WO2008027050A1 - Pile au lithium - Google Patents

Pile au lithium Download PDF

Info

Publication number
WO2008027050A1
WO2008027050A1 PCT/US2006/034119 US2006034119W WO2008027050A1 WO 2008027050 A1 WO2008027050 A1 WO 2008027050A1 US 2006034119 W US2006034119 W US 2006034119W WO 2008027050 A1 WO2008027050 A1 WO 2008027050A1
Authority
WO
WIPO (PCT)
Prior art keywords
cell
cathode
lithium
anode
phosphorus
Prior art date
Application number
PCT/US2006/034119
Other languages
English (en)
Inventor
Floris Y. Tsang
Original Assignee
Tsang Floris Y
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tsang Floris Y filed Critical Tsang Floris Y
Priority to PCT/US2006/034119 priority Critical patent/WO2008027050A1/fr
Publication of WO2008027050A1 publication Critical patent/WO2008027050A1/fr

Links

Classifications

    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte

Definitions

  • the present invention relates to a lithium battery suitable for providing power for electronic devices.
  • the invention relates to a lithium battery composition, its method of operation, and its method of assembly.
  • Cells and batteries based on lithium metal come in many different forms and are used to power a wide range of electronic devices and instruments. Their distinguishing feature is the use of lithium metal (or a lithium metal alloy) as the anode. Like other electrochemical cells they require a counter electrode or cathode and a lithium-ion conducting electrolyte joining the two electrodes. The anode and counter electrode must also be electronically separated. Since most lithium cell electrolytes are liquid, this is usually accomplished through the use of an insulating porous film impregnated with the electrolyte, sandwiched between the two electrodes. [0006] A wide range of cathode materials have been used or proposed for use in cells of this configuration. Some desirable properties for cathode materials include high voltage, high energy density, compatibility with the electrolyte, and high conductivity when utilized in a cell.
  • lithium metal batteries with liquid electrolytes and porous separators include lithium/carbon monofluoride, lithium/iron disulfide, lithium/manganese dioxide and lithium/silver vanadium oxide. These cells operate well at room temperature with relatively high power and energy density. Other cathode materials have been proposed. Of particular relevance to this invention, a liquid electrolyte cell with a porous polymer separator in this classic configuration has been reported in the journal Dopovidi Natsional 'noi Akademii Nauk Ukraini, 1997, 3, p.154 utilizing a lithium anode and a cathode containing black phosphorus.
  • a number of lithium cells have been developed that utilize a solid electrolyte, which can function both as the separator and the electrolyte.
  • Solid electrolytes for lithium cells must be both lithium ion conducting and electronically insulating.
  • solid state materials identified over the years as suitable for use as electrolytes for lithium cells including lithium iodide, lithium phosphide, LiPON and LiSiCON. Most of these materials are glassy in nature and their lithium ion conductivities can vary greatly based on their form, specific composition and temperature of operation.
  • Other solid electrolytes include polyethylene oxide/lithium salt composites and solid polymer gel electrolytes.
  • the solid electrolyte material can be applied as a thin layer between the anode and cathode and if necessary mixed with the active anode and cathode materials within the electrodes.
  • Some examples of cathode materials used or proposed for use in such cells include sulfur, iodine, and lithium transition metal oxides such lithium vanadium oxide, lithium iron phosphate, and lithium cobalt oxide.
  • Cells made with solid electrolytes often have advantages in terms of storage stability, energy density, ease of manufacture, wide temperatures of operation and resistance to shock and vibration.
  • the lithium/iodine cell is unique in that the reaction between the anode and cathode itself generates the solid electrolyte phase, lithium iodide (LiI). Since the solid electrolyte phase is generated in-situ, there is no need to apply a solid electrolyte film to either the anode or cathode prior to cell assembly leading to advantages in energy density, manufacturability and life. Such a process also prevents shorting of the cell via self-healing, making them highly reliable and safe. The electrolyte propagates through the active materials as the cell is discharged and more reaction product or electrolyte is formed.
  • LiI lithium iodide
  • the present invention relates to the composition of a new solid-state lithium battery comprising a lithium-containing anode, preferably lithium metal, and a phosphorus-containing cathode.
  • the cathode may comprise any of a number of electronically conductive allotropes of phosphorus, herein referred to as a group as black phosphorus.
  • black phosphorus is electronically conductive allowing for ongoing reductive chemical reaction with lithium during cell discharge.
  • At least one form of conductive black phosphorus has a graphite-like structure and is the thermo dynamically stable form of phosphorus.
  • the black phosphorus electrode may contain an electronically conductive phase to further enhance the conductivity of the cathode electrode and reduce the cathode impedance.
  • the electronically conductive phase is rendered non-conductive with cell discharge.
  • the cell discharge reaction converts an electronically conductive cathode, black phosphorus, to a lithium-ion conducting electrolyte, lithium phosphide, effectively propagating the electrolyte and electrochemical reaction-front toward the cathode.
  • the cell composition includes, but is not limited to, a lithium anode, a black phosphorus based cathode and an in-situ formed solid electrolyte/separator formed from the reaction product of lithium and black phosphorus.
  • a cell structure and method of assembly for the solid-state lithium/black phosphorus cell wherein the lithium based anode and the black phosphorus based cathode are brought into direct contact during assembly.
  • a thin lithium phosphide layer may form instantaneously at the interface of the two electrodes, electrochemically via an initial internal "short".
  • the in-situ formation of the electrolyte layer at the interface is self-limiting since the formed layer is electronically insulating.
  • the cell can be assembled without a pre-existing separator or electrolyte phase. Subsequent discharge of the cell through an external circuit will propagate the solid lithium phosphide electrolyte while maintaining electronic separation of the anode and cathode.
  • Such a cell is not susceptible to failure from the formation of shorts and is thus highly reliable.
  • an initial lithium ion-conducting layer is pre- applied to the anode, cathode or both electrodes before assembly of the cell.
  • a lithium/phosphorus battery constructed with a conventional bipolar configuration wherein multiple layers of the anode and cathode electrodes are stacked in series to create a high voltage battery.
  • FIG. 1 is a schematic illustration of a solid-state lithium anode/black phosphorus cathode cell after initial assembly and during discharge in accordance with the invention.
  • the solid-state electrochemical cell of this invention comprises a lithium based anode electrode and a cathode electrode containing an electronically conductive allotrope of phosphorus. While there are a number of conductive forms of phosphorus that have been reported, each with slightly different properties, we will refer to them as a group herein as black phosphorus. The reaction between lithium and black phosphorus can produce lithium phosphide, a well-known Li-ion conductor, some forms of which have demonstrated very high ionic conductivity ( ⁇ 10 "3 /Ohm-cm).
  • FIG 1. illustrates one embodiment of a cell of this invention wherein the cell is shown both immediately after assembly 5 and during discharge 6.
  • a lithium metal anode electrode 1 is placed in contact with a black phosphorus cathode electrode 2, immediately resulting in the formation of a lithium phosphide layer 3 at the interface due to the reaction of the lithium anode 1 and the phosphorus cathode 2.
  • the in-situ formed, insulating lithium phosphide layer 3 may act as both the separator and the electrolyte for the cell, first preventing further chemical reaction or shorting of the lithium and phosphorus electrodes 1 and 2 because it is an insulating layer, and second keeping the anode and cathode 1 and 2 in electrochemical contact because it is a lithium ion conductive material.
  • Such a cell is highly stable and is not susceptible to damage from internal cell shorts because they will be self-limiting as the short is isolated by the formation of insulating lithium phosphide. In many lithium battery systems without such a self-healing mechanism, shorting of the anode and cathode can result in catastrophic failure of the cell with the potential for cell rupture, fire or explosions.
  • the cell may be discharged through an external circuit.
  • discharge 6 the electrons flow from the negative anode electrode 1 to the positive cathode electrode 2 to reduce the phosphorus material of the cathode 2.
  • lithium ions migrate from the lithium anode 1, through the existing lithium phosphide ion conductive layer 4 towards the cathode electrode 2 where they react with the phosphorus present at the lithium phosphide layer/phosphorus layer interface to form more lithium phosphide.
  • the lithium phosphide layer 4 self-propagates in the direction of the cathode 2 as the cell is discharged, continuing to act as the cell electrolyte and separator by maintaining electrochemical contact between the anode and cathode 1 and 2 and allowing for ongoing electrochemical reaction. Opening the circuit will stop electron flow and will prevent further reaction of the lithium and phosphorus in the cell.
  • the cell can be used to power electronic devices.
  • the structure and assembly of the cell is similar to that known for a lithium iodine cell, which can also be assembled without a preexisting separator or electrolyte.
  • a lithium iodine cell the lithium anode reacts with the iodine cathode to form a lithium ion conducting, lithium iodide layer between the anode and cathode.
  • the lithium phosphorus cell of this invention has certain advantages over a comparable lithium iodine cell.
  • the in-situ formed lithium phosphide electrolyte may have a much higher lithium ion conductivity than a lithium iodide electrolyte.
  • the theoretical capacity and energy density of a cell based on the formation of lithium phosphide from lithium and phosphorus can be much greater than that for the formation of lithium iodide from lithium and iodine.
  • the inherent electronic conductivity of iodine is very low unless a conductive adduct is formed with the iodine phase prior to cell assembly, typically utilizing a pyridine-containing polymer.
  • the addition of the essentially inactive polymer phase effectively reduces the theoretical capacity of the cell whereas the black phosphorus active material is inherently electronically conductive.
  • Black phosphorus material for use as the cathode may be produced by any number of methods. Some examples include high-pressure and temperature conversion of other non-conductive allotropes of phosphorus to black phosphorus, precipitation of black phosphorus from bismuth melts containing yellow phosphorus, and mercury catalyzed formation of black phosphorus from yellow phosphorus seeded with black phosphorus. Properties such as structure, crystallinity, morphology, purity and conductivity of black phosphorus materials made by different methods may vary and thus may affect the overall performance of the cell of this invention. Thus the synthesis of the cathode material may be modified to produce the black phosphorus material with the most ideal characteristics for a specified cell application.
  • the desirable properties of the black phosphorus cathode material may be high conductivity, high crystallinity and high purity to maximize the overall energy density of the cell whereas other properties may be critical to maximize the overall power capability of the cell.
  • the black phosphorus material may be collected as a powder or as a solid monolith or as a thin film after synthesis.
  • the black phosphorus cathode may be a dense, substantially single-phase monolith.
  • the cathode may comprise black phosphorus and an auxiliary electronic conductor phase to improve the conductivity of the cathode, improve the cathode utilization during discharge or to reduce the overall cell impedance.
  • the electronic conductor phase may be selected from any number of conductive materials such as, but not limited to, carbon, metals or metal alloys, or polymeric materials, which may take the form of powders, fibers, films or continuous arrays.
  • the auxiliary electronic conductor phase may be mixed with or applied to the black phosphorus phase prior to cell assembly.
  • the composite may be pressed into a pellet, coated onto a conductive substrate or otherwise deposited into the cell.
  • the discharge product of a black phosphorus cathode containing an auxiliary conductive phase is substantially electronically non- conductive. In certain embodiments of the cell this may be necessary to prevent the formation of a continuous electronically conductive path connecting the lithium anode to the current collector of the cathode through the electronically conductive phase, resulting in a permanently shorted cell.
  • the discharge product between lithium and the composite black phosphorus/electronically conductive phase cathode may be rendered electronically non- conductive by a number of mechanisms including, but not limited to, effectively breaking the conductive path through the volumetric expansion of the phosphorus cathode upon formation of the lithium phosphide product.
  • the lithium anode may be lithium metal.
  • the lithium phosphorus cell is assembled without a preexisting separator or electrolyte by placing the lithium anode and phosphorus cathode in contact with each other to form a lithium phosphide layer in-situ that effectively separates the anode and cathode.
  • the anode is connected electronically to the negative side of the cell container (negative terminal) and the cathode is connected electronically to the positive side of the cell container (positive terminal).
  • the two terminals of the cell container are electronically isolated from each other.
  • the anode and cathode material may be connected to the negative and positive terminals physically by applying pressure, or they may be coated onto a current collector that is electronically welded or otherwise electronically attached to their respective terminals.
  • the cell is assembled with a pre-existing ion-conductive interfacial layer sandwiched between the anode and cathode.
  • the pre-existing ion conductive layer will act as the initial separator and electrolyte and may impart improved interfacial properties to the electrodes, improved contact between the electrodes when assembled, and improved cell performance.
  • the pre-existing layer may be applied to the lithium anode electrode surface, to the phosphorus cathode electrode surface or to both prior to cell assembly.
  • the pre-existing ion conductive interfacial layer may be selected from a number of materials including, but not limited to, the glassy ceramic materials such as LiPON and LiSICON, or the materials Li 3 N, Li 3 P, Li 2 O, LiI, polyethylene oxide/lithium salt, or a solid polymer gel electrolyte.
  • the glassy ceramic materials such as LiPON and LiSICON, or the materials Li 3 N, Li 3 P, Li 2 O, LiI, polyethylene oxide/lithium salt, or a solid polymer gel electrolyte.
  • the cell of this invention may be encased in a sealed container suitable for electrochemical cells, wherein the positive cathode side and negative anode side are electrically insulated from each other.
  • a battery with a bipolar configuration may be assembled using stacks of electrodes to provide higher voltages and greater power.
  • the cell of this invention is suitable for use as a power source for electronic devices, instruments and sensors, and may range in size from very large (> 2Ah) to very small size micro- batteries.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Primary Cells (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne une pile au lithium à semi-conducteur comprenant une anode (1) contenant du lithium et une cathode (2) contenant du phosphore. La cathode peut comprendre n'importe quel nombre d'allotropes électriquement conducteurs du phosphore, mentionnés comme étant un groupe de phosphore noir. Un produit de décharge solide de la pile agit en tant qu'électrolyte (3) pour la pile. La cathode peut comprendre une phase de conducteur électronique auxiliaire pour améliorer la conductivité de la cathode, améliorer l'utilisation de la cathode pendant la décharge et réduire l'impédance de pile globale.
PCT/US2006/034119 2006-08-29 2006-08-29 Pile au lithium WO2008027050A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2006/034119 WO2008027050A1 (fr) 2006-08-29 2006-08-29 Pile au lithium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2006/034119 WO2008027050A1 (fr) 2006-08-29 2006-08-29 Pile au lithium

Publications (1)

Publication Number Publication Date
WO2008027050A1 true WO2008027050A1 (fr) 2008-03-06

Family

ID=39136208

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2006/034119 WO2008027050A1 (fr) 2006-08-29 2006-08-29 Pile au lithium

Country Status (1)

Country Link
WO (1) WO2008027050A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013152030A1 (fr) * 2012-04-02 2013-10-10 Ceramatec, Inc. Batterie à séparateur en structure de nid d'abeilles non poreux conducteur des ions de métaux alcalins
CN105762406A (zh) * 2016-05-10 2016-07-13 北京石油化工学院 一种有机型锌离子二次电池
CN112259741A (zh) * 2020-09-28 2021-01-22 江汉大学 一种集流体及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953230A (en) * 1975-04-25 1976-04-27 General Electric Company Sealed lithium-phosphorous cell
US4826743A (en) * 1987-12-16 1989-05-02 General Motors Corporation Solid-state lithium battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953230A (en) * 1975-04-25 1976-04-27 General Electric Company Sealed lithium-phosphorous cell
US4826743A (en) * 1987-12-16 1989-05-02 General Motors Corporation Solid-state lithium battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PRISYAZHNII V.D. ET AL.: "Synthesis and Properties of Black Phosphorus", DOPOVIDI NATSIONAL'NOI AKADEMII NAUK UKRAINI, vol. 3, 1997, pages 154 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013152030A1 (fr) * 2012-04-02 2013-10-10 Ceramatec, Inc. Batterie à séparateur en structure de nid d'abeilles non poreux conducteur des ions de métaux alcalins
CN105762406A (zh) * 2016-05-10 2016-07-13 北京石油化工学院 一种有机型锌离子二次电池
CN112259741A (zh) * 2020-09-28 2021-01-22 江汉大学 一种集流体及其制备方法和应用

Similar Documents

Publication Publication Date Title
US7413582B2 (en) Lithium battery
US10847805B2 (en) Current collector clad with lithium ion conducting solid electrolyte
US7326493B2 (en) Lithium electrochemical generator comprising at least a bipolar electrode with conductive aluminium or aluminium alloy substrates
US5576119A (en) Rechargeable electrochemical alkali-metal cells
US5512389A (en) Rechargeable non-aqueous thin film lithium battery
JP3531866B2 (ja) 薄膜固体リチウムイオン二次電池
US9673478B2 (en) Multi-layer coatings for bipolar rechargeable batteries with enhanced terminal voltage
US11430994B2 (en) Protective coatings for lithium metal electrodes
KR20190030176A (ko) 고체 전해질을 포함하는 전고체 전지용 전극
CN113130847A (zh) 包括双极组件的电池组的电极层叠配置
KR20130130675A (ko) 쌍극 전극을 함유하는 장방형 전지를 포함하는 배터리
JPH11283664A (ja) 固体電解質電池
US20200052304A1 (en) Energy storage, bipolar electrode arrangement and method
KR20140053106A (ko) 리튬 이온 2차 전지
JP2010056067A (ja) コイン型リチウム二次電池
KR20190026873A (ko) 금속 도금-기반의 전기 에너지 저장 셀
JP2003242965A (ja) アルカリ金属イオン電気化学電池用の２枚の正極集電体
WO2008027050A1 (fr) Pile au lithium
US20070266554A1 (en) Electrochemical cell with moderate-rate discharging capability and method of production
JP4845245B2 (ja) リチウム電池
WO2019231892A1 (fr) Configuration d'électrode avec un séparateur d'inhibition de saillie
JP2000285910A (ja) リチウム電池
JP2001015125A (ja) リチウム電池
JP2010205739A (ja) リチウム電池
CN112103572A (zh) 基于复合材料电极的复合动力固态储能电芯

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 06814036

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU

122 Ep: pct application non-entry in european phase

Ref document number: 06814036

Country of ref document: EP

Kind code of ref document: A1