International Business Machines Corporation

John C Collins

Devendra K Sadana

Joel Pereira De Souza

Teodor Krassimirov Todorov

Ali Afzali-Ardakani

Stephen W Bedell

John M Papalia

John Albrecht Ott

Mahadevaiyer Krishnan

Adele L Pacquette

Paul Stephen Andry

Bucknell Chapman Webb

Robert David Allen

David Lee Rath

Robert L Bruce

Young-Hye Na

Jangwoo Kim

Marinus J P Hopstaken

John J DeFazio

Matthew Peter Sagianis

One or more trenches in a silicon substrate have an electrically active surface at a trench base and metal layer disposed on the electrically active surface. Precursor materials are disposed and/or formed on the metal layer in the trench. An anode is patterned either exclusively in the 3D trench or in the 3D trench, sidewalls and field of the substrate, where the anode patterning transforms and/or moves the precursor materials in the trench into some novel compositions of matter and other final operational structures for the device, e.g. layers of metallic Lithium for energy storage and different concentrations of Lithium-silicon species in the substrate. A multi-faceted mechanism is disclosed for Al2O3 silicon interfacial additives. When the anode is patterned both in and outside the 3D wells, Al2O3 provides an for electron-conductive Li-metal interface that enables homogenous plating on both the insulated substrate field as well as active silicon trench base where Al2O3 acts as a barrier to Li—Si diffusion. When the anode is patterned only in the 3D trench, Al2O3 additive creates a robust, flexible, Li-permeable interface upon charge cycling, which preserves the 3D textured structure of the porous silicon anode. Additionally, the Al2O3 additive is mobilized deeper into the bulk silicon in parallel with Li+ and a conductive plasticizer upon progressive cycling—where the lithiated Al2O3 particles nucleate at defect sites and prevent mechanical degradation of the silicon anode through a combined bridge and spacer mechanism. By selecting different defined anode patterns to deposit on the 3D substrate, final operational characteristics, properties, structures, and charge storage performance for the device can be predictably designed and manufactured.

Aluminum oxide protected lithium metal tunable 3D silicon batteries

Energy storage method using aluminum oxide protected lithium metal tunable 3D silicon batteries

Making a rechargeable Lithium energy storage device begins by forming one or more trenches in a solid silicon substrate. One or more region interface precursors are deposited in the trench followed by one or more anode materials, one or more solid polymer electrolytes (SPE), and one or more cathode materials. Electrically cycling transforms the battery structures prior to full operation of the battery. Some, or all, of the process steps can be performed while the materials are within the trench, i.e. in-situ.

Method of making a lithium energy storage device

A method of forming a solid-state lithium ion rechargeable battery may include depositing a metal layer onto a top surface of a substrate, depositing a handle layer onto a top surface of the metal layer, wherein a portion of the handle layer overlaps the metal layer and the substrate, spalling a portion of the substrate thereby forming a spalled substrate layer, porosifying the spalled substrate layer thereby forming a porous substrate layer, depositing an electrolyte layer onto a top surface of the porous substrate layer, wherein the electrolyte layer is in direct contact with the porous substrate layer, and depositing a cathode onto a top surface of the electrolyte layer. The method may include depositing a cathode contact layer onto a top surface of the cathode, wherein the cathode contact layer is in direct contact with the cathode. The porous substrate layer may be made of silicon.

Solid state lithium ion rechargeable battery

A semiconductor device structure and method for forming the same is disclosed. The structure incudes a silicon substrate having at least one trench disposed therein. An electrical and ionic insulating layer is disposed over at least a top surface of the substrate. A plurality of energy storage device layers is formed within the one trench. The plurality of layers includes at least a cathode-based active electrode having a thickness of, for example, at least 100 nm and an internal resistance of, for example, less than 50 Ohms/cm. The method includes forming at least one trench in a silicon substrate. An electrical and ionic insulating layer(s) is formed and disposed over at least a top surface of the silicon substrate. A plurality of energy storage device layers is formed within the trench. Each layer of the plurality of energy storage device layers is independently processed and integrated into the trench.

Fabrication of all-solid-state energy storage devices

A composition includes an electrode made of Lithium Manganese Oxyfluoride (LMOF). A single layer separator adheres to a surface of the electrode, is a dielectric that is conductive for Lithium ions but not electrons, and has top and bottom sides. A solid polymer electrolyte (SPE) saturates the electrode so that the LMOF is between 55 percent and 85 percent by mass of a composition of the LMOF electrode and the SPE is between 7.5 percent and 20 percent by mass of the composition of the LMOF electrode. The SPE saturates the separator so that the SPE resides both on the separator top and bottom sides so that the SPE residing on the separator top side contacts the surface. The LMOF exhibits X-Ray Diffraction spectrum peaks between twenty-two and twenty-four 2-theta degrees, between forty-eight and fifty 2-theta degrees, between fifty-four and fifty-six 2-theta degrees, and between fifty-six and fifty-eight 2-theta degrees.

3D textured composite silicon anode and fluorinated lithium compound electrochemical cell

A silicon-based electrode forms an interface with a layer pair being: 1. a thin, semi-dielectric layer made of a lithium (Li) compound, e.g. lithium fluoride, LiF, disposed on and adheres to the electrode surface of the silicon-based electrode and 2. an molten-ion conductive layer of a lithium containing salt (lithium salt layer) disposed on the semi-dielectric layer. One or more device layers can be disposed on the layer pair to make devices such as energy storage devices, like batteries. The interface has a low resistivity that reduces the energy losses and generated heat of the devices.

Low resistance composite silicon-based electrode

An energy storage device sits within a trench with electrically insulated sides within a substrate. Within the trench there is an anode, an electrolyte disposed on the anode, and a cathode structure disposed on the electrolyte. Variations of an electrically conductive contact are disposed on and in electrical contact with the cathode structure. At least part of the conductive contact is disposed within the trench and the conductive contact partially seals the anode, electrolyte, and cathode structure within the trench. Conductive and/or non-conductive adhesives are used to complete the seal thereby enabling full working electrochemical devices where singulation of the devices from the substrate enables high control of device dimensionality and footprint.

Encapsulating in-situ energy storage device with electrode contact

An energy storage device is provided that includes a pre-lithiated silicon based anode and a carbon nanotube based cathode. The pre-lithiated silicon anode has a porous region and a non-porous region. The full cell energy storage device has high electrochemical performance which exhibits greater 200 rechargeable cycles with less than 25% after 10 charge discharge cycles relative to the first discharge cycle, a maximum specific discharge capacity greater than 300 mAh/g and a specific capacity of greater than 100 mAh/g for over 130 cycles. Such an energy storage device is scalable for a wide array of applications due to its wafer level processing and silicon-based substrate integrability.

Energy storage device containing a pre-lithiated silicon based anode and a carbon nanotube based cathode

A battery includes a cathode with a metal halide and an electrically conductive material, wherein the metal halide acts as an active cathode material; a porous silicon anode with a surface having pores with a depth of about 0.5 microns to about 500 microns, and a metal on the surface and in at least some of the pores thereof; and an electrolyte contacting the anode and the cathode, wherein the electrolyte includes a nitrile moiety.

Porous silicon anode for rechargeable metal halide battery

A catholyte-like material including a cathode material and an interfacial additive layer for providing a lithium ion energy storage device having low impedance is disclosed. The interfacial additive layer, which is composed of vapor deposited iodine, is present between the cathode material and an electrolyte layer of the device. The presence of such an interfacial additive layer increases the ion and electron mobile dependent performances at the cathode material interface due to significant decrease in the resistance/impedance that is observed at the respective interface as well as the impedance observed in the bulk of the device. The catholyte-like material of the present application can be used to provide a lithium ion energy storage device having high charge/discharge rates and/or high capacity.

Lithium ion energy storage device containing a vapor deposited iodine interfacial layer

An energy storage device has all components, e.g. anode, electrolyte, and cathode contained and sealed with a trench in a substrate. Various methods and structures are disclosed for sealing the components. In some embodiments, a sealer or sealing layer seals the components. One embodiment uses a tension clamp to contain the components with additional pressure. Another embodiment uses a cathode structure cup which is held in place in the substrate via sidewall trench features. Different external connections to the device are disclosed. The invention enables full three-dimensional components to be created and contained entirely within the substrate during assembly, curing, galvanic cycling and other manufacturing processes and provides improved sealing of the components during device operation.

Encapsulating in-situ energy storage device with cathode contact

A three dimensional (3D) In-Silicon energy storage device is provided by a method that includes forming a thick dielectric material layer on a surface of a silicon based substrate. A 3D trench is then formed into the dielectric material layer and the silicon based substrate, and thereafter a dielectric material spacer is formed, in addition to the dielectric remaining on the field of the substrate, as well as along a sidewall of the 3D trench, and on a first portion of a sub-surface of the silicon based substrate that is present at a bottom of the 3D trench. A second portion of the sub-surface of the silicon based substrate that is present in the 3D trench remains physically exposed. Active energy storage device materials can then be formed laterally adjacent to the dielectric material spacer that is within the 3D trench and on the dielectric material layer.

High throughput insulation of 3D in-silicon high volumetric energy and power dense energy storage devices

An interfacial additive layer for decreasing the interfacial resistance/impedance of a silicon based electrode-containing device such as, for example, an energy storage device or a micro-resistor, is disclosed. The interfacial additive layer, which is composed of a molten lithium containing salt, is formed between a silicon based electrode and a solid polymer electrolyte layer of the device. The presence of such an interfacial additive layer increases the ion and electron mobile dependent performances at the silicon based electrode interface due to significant decrease in the resistance/impedance that is observed at the respective interface as well as the impedance observed in the bulk of the device.

Molten ion conductive salt/silicon interface for decreased interfacial resistance

A Lithium energy storage device comprising a cathode, electrolyte, anode, and substrate. The materials contained in the anode and electrolyte region are electrochemically altered during initial formation and exposed to current cycles to create a lower impedance composite anode. The resulting composite anode bottom is a bi-layer comprising: i. a lithium metal layer and ii. a silicon-based interphase layer. The bi-layer acts as a barrier to inhibit Lithium ions from entering or leaving a Lithium saturated substrate, once the interphase surface is formed and the substrate is saturated with Lithium ions. This prevents cell failure from large volume changes/stresses during charge/discharge cycles and enables a significant decrease in cell impedance to enable better rechargeable cell performance.

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Poughkeepsie, NY, United States of America

John C Collins