M is a metal from the series of Co, Mn, or Ni and or combinations thereof.
  • a commercial horizontal cold walled LPCVD reactor (Aixtron 200RF) has been employed for the deposition of the LiCoO 2 cathode material, t-butyl lithium and Cobalt di-carbonyl cyclopentadienyl were used as precursors for respectively Li and Co upon using Ar as carrier gas to transport the vapor from the bubbler to the reactor.
  • the Cobalt and lithium precursor were mixed with oxygen in the reaction chamber.
  • Deposition temperatures are typically between 300 C and 500 C.
  • RuO 2 Ruthenium cyclopentadienyl Ru(Cp) 2 has been employed as Ru precursor source in combination with oxygen in a temperature range between 275 C and 450 C.
  • Upon switching the precursor flows a nanolaminated stack can be grown of the two alternating materials.
  • the thickness of the Li intercalating compound is preferably larger than the thickness of the inert matrix material.
  • the growth behavior of the matrix and intercalating cathode material on top of each other depends on the reactivity of the underlying substrate i.e. the density of reactive groups on the surface. If e.g. the RuO 2 matrix film is grown in a layer by layer fashion as is normally employed in Atomic Layer Deposition, the RuO 2 film tend to have difficulties to nucleate on the underlying substrate. If only very thin films are grown (i.e. a small number of growth cycles is applied) the RuO 2 film starts to grow in an island like fashion and remain discontinuous if not too thick films are grown. This typically occurs at higher deposition temperatures and/or the use of bulky ligands where steric hindrance start to play a role.
  • Co, Ni, with the olivine structure demonstrate reversible lithium extraction and insertion in LiFeP04 and can be used as active cathode material.
  • LiFePO 4 the following precursors can be used as an example: t-butyl lithium (Lithium precursor), trimethylphosphate (phosphorous precursor) and ferrocene (bis( 5 cyclop entadienyl)iron) (Iron precursor). Deposition takes place at a temperature of 350 0 C.

Abstract

La présente invention concerne une pile à électrolyte solide Li-ion, rechargeable, modifiée, intégrée à du silicium 3D. Plusieurs modèles de piles 2D ou 3D intégrées, actuellement utilisés, ont été décrits dans l'art antérieur. Des concepts novateurs (intégration 3D) de piles à électrolyte entièrement solide Li-ion, rechargeables, à couches minces, ont été précédemment décrits dans le brevet WO2005/027245A2. Ces dispositifs de stockage d'énergie peuvent être utilisés de façon avantageuse comme sources de fourniture de puissance dans diverses applications comme, par exemple, des dispositifs OLED, des dispositifs de détection de présence, des dispositifs implantables, des cartes à puce intelligentes et des prothèses auditives. Un des problèmes liés à ce type de pile à électrolyte solide est la dilatation ou la contraction volumique des électrodes actives (anode et cathode) résultant de l'intercalation de lithium dans les électrodes susmentionnées ou l’élimination de lithium à partir des électrodes. Ce changement de volume provoque inévitablement une contrainte et peut donc compromettre la stabilité mécanique du dispositif et, par voie de conséquence, entraîner une diminution de sa durée de service. Dans des structures à rapport d'aspect élevé en particulier, comme des tranchées, des colonnes ou des trous par exemple, des régions de forte courbure seront source de problèmes. Afin de réduire cette dilatation volumique, il est impératif de choisir très précisément les matériaux actifs, à savoir l'anode et cathode (de façon à obtenir une excellente compatibilité chimique des électrodes) et de faire en sorte que leurs géométries correspondent (compatibilité géométrique des électrodes).
PCT/IB2009/053920 2008-09-17 2009-09-08 Dispositif électrochimique 2d ou 3d employant des électrodes actives composites WO2010032159A1 (fr)

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