WO2016080912A1 - Batterie rechargeable au lithium-ion tout solide - Google Patents

Batterie rechargeable au lithium-ion tout solide Download PDF

Info

Publication number
WO2016080912A1
WO2016080912A1 PCT/SG2015/050457 SG2015050457W WO2016080912A1 WO 2016080912 A1 WO2016080912 A1 WO 2016080912A1 SG 2015050457 W SG2015050457 W SG 2015050457W WO 2016080912 A1 WO2016080912 A1 WO 2016080912A1
Authority
WO
WIPO (PCT)
Prior art keywords
cathode
solid
solid electrolyte
silicon
lithium
Prior art date
Application number
PCT/SG2015/050457
Other languages
English (en)
Inventor
Yihua Wang
Yuan Chen
Li Lu
Original Assignee
National University Of Singapore
Republic Polytechnic
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 National University Of Singapore, Republic Polytechnic filed Critical National University Of Singapore
Publication of WO2016080912A1 publication Critical patent/WO2016080912A1/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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • H01M4/0426—Sputtering
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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 an all-solid-state lithium-ion battery and a production method thereof.
  • Batteries are a useful source of stored energy that can be incorporated into a number of systems.
  • Rechargeable lithium-ion batteries are attractive energy storage systems for portable electronics and electric and hybrid-electric vehicles because of their high specific energy compared to other electrochemical energy storage devices.
  • a lithium-ion battery is composed mainly of a cathode, an anode, and an electrolyte layer disposed between the cathode and the anode (e.g., a layer consisting of a liquid electrolyte or a solid electrolyte).
  • the cathode and/or the anode is made using a coating solution (e.g., a solution of a slurry form or a paste form) for formation of the electrode containing an active material for the corresponding electrode, a binder, and a conductive aid.
  • All-solid-state thin film lithium ion batteries are deemed a promising replacement for liquid electrolyte-based lithium-ion batteries owing to their superior cycle life, compact structure, high energy and power densities with an extremely low self-discharge rate.
  • the state-of-art all-solid-state lithium-ion batteries mainly use thermal-evaporated lithium metal as anode which considerably undermines their cost-effectiveness and also raises safety concerns of lithium explosion.
  • the major problem that impedes all-solid-state lithium-ion batteries from wide commercialization lies in their extremely expensive fabrication cost in that the fabrication process consists of a series of physical vapor deposition in vacuum environment.
  • the current rechargeable lithium-ion batteries research efforts are mainly focusing on the application of Li-ion batteries for automotive applications. In order to achieve the desired performance for automotive applications, cathodes with larger storage capacities and higher operating voltages, along with electrolytes having a larger stability window are on demand to produce more durable and high power batteries.
  • High voltage spinel Li-Ni-Mn-0 cathodes have attracted much attention as alternatives to conventional layered cathodes.
  • Spinel LiNio.5Mn1.5O4 is of special interest because the material has a reaction voltage near 4.7 V vs. Li and a theoretical gravimetric capacity of ⁇ 147 mAh/g.
  • the operation at high voltages stems from the oxidation of Ni ions.
  • the structural stability can be kept due to Mn ions.
  • spinel Li-Ni-Mn-0 cathodes have very high rate capability due to the 3D diffusion pathways for Li ions inside the spinel structure.
  • CEI Cathode Electrolyte Interface
  • Thin film electrodes are an ideal platform to understand how the coating reduces capacity losses. This is very useful for studying the surface charge transfer kinetics or the bulk diffusion across particles of known dimensions. Moreover, no binder or additives are used, which facilitates the study of properties inherent to the high voltage cathode material.
  • Lithium metal can be a conversion anode in a thin film battery.
  • Lithium metal commonly used as anode in micro-batteries has a very low melting point (181°C) that appears to be incompatible with the solder-reflow connecting electronic component operation.
  • Due to the high activity of metal lithium currently successful commercial thin-film batteries are manufactured through vacuum or inert gas protecting continuous process without breaking vacuum.
  • this vacuum transfer equipment suggested by the US Department of Energy is extremely expensive.
  • the thermal-evaporated lithium metal process often makes lithium phosphorus oxynitride (LiPON) electrolyte overheated above 200 °C, which results in the crystallization and reduction of the Li-ion conductivity of LiPON layer and subsequent failure of all-solid-state thin-film battery.
  • LiPON lithium phosphorus oxynitride
  • Silicon has a huge volume change and is easy to be pulverized during lithium insertion, thus most researchers did not consider it as the anode material in thin-film battery.
  • sputtering process of silicon often makes LiPON layer overheated above 200 °C or breakage, which makes the full battery lack of electrochemical activity.
  • a group has successfully fabricated electrochemically active LiCo0 2 /LiPON/Si all-solid-state nanobatteries for the first time through Focused Ion Beam (FIB) equipment etc. 141 . They have claimed that to get the electrochemically active thin-film batteries, the thin-film batteries require biasing in the FIB immediately after fabrication either using the complete isolation or the pseudoisolation scheme from the thin film battery. Obviously, it is an expensive process and very difficult to scale up for production. What is needed, therefore, is to provide a thin film lithium ion battery that is relatively inexpensive and easy to produce and has high power density and long life.
  • FIB Focused Ion Beam
  • the thin film lithium ion battery of the present invention may typically include a case, an anode, a cathode, and a solid electrolyte layer.
  • the anode, cathode, and the solid electrolyte layer are encapsulated in the case.
  • the solid electrolyte is located between the anode and the cathode.
  • the cathode includes a cathode current collector and a cathode material layer disposed on a surface of the cathode current collector.
  • the anode includes an anode current collector and an anode material layer disposed on a surface of the anode current collector.
  • an all-solid-state lithium-ion battery cell comprising: (a) a cathode electrode, the cathode electrode comprising a lithium nickel manganese oxide; (b) an anode electrode, the anode electrode comprising a silicon material; and (c) a solid electrolyte disposed between the cathode electrode and the anode electrode, the solid electrolyte is UPON.
  • cathode and “anode”, it is meant to refer to any such electrode containing a cathode or anode material capable of implementing reversible progress of occlusion and release of lithium ions, desorption and insertion of lithium ions, or doping and dedoping with lithium ions.
  • solid electrolyte it is meant to include no particular restrictions on the solid electrolyte layer as long as it has the conductivity of lithium ions.
  • the lithium nickel manganese oxide has a spinel structure having a formula LiMni.5Nio.5O4.
  • the weight ratio of manganese and nickel in the lithium nickel manganese oxide may be between 2.50 to 2.82.
  • the weight ratio is 2.52.
  • the weight ratio may be 2.808.
  • the weight ratio of manganese and nickel may be about 1.
  • the cathode and anode electrodes each comprises a current collector.
  • the current collector may be any suitable electronic conductive material.
  • the current collector may be any one selected from the group comprising: platinum, copper and gold.
  • the cathode electrode may comprise any one selected from the group comprising: LiCo0 2 , LiMn 2 0 4 , LiCoMnNiO, and LiFeP0 4 .
  • the anode electrode may comprise any one selected from the group comprising: Sn and SnO.
  • the solid electrolyte may comprise any one selected from the group comprising: LiSiCON.
  • a plurality of battery cells are stacked with each other to form a battery.
  • a battery may be used to provide power for RFID, chip memory backup, smartcards, wireless sensors, smart bandages, and low power consumption devices, etc.
  • the LiPON solid electrolyte has an ionic conductivity of about 2.2 x 10 "6 S/m.
  • the thickness of the cathode and anode electrodes are 750 nm and 150 nm respectively.
  • a method for making an all- solid-state lithium-ion battery cell comprising: (a) forming a cathode electrode by depositing a cathode material on a substrate, the cathode material comprising a lithium nickel manganese oxide; (b) forming a solid electrolyte on the cathode, the solid electrolyte comprising LiPON; and (c) applying an anode electrode in operable contact with the solid electrolyte, the anode electrode comprising a silicon material.
  • the battery cell is formed by depositing the silicon anode on top of the solid electrolyte.
  • the cathode material is formed on the surface of the substrate by a physical deposition method.
  • the physical deposition method is a sputter deposition method comprising sputtering the substrate with a lithium nickel manganese oxide composite target in the presence of argon gas. It is understood to the skilled person that any suitable gas may be used to carry out the physical sputter deposition method.
  • the layer of lithium nickel manganese oxide deposited on the substrate may be between 50nm to 2000nm in thickness.
  • the sputtering is RF magnetron sputtering.
  • Sputter deposition is a physical vapour deposition method of thin film deposition by sputtering.
  • the substrate is a silicon wafer.
  • the silicon wafer may be coated with any material selected from the group comprising: platinum, copper and gold.
  • the LiPON electrolyte is formed by a sputter deposition method comprising sputtering the cathode electrode with a Li 3 P0 4 ceramic target in the presence of a nitrogen process gas.
  • the anode electrode is prepared by depositing a silicon material onto the solid electrolyte.
  • a 50 nm to 500 nm thin silicon thin film is deposited on the solid electrolyte by a sputtering method.
  • a platinum material, or any other conductive material, may be deposited on the silicon anode electrode.
  • a method for making a cathode electrode comprising: (a) providing a substrate coated with a conductive current collector; and (b) depositing a lithium nickel manganese oxide layer on the substrate by sputtering the substrate with a LiMn1.5Nio.5C composite target.
  • the sputtered lithium nickel manganese oxide layer is annealed for 2 hours at 50CTC.
  • a method of operating a battery comprising the steps of: (a) providing a battery cell according to the first aspect of the present invention; and (b) operating the battery at a voltage of between 3.0V and 4.55V.
  • the full thin-film battery shows excellent intercalation property and stability for cycling in the potential range from 3.0 to 4.55 V.
  • the properties of full all-solid-state spinel Li-Ni-Mn-O/LiPON/Si cells have not been reported in prior literature.
  • FIG. 1 SEM images showing surface morphology and particle size of the post-annealed films according to an embodiment of the present invention.
  • Figure 7 SEM cross section image of a Li-Ni-Mn-O/LiPON/Si full battery according to an embodiment of the present invention.
  • Figure 8. Electro-chemical performance of spinel Li-Ni-Mn-O/LiPON/Si full battery according to an embodiment of the present invention.
  • Figure 9 Voltage curve of spinel Li-Ni-Mn-O/LiPON/Si battery according to an embodiment of the present invention cycled at a current of 0.02 mA.
  • Figure 10 A schematic showing a thin film all-solid-state lithium-ion battery according to an embodiment of the present invention.
  • a spinel Li-Ni-Mn-O/LiPON/Si-based all-solid-state Li-ion battery has been successfully developed using sputter-deposition technique.
  • This Li-free all-solid- state Li-ion battery exhibited a high cut-off voltage of 4.55 V and superior cycling stability in a wide potential range from 3.0 to 4.55 V.
  • the highest specific capacity of the spinel Li-Ni- Mn-O/LiPON/Si-based all-solid-state Li-ion battery achieved so far is 30 ⁇ 2 and further optimization is currently underway.
  • FIG 10 is a schematic sectional view showing a basic configuration of a preferred embodiment of the thin film all-solid-state lithium-ion battery cell of the present invention.
  • the all-solid-state lithium-ion battery cell 20 shown in Figure 10 is composed mainly of a cathode 5 and an anode 10, and a solid electrolyte layer 15 disposed between the cathod 5 and anode 10.
  • the "anode” and “cathode” herein are based on the polarities during discharge of the lithium-ion battery 1. The preparation of the thin films according to the present invention will be described in greater detail below.
  • a Denton Discovery system was used for the all-solid-state thin film battery fabrication. During the film deposition, the target-substrate distance was kept at 5 cm.
  • the cathode Li- Ni-Mn-0 films were deposited onto Pt-coated silicon wafer substrates using RF magnetron sputtering with a LiMn1.5Nio.5O4 composite target.
  • the LiPON electrolyte thin films were also deposited using the same system with a ceramic target of Li 3 P0 4 using a nitrogen process gas.
  • the anode amorphous silicon thin films were grown using DC sputtering mode.
  • Thin film characterization Scanning Electron Microscope (SEM) and Energy Dispersive X-ray analysis (EDX) were obtained using a JEOL SEM equipped with an EDAX detector.
  • X-ray Diffraction (XRD) scans were acquired with a Bruker D8 Advance system. Electrochemical measurements were conducted inside an Ar-filled glovebox. For the electrochemical measurements, 750 nm Li- Ni-Mn-0 thin film (annealed in air at 500 for 2 h), 1000 nm UPON and 150 nm silicon were used.
  • the sputtered Li-Ni-Mn-0 thin films were annealed for two hours at different temperatures: 300, 400, 500, 600, and 700 °C. They all showed the spinel crystalline. However, Li-Ni-Mn-0 layer cracking was found for some samples during annealing. The SEM results of the sputtered Li-Ni-Mn-0 thin film after annealing at 500 °C are showed in Fig la. The weak adhesion between Li-Ni-Mn-0 layer and the Pt metal layer on silicon wafer substrate might be due to the different coefficient of expansion of layers and strong air convection produced by the oven fan during the annealing. More cracking on Li-Ni-Mn-0 thin film can be seen when the annealing at higher temperatures.
  • the UPON electrolyte layer was deposited by RF magnetron sputtering from a ceramic target of Li 3 P0 4 using a nitrogen process gas. Although the nitrogen partial pressure exceeds that of the oxygen in the plasma, only a small amount of nitrogen replaces the oxygen in the composition, and this nitrogen has a profound effect on the ion conductivity and electrochemical stability' 7 '.
  • nitrogen gas pressure, nitrogen flow speed, sputtering power, cooling substrate speed and sputtering time an amorphous LiPON layer can be obtained.
  • the LiPON layer can be easy crystallized at temperatures above 200 °C, it is important to grow the amorphous LiPON layer at low temperature so that Li-ion conductivity can be better than 10 "6 S/m.
  • the ionic conductivity of the LiPON electrolyte was characterized in a sandwiched Pt-LiPON-Ti structure by means of AC impedance spectroscopy. As shown in Fig. 3, the impedance spectra of a 1 ⁇ LiPON electrolyte exhibit two sequent semi-circular curves in the Nyquist plot. The first semi-circle represents the Li-ion transport in LiPON while the second arises from the Li-ion transfer at the LiPON-Ti interface.
  • the ionic conductivity of the sputter-deposited LiPON thin film was calculated to be around 2.2xl0 ⁇ 6 S/cm, which is comparable to 2.0xl0 "6 S/cm as reported by Nancy J. Dudney' 71 .
  • the deposited LiPON thin film degrades and exhibits numerous flower-like pin-holes after 2 mins exposure in air, as shown in Figure 4b. This confirms that the LiPON film is not compatible with the ambient humidity and air [3, 41 . The degradation of LiPON might result in poor performance of lithium battery.
  • Amorphous Silicon thin film anode Silicon is a promising candidate as the negative electrode for Li-ion conventional liquid electrolyte- based cells due to its high volumetric specific capacity, its ability to insert/deinsert lithium at a low average voltage (around 0.25 V).
  • this high volumetric capacity in the non-lithiated state is correlated with huge volume change during lithium insertion (increased by four times). This behavior is often at the beginning of a severe capacity fading, due to the formation of cracks and disintegration of both the active material and the electrode as well as a resulting loss of electrical contacts. These phenomena are amplified because of the reaction with liquid electrolytes.
  • silicon nano-wire and nano-tube were developed 181 . It is believed that the reduction of silicon particle size to nanometers could be somewhat helpful in powder-based silicon anodes.
  • Silicon thin films can be prepared by sputtering, a technique widely used in microelectronics industry. It has been reported that amorphous silicon thin film shows a more stable reversible capacity close to 3500 mAh/g during 200 cycles, and a greater adhesion to the current collector. No evidence of crack or damage was observed in the SEM images even after 500 cycles. Moreover, despite a well-known low lithium diffusion coefficient, the cells was successfully charged and discharged at a very high current density' 61 .
  • a 300 nm amorphous silicon thin film was deposited on copper foil.
  • Figure 5 shows the surface morphology and particle size of amorphous silicon thin film on copper current collector.
  • Figure 6 shows the electro-chemical performance of silicon thin film in liquid electrolyte 1.2M LiPF 6 in vinylene carbonate additive and ethylene carbonate/dimethyl carbonate (EC/DMC 3:7 per volume) mixture, where pure metal Li was used as the counter electrode and a piece of Celgard film as the separator, in a 2032 coin case.
  • the silicon nano-film measured in a liquid electrolyte shows a good retention of capacity as it can retain about 85% of the reversible capacity. 4.
  • the all-solid-state thin film batteries were prepared with 750 nm spinel Li-Ni-Mn-0 cathode and 150 nm Si anode.
  • the active area was 2.25 cm 2 , and the solid electrolyte LiPON was used.
  • the full cells were tested in a glove box.
  • the full battery was cycled between 4.55 and 3 V under a rate of C/2.
  • a SEM cross section of full battery is shown in Fig. 7.
  • the theoretical capacity for the stoichiometric spinel Li-Ni-Mn-0 is 65.5 ⁇ /cm 2 / m, assuming a gravimetric capacity of 146.7 mAh/g and 4.47 g/ cm 3 density 11, 2] . Based on the result of silicon anode testing, the 150 nm silicon anode capacity is enough to fit for that of spinel Li-Ni-Mn-0 cathode.
  • Figure 8 shows the capacity degradation of the full battery.
  • Spinel LiNio.5M n1.5O_. has a reaction voltage near 4.7 V vs. metal Li.
  • Our full battery spinel Li-Ni-Mn-O/LiPON/Si voltage difference is 4.55 V. This means the prepared spinel Li-Ni-Mn-0 material can be charged above 4.75 V vs. metal Li.
  • the capacity retention is between 100% and 92% for the cycles from cycle 3.
  • the coulombic efficiency of the full battery between cycled between 4.55 and 3.0 V is above 95% from cycle 3.
  • the capacity loss of the full battery might be due to the following reasons: (1) Li ions lacking in electrolyte, degradation of Si anode, and oxygen defection on the cathode that consumes Li ions from the electrolyte; (2) low lithium ion diffusion speed inserting/deserting from Si anode; (3) LiPON electrolyte decomposition on the surfaces.
  • the capacity degradation is more complex and differs from existing models that predict the cycling performance of the full battery based on liquid electrolyte.
  • liquid electrolyte was cycled between 4.55 and 3 V at a rate of C/2 between silicon anode and spinel Li-Ni- Mn-0 cathode
  • the discharge capacity can decrease to zero, which might be attributed to the continuous electrolyte decomposition at high voltages, resulting in the formation of a CEI [1"31 .
  • Figure 9 shows that solid LiPON can function well in the spinel Li-Ni-Mn-O/LiPON/Si battery cycled at a current of 0.02 mA. LiPON clearly has an effect on the capacity retention of full cells cycled between 4.55 and 3 V.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne une batterie au lithium-ion tout solide et son procédé de production. Plus particulièrement, l'invention concerne un élément de batterie au lithium-ion tout solide, comprenant : (a) une électrode de cathode, l'électrode de cathode comprenant un oxyde de lithium-nickel-manganèse ; (b) une électrode d'anode, l'électrode d'anode comprenant un matériau à base de silicium ; et (c) un électrolyte solide disposé entre l'électrode de cathode et l'électrode d'anode, l'électrolyte solide étant du LiPON.
PCT/SG2015/050457 2014-11-18 2015-11-18 Batterie rechargeable au lithium-ion tout solide WO2016080912A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201462081064P 2014-11-18 2014-11-18
US62/081,064 2014-11-18

Publications (1)

Publication Number Publication Date
WO2016080912A1 true WO2016080912A1 (fr) 2016-05-26

Family

ID=56014300

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SG2015/050457 WO2016080912A1 (fr) 2014-11-18 2015-11-18 Batterie rechargeable au lithium-ion tout solide

Country Status (1)

Country Link
WO (1) WO2016080912A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110085917A (zh) * 2019-04-28 2019-08-02 天津瑞晟晖能科技有限公司 全固态锂离子电池及其制备方法和用电设备
CN112736282A (zh) * 2020-12-26 2021-04-30 维达力实业(深圳)有限公司 固态电解质、固态电池、固态电池制造设备及制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140106186A1 (en) * 2012-10-12 2014-04-17 Ut-Battelle, Llc LIPON COATINGS FOR HIGH VOLTAGE AND HIGH TEMPERATURE Li-ION BATTERY CATHODES
US20140308570A1 (en) * 2011-11-02 2014-10-16 I-Ten Method for the production of thin-film lithium-ion microbatteries and resulting microbatteries
US20140308576A1 (en) * 2011-11-02 2014-10-16 I-Ten Method for manufacturing all-solid-state thin-film batteries

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140308570A1 (en) * 2011-11-02 2014-10-16 I-Ten Method for the production of thin-film lithium-ion microbatteries and resulting microbatteries
US20140308576A1 (en) * 2011-11-02 2014-10-16 I-Ten Method for manufacturing all-solid-state thin-film batteries
US20140106186A1 (en) * 2012-10-12 2014-04-17 Ut-Battelle, Llc LIPON COATINGS FOR HIGH VOLTAGE AND HIGH TEMPERATURE Li-ION BATTERY CATHODES

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BROWNING, JAMES F. ET AL.: "In Situ Determination of the Liquid/Solid Interface Thickness and Composition for the Li Ion Cathode LiMn1.5Ni0.504", ACS APPLIED MATERIALS & INTERFACES, vol. 6, no. 21, 2014, pages 18569 - 18576, [retrieved on 20141006] *
LI, JUCHUAN ET AL.: "Artificial solid electrolyte interphase to address the electrochemical degradation of silicon electrodes", ACS APPLIED MATERIALS & INTERFACES, vol. 6, no. 13, 2014, pages 10083 - 10088, [retrieved on 20140613] *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110085917A (zh) * 2019-04-28 2019-08-02 天津瑞晟晖能科技有限公司 全固态锂离子电池及其制备方法和用电设备
CN112736282A (zh) * 2020-12-26 2021-04-30 维达力实业(深圳)有限公司 固态电解质、固态电池、固态电池制造设备及制备方法
CN112736282B (zh) * 2020-12-26 2022-07-12 维达力实业(深圳)有限公司 固态电解质、固态电池、固态电池制造设备及制备方法

Similar Documents

Publication Publication Date Title
US10497927B2 (en) Methods of applying self-forming artificial solid electrolyte interface (SEI) layer to stabilize cycle stability of electrodes in lithium batteries
JP7287904B2 (ja) 固体電解質中の金属の伝播を抑制する方法
US20200194831A1 (en) Solid electrolyte sheet, method for manufacturing same, and sodium ion all-solid-state secondary cell
KR101935365B1 (ko) 플렉서블 고체전해질, 이를 포함하는 전고체형 리튬전지, 및 이의 제조방법
JP2024023248A (ja) リチウム金属アノードのための、カルコゲナイドを用いたエクスシトゥ固体電解質界面修飾
KR101166019B1 (ko) 도전제, 이를 포함하는 리튬 이차 전지 양극용 슬러리 조성물 및 이를 포함하는 리튬 이차 전지
WO2015068268A1 (fr) Cellule entièrement à semi-conducteurs, électrode pour cellule entièrement à semi-conducteurs, et procédé de fabrication associé
KR20180077287A (ko) 이온 전도성 화합물 및 관련 용도
KR20210048607A (ko) 애노드 활성 물질, 캐소드 활성 물질, 및 고체-상태 전해질에 대한 나노-엔지니어링된 코팅 및 나노-엔지니어링된 코팅을 함유하는 배터리의 제조 방법
WO2016025866A1 (fr) Matériaux de conversion dopés pour cathodes de batterie secondaire
Tan et al. Controllable crystalline preferred orientation in Li–Co–Ni–Mn oxide cathode thin films for all-solid-state lithium batteries
US20200280093A1 (en) Solid-State Battery Electrolyte Having Increased Stability Towards Cathode Materials
CN102668190A (zh) 固体电解质电池和正极活性物质
WO2019032514A1 (fr) Conducteur mixte ionique et électronique pour batterie tout solide
Wang et al. High-stability 5 V spinel LiNi0. 5Mn1. 5O4 sputtered thin film electrodes by modifying with aluminium oxide
EP2503634B1 (fr) Procédé de fabrication d'une batterie rechargeable de type lithium-ion
KR102533760B1 (ko) 리튬화된 비정질 규소산화물 전극의 제조방법, 이에 의하여 제조된 리튬화된 비정질 규소산화물 전극 및 이를 포함하는 리튬황전지
Hu et al. Roles of Al-doped ZnO (AZO) modification layer on improving electrochemical performance of LiNi 1/3 Co 1/3 Mn 1/3 O 2 thin film cathode
WO2016080912A1 (fr) Batterie rechargeable au lithium-ion tout solide
Chen et al. A high-voltage all-solid-state lithium-ion battery with Li–Mn–Ni–O and silicon thin-film electrodes
CN108539151B (zh) 二次电池用电极材料及二次电池
KR101567884B1 (ko) 이차 전지용 음극 및 그 제조 방법
Suzuki et al. Development of All-solid-state Thin-film Secondary Battery for MEMS and IoT Device
KR20080086121A (ko) 리튬 이차 전지용 음극 활물질, 이의 제조방법 및 이를포함하는 리튬 이차 전지
KR20150055186A (ko) 전극 및 그 제조 방법, 이를 구비하는 전지

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: 15861471

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15861471

Country of ref document: EP

Kind code of ref document: A1