WO2018170679A1 - Electrode active material, a process for preparing said electrode active material, and a cathode and a battery containing said electrode active material - Google Patents

Electrode active material, a process for preparing said electrode active material, and a cathode and a battery containing said electrode active material Download PDF

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Publication number
WO2018170679A1
WO2018170679A1 PCT/CN2017/077300 CN2017077300W WO2018170679A1 WO 2018170679 A1 WO2018170679 A1 WO 2018170679A1 CN 2017077300 W CN2017077300 W CN 2017077300W WO 2018170679 A1 WO2018170679 A1 WO 2018170679A1
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active material
electrode active
lithium metal
lithium
metal oxide
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PCT/CN2017/077300
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French (fr)
Inventor
Nahong ZHAO
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Robert Bosch Gmbh
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Priority to CN201780088749.8A priority Critical patent/CN110447127A/en
Priority to PCT/CN2017/077300 priority patent/WO2018170679A1/en
Publication of WO2018170679A1 publication Critical patent/WO2018170679A1/en

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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
    • 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
    • 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
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of 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
    • H01M4/362—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
    • H01M4/36—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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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

Definitions

  • the present invention relates to an electrode active material, which contains a granular lithium metal oxide, wherein the granular lithium metal oxide is coated with a polyacrylonitrile coating layer, and sulfur is loaded in the polyacrylonitrile coating layer.
  • the present invention further relates to a process for preparing said electrode active material, to a cathode containing said electrode active material, and to a battery containing said cathode.
  • the overall performance of current lithium ion batteries are mainly decided by the internal materials and their structures, especially by the cathodes, such as exhibiting lower specific capacities compared with graphite anode, such as instable cathode/electrolyte interface.
  • the cost of cathode material dominates 30%of the total value.
  • spinel LiMn 2 O 4 As for spinel LiMn 2 O 4 , it is low cost and capable of fast charge-discharge, but its capacity is low, only 120 mAh/g or so. Besides, the poor interface compatibility in between LiMn 2 O 4 material and liquid carbonate-based electrolyte causes severe side reactions and synchronizes with intrinsic John-Teller effect, thus results in material dissolution and poor cycling stability, especially at high temperature.
  • Lithium-rich lithium-nickel-cobalt-manganese-oxide (High-Energy NCM cathode material, HE-NCM) has high capacity, about 250 mAh/g, but exists similar problem during charge and discharge. Besides, interface problem also improves the oxygen losing and synchronize the intrinsic structure change from layer structure to spinel structure, which causes voltage decay and energy loss.
  • Lithium-nickel-cobalt-aluminum-oxide (NCA cathode material) is superior regarding to its cyclability and capacity (about 190 mAh/g or so) , but the poor stability at high temperature brings obvious safety defect to the battery.
  • the current carbonate-based electrolyte will start to break down chemically once it comes in contact with the lithium metal oxide, no matter the electrochemical process starts or not, which leads to complex problems and a poor cycling performance.
  • the discomposition reaction can be accelerated at a high temperature.
  • the performances of the cathode and the instable cathode/electrolyte interface are still the limitations for their further development in terms of low capacity, high cost, and instable cycling performance at a high temperature.
  • the object of the present invention is to provide an electrode active material with a low cost, a high capacity, a good stability and a good cycling performance especially at high temperature.
  • Said object can be achieved by an electrode active material, which contains a granular lithium metal oxide, wherein the granular lithium metal oxide is coated with a polyacrylonitrile coating layer, and sulfur is loaded in the polyacrylonitrile coating layer.
  • Said object can be achieved by a process for preparing the electrode active material according to the present invention, said process including the following steps:
  • a cathode for lithium ion batteries or lithium-sulfur batteries which contains the electrode active material according to the present invention.
  • a battery which contains the cathode according to the present invention.
  • Figure 1 is a schematic diagram of the electrode active material according to the present invention.
  • the present invention relates to an electrode active material, which contains a granular lithium metal oxide, wherein the granular lithium metal oxide is coated with a polyacrylonitrile coating layer, and sulfur is loaded in the polyacrylonitrile coating layer.
  • Figure 1 is a schematic diagram of the electrode active material according to the present invention, which contains a granular lithium metal oxide 1 as the core, wherein the granular lithium metal oxide 1 is coated with a polyacrylonitrile coating layer 2 as the shell, and sulfur is loaded in the polyacrylonitrile coating layer 2.
  • the interface property of the granular lithium metal oxides can be greatly improved by the specific core-shell structure as shown in Figure 1.
  • the granular lithium metal oxide has an average diameter of 100 nm –20 ⁇ m, preferably 500 nm –10 ⁇ m.
  • the polyacrylonitrile coating layer has a thickness of 10 nm –500 nm, preferably 10 nm –200 nm.
  • the sulfur load amount in the polyacrylonitrile coating layer 2 can be 2 –20 wt. %, preferably 5 –10 wt. %, based on the total weight of the electrode active material.
  • the granular lithium metal oxide can be made from one or more lithium metal oxides.
  • the lithium metal oxides can be binary, ternary or quaternary lithium metal oxides, for example selected from the group consisting of lithium nickel oxide, lithium cobalt oxide, lithium manganese oxide, lithium nickel cobalt oxide, and lithium nickel cobalt manganese oxide.
  • the specific examples of the granular lithium metal oxides can be spinel LiMn 2 O 4 (lithium manganese oxide or lithium manganate) , HE-NCM (High Energy Lithium Nickel Cobalt Manganese Oxide) and NCA (Lithium Nickel Cobalt Aluminum Oxide) .
  • the present invention relates to a process for preparing the electrode active material according to the present invention, said process including the following steps:
  • the granular lithium metal oxide precursor can be prepared by co-precipitation or sol-gel method from a lithium salt and one or more transition metal salts, wherein the transition metal can be selected from the group consisting of nickel, cobalt, and manganese.
  • the granular lithium metal oxides can be prepared from the granular lithium metal oxide precursors by sintering at a high temperature.
  • the granular lithium metal oxide can be made from one or more lithium metal oxides.
  • the lithium metal oxides can be binary, ternary or quaternary lithium metal oxides, for example selected from the group consisting of lithium nickel oxide, lithium cobalt oxide, lithium manganese oxide, lithium nickel cobalt oxide, and lithium nickel cobalt manganese oxide.
  • the specific examples of the granular lithium metal oxides can be spinel LiMn 2 O 4 , HE-NCM and NCA.
  • the granular lithium metal oxide precursor or the granular lithium metal oxide can be dispersed into a polyacrylonitrile solution, for example by vigorous stirring or sonication.
  • concentration of the polyacrylonitrile solution is not particularly limited, for example 3 –20 wt. %, preferably 5 –15 wt. %, more preferably 6 –10 wt. %, and can be determined according to the desired thickness of the polyacrylonitrile coating layer.
  • the solvent for said polyacrylonitrile solution or dispersion is not particularly limited, for example DMF, TMF, THF, or NMP.
  • the molecular weight (Mn) of the polyacrylonitrile used here is not particularly limited, and can be for example 50,000 –800,000 g/mol, preferably 100,000 –500,000 g/mol.
  • the granular lithium metal oxide precursor or the granular lithium metal oxide can be coated with a polyacrylonitrile coating layer 2 after the solvent has been evaporated.
  • the way of evaporating the solvent is not particularly limited here.
  • the solvent can be evaporated under stirring, preferably at an elevated temperature, for example about 50 °C, in an oven.
  • the product of step 3) can be annealed in the presence of sulfur in the presence of sulfur at a temperature of 280 –450 °C for 1 –4 hours.
  • the product of step 3) can be sealed in an autoclave under an inert atmosphere, for example nitrogen or argon, and heated in the presence of sulfur at a temperature of 280 –450 °C, preferably 300 –420 °C, more preferably 350 –400 °C, with a fast heating speed.
  • sulfur in step 4) can be loaded in the polyacrylonitrile coating layer 2 at an amount of 2 –20 wt. %, preferably 5 –10 wt. %, based on the total weight of the electrode active material.
  • the electrode active material according to the present invention can be mixed with carbon black and poly- (vinyl difluoride) (PVDF) and pasted on an Al foil.
  • PVDF poly- (vinyl difluoride)
  • Lithium foil can be used as the counter electrode, and assembled with a separator and carbonate electrolyte consisted of LiPF 6 salt and ethylene carbonate solvent.
  • the granular lithium metal oxides can be completely blocked or encapsulated by the polyacrylonitrile coating layer 2 (SPAN, sulfur/polyacrylonitrile) , which is loaded with sulfur, and left no direct contact with the liquid electrolyte, so as to inhibit both the metal dissolution and the electrolyte decomposition reaction usually.
  • SPAN polyacrylonitrile coating layer 2
  • sulfur loaded in the polyacrylonitrile coating layer is reactive to lithium ions and also acts as the cathode active material.
  • the cost of sulfur is expected to be much lower than the metal oxide cathode active material in the long term.
  • the core-shell cathode active material with a SPAN coating layer according to the present invention shows a better material compatibility and a better electrochemical stability with the electrolyte, and thus prominent electrochemical performances and a higher energy density can be achieved as well.
  • the cathode active material with a SPAN coating layer according to the present invention is suitable to encounter with the lithiated anode or the anode containing lithium, and that the amount of lithium in the anode can be calculated in view of the proportion of SPAN in the cathode.
  • the present invention relates to a cathode for lithium ion batteries or lithium-sulfur batteries, which contains the electrode active material according to the present invention.
  • the present invention relates to a battery, which contains the cathode according to the present invention.
  • the battery can be a lithium ion battery or a lithium-sulfur battery.
  • Electrodes active material include, but are not limited to, high-energy-density lithium ion batteries with acceptable high power density for energy storage applications, such as power tools, photovoltaic cells and electric vehicles.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

An electrode active material, which contains a granular lithium metal oxide(1), wherein the granular lithium metal oxide(1) is coated with a polyacrylonitrile coating layer(2), and sulfur is loaded in the polyacrylonitrile coating layer(2). Provided is a process for preparing said electrode active material, a cathode containing said electrode active material, and a battery containing said cathode.

Description

ELECTRODE ACTIVE MATERIAL, A PROCESS FOR PREPARING SAID ELECTRODE ACTIVE MATERIAL, AND A CATHODE AND A BATTERY CONTAINING SAID ELECTRODE ACTIVE MATERIAL Technical Field
The present invention relates to an electrode active material, which contains a granular lithium metal oxide, wherein the granular lithium metal oxide is coated with a polyacrylonitrile coating layer, and sulfur is loaded in the polyacrylonitrile coating layer. The present invention further relates to a process for preparing said electrode active material, to a cathode containing said electrode active material, and to a battery containing said cathode.
Background Art
The overall performance of current lithium ion batteries are mainly decided by the internal materials and their structures, especially by the cathodes, such as exhibiting lower specific capacities compared with graphite anode, such as instable cathode/electrolyte interface. Besides, among all components including cathode, anode, separator, electrolyte and battery housing, the cost of cathode material dominates 30％of the total value.
As for spinel LiMn2O4, it is low cost and capable of fast charge-discharge, but its capacity is low, only 120 mAh/g or so. Besides, the poor interface compatibility in between LiMn2O4 material and liquid carbonate-based electrolyte causes severe side reactions and synchronizes with intrinsic John-Teller effect, thus results in material dissolution and poor cycling stability, especially at high temperature.
Lithium-rich lithium-nickel-cobalt-manganese-oxide (High-Energy NCM cathode material, HE-NCM) has high capacity, about 250 mAh/g, but exists similar problem during charge and discharge. Besides, interface problem also improves the oxygen losing and synchronize the intrinsic structure change from layer structure to spinel structure, which causes voltage decay and energy loss.
Lithium-nickel-cobalt-aluminum-oxide (NCA cathode material) is superior regarding to its cyclability and capacity (about 190 mAh/g or so) , but the poor stability at high temperature brings obvious safety defect to the battery.
Besides, the current carbonate-based electrolyte will start to break down chemically once it comes in contact with the lithium metal oxide, no matter the electrochemical process starts or not, which leads to complex problems and a poor cycling performance. The discomposition reaction can be accelerated at a high temperature. Overall, the performances of the cathode and the instable cathode/electrolyte interface are still the limitations for their further development in terms of low capacity, high cost, and instable cycling performance at a high temperature.
Summary of Invention
The object of the present invention is to provide an electrode active material with a low cost, a high capacity, a good stability and a good cycling performance especially at high temperature.
Said object, according to one aspect, can be achieved by an electrode active material, which contains a granular lithium metal oxide, wherein the granular lithium metal oxide is coated with a polyacrylonitrile coating layer, and sulfur is loaded in the polyacrylonitrile coating layer.
Said object, according to another aspect, can be achieved by a process for preparing the electrode active material according to the present invention, said process including the following steps:
1) preparing one or more granular lithium metal oxide precursors or one or more granular lithium metal oxides；
2) dispersing the granular lithium metal oxide precursor or the granular lithium metal oxide in a polyacrylonitrile solution；
3) evaporating the solvent of the polyacrylonitrile solution；
4) annealing the product of 3) in the presence of sulfur at a temperature of 280 –450 ℃. According to another aspect of the present invention, a cathode for lithium ion batteries or lithium-sulfur batteries is provided, which contains the electrode active material according to the present invention.
According to another aspect of the present invention, a battery is provided, which contains the cathode according to the present invention.
Brief Description of Drawings
Each aspect of the present invention will be illustrated in more detail in conjunction with the accompanying drawings, wherein :
Figure 1 is a schematic diagram of the electrode active material according to the present invention.
Detailed Description of Preferred Embodiments
All publications, patent applications, patents and other references mentioned herein, if not otherwise indicated, are explicitly incorporated by reference herein in their entirety for all purposes as if fully set forth.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range  limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
The present invention, according to one aspect, relates to an electrode active material, which contains a granular lithium metal oxide, wherein the granular lithium metal oxide is coated with a polyacrylonitrile coating layer, and sulfur is loaded in the polyacrylonitrile coating layer.
Figure 1 is a schematic diagram of the electrode active material according to the present invention, which contains a granular lithium metal oxide 1 as the core, wherein the granular lithium metal oxide 1 is coated with a polyacrylonitrile coating layer 2 as the shell, and sulfur is loaded in the polyacrylonitrile coating layer 2. The interface property of the granular lithium metal oxides can be greatly improved by the specific core-shell structure as shown in Figure 1.
In accordance with an embodiment of the electrode active material according to the present invention, the granular lithium metal oxide has an average diameter of 100 nm –20 μm, preferably 500 nm –10 μm.
In accordance with another embodiment of the electrode active material according to the present invention, the polyacrylonitrile coating layer has a thickness of 10 nm –500 nm, preferably 10 nm –200 nm.
In accordance with another embodiment of the electrode active material according to the present invention, the sulfur load amount in the polyacrylonitrile coating layer 2 can be 2 –20 wt. ％, preferably 5 –10 wt. ％, based on the total weight of the electrode active material.
In accordance with another embodiment of the electrode active material according to the present invention, the granular lithium metal oxide can be made from one or more lithium metal oxides. The lithium metal oxides can be binary, ternary or quaternary lithium metal oxides, for example selected from the group consisting of lithium nickel oxide, lithium cobalt oxide, lithium manganese oxide, lithium nickel cobalt oxide, and lithium nickel cobalt manganese oxide. The specific examples of the granular lithium metal oxides can be spinel LiMn2O4 (lithium manganese oxide or lithium manganate) , HE-NCM (High Energy Lithium Nickel Cobalt Manganese Oxide) and NCA (Lithium Nickel Cobalt Aluminum Oxide) .
The present invention, according to another aspect, relates to a process for preparing the electrode active material according to the present invention, said process including the following steps:
1) preparing one or more granular lithium metal oxide precursors or one or more granular lithium metal oxides；
2) dispersing the granular lithium metal oxide precursor or the granular lithium metal oxide into a polyacrylonitrile solution；
3) evaporating the solvent of the polyacrylonitrile solution；
4) annealing the product of 3) in the presence of sulfur at a temperature of 280 –450 ℃.
1) Preparation of granular lithium metal oxide precursors or granular lithium metal oxides In accordance with an embodiment of the process according to the present invention, the granular lithium metal oxide precursor can be prepared by co-precipitation or sol-gel method from a lithium salt and one or more transition metal salts, wherein the transition metal can be selected from the group consisting of nickel, cobalt, and manganese. The granular lithium metal oxides can be prepared from the granular lithium metal oxide precursors by sintering at a high temperature.
The granular lithium metal oxide can be made from one or more lithium metal oxides. The lithium metal oxides can be binary, ternary or quaternary lithium metal oxides, for example selected from the group consisting of lithium nickel oxide, lithium cobalt oxide, lithium manganese oxide, lithium nickel cobalt oxide, and lithium nickel cobalt manganese oxide. The specific examples of the granular lithium metal oxides can be spinel LiMn2O4, HE-NCM and NCA.
2) Dispersing into a polyacrylonitrile solution
The granular lithium metal oxide precursor or the granular lithium metal oxide can be dispersed into a polyacrylonitrile solution, for example by vigorous stirring or sonication. The concentration of the polyacrylonitrile solution is not particularly limited, for example 3 –20 wt. ％, preferably 5 –15 wt. ％, more preferably 6 –10 wt. ％, and can be determined according to the desired thickness of the polyacrylonitrile coating layer. The solvent for said polyacrylonitrile solution or dispersion is not particularly limited, for example DMF, TMF, THF, or NMP. The molecular weight (Mn) of the polyacrylonitrile used here is not particularly limited, and can be for example 50,000 –800,000 g/mol, preferably 100,000 –500,000 g/mol.
3) Evaporating the solvent
The granular lithium metal oxide precursor or the granular lithium metal oxide can be coated with a polyacrylonitrile coating layer 2 after the solvent has been evaporated. The way of evaporating the solvent is not particularly limited here. For example, the solvent can be evaporated under stirring, preferably at an elevated temperature, for example about 50 ℃, in an oven.
4) Annealing
The product of step 3) can be annealed in the presence of sulfur in the presence of sulfur at a temperature of 280 –450 ℃ for 1 –4 hours. In particular the product of step 3) can be sealed in an autoclave under an inert atmosphere, for example nitrogen or argon, and heated in the presence of sulfur at a temperature of 280 –450 ℃, preferably 300 –420 ℃, more preferably 350 –400 ℃, with a fast heating speed.
In accordance with another embodiment of the process according to the present invention, in step 4) , sulfur can be loaded in the polyacrylonitrile coating layer 2 at an amount of 2 –20 wt. ％, preferably 5 –10 wt. ％, based on the total weight of the electrode active material.
Preparation of working electrode
The electrode active material according to the present invention can be mixed with carbon black and poly- (vinyl difluoride) (PVDF) and pasted on an Al foil. Lithium foil can be used as the counter electrode, and assembled with a separator and carbonate electrolyte consisted of LiPF6 salt and ethylene carbonate solvent.
The granular lithium metal oxides can be completely blocked or encapsulated by the polyacrylonitrile coating layer 2 (SPAN, sulfur/polyacrylonitrile) , which is loaded with sulfur, and left no direct contact with the liquid electrolyte, so as to inhibit both the metal dissolution and the electrolyte decomposition reaction usually.
On the other hand, sulfur loaded in the polyacrylonitrile coating layer (SPAN) is reactive to lithium ions and also acts as the cathode active material. The cost of sulfur is expected to be much lower than the metal oxide cathode active material in the long term.
The core-shell cathode active material with a SPAN coating layer according to the present invention shows a better material compatibility and a better electrochemical stability with the electrolyte, and thus prominent electrochemical performances and a higher energy density can be achieved as well.
It should be noted that the cathode active material with a SPAN coating layer according to the present invention is suitable to encounter with the lithiated anode or the anode containing lithium, and that the amount of lithium in the anode can be calculated in view of the proportion of SPAN in the cathode.
The present invention, according to another aspect, relates to a cathode for lithium ion batteries or lithium-sulfur batteries, which contains the electrode active material according to the present invention.
The present invention, according to further aspect, relates to a battery, which contains the cathode according to the present invention. Preferably the battery can be a lithium ion battery or a lithium-sulfur battery.
Potential applications of the electrode active material according to the present invention include, but are not limited to, high-energy-density lithium ion batteries with acceptable high power density for energy storage applications, such as power tools, photovoltaic cells and electric vehicles.
While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. The attached claims and their equivalents are intended to cover all the modifications, substitutions and changes as would fall within the scope and spirit of the invention.

Claims (10)

  1. An electrode active material, characterized in that the electrode active material contains a granular lithium metal oxide (1) , the granular lithium metal oxide (1) is coated with a polyacrylonitrile coating layer (2) , and sulfur is loaded in the polyacrylonitrile coating layer (2) .
  2. The electrode active material of claim 1, characterized in that the granular lithium metal oxide (1) has an average diameter of 100 nm–20 μm, preferably 500 nm–10 μm.
  3. The electrode active material of claim 1 or 2, characterized in that the polyacrylonitrile coating layer (2) has a thickness of 10 nm–500 nm, preferably 10 nm–200 nm.
  4. The electrode active material of any one of claims 1 to 3, characterized in that the sulfur load amount in the polyacrylonitrile coating layer (2) is 2–20 wt. ％, preferably 5–10 wt. ％, based on the total weight of the electrode active material.
  5. The electrode active material of any one of claims 1 to 4, characterized in that the granular lithium metal oxide (1) is made from one or more lithium metal oxides, which are selected from the group consisting of lithium nickel oxide, lithium cobalt oxide, lithium manganese oxide, lithium nickel cobalt oxide, and lithium nickel cobalt manganese oxide.
  6. A process for preparing the electrode active material of any one of claims 1 to 5, said process including the following steps:
    1) preparing one or more granular lithium metal oxide precursors or one or more granular lithium metal oxides；
    2) dispersing the granular lithium metal oxide precursor or the granular lithium metal oxide in a polyacrylonitrile solution；
    3) evaporating the solvent of the polyacrylonitrile solution；
    4) annealing the product of 3) in the presence of sulfur at a temperature of 280–450℃.
  7. The process of claim 6, characterized in that the granular lithium metal oxide precursor is prepared by co-precipitation or sol-gel method from a lithium salt and one or more transition metal salts, which are selected from the group consisting of nickel, cobalt, and manganese.
  8. The process of claim 6 or 7, characterized in that in step 4) , sulfur is loaded in the polyacrylonitrile coating layer (2) at an amount of 2–20 wt. ％, preferably 5–10 wt. ％, based on the total weight of the electrode active material.
  9. A cathode for lithium ion batteries or lithium-sulfur batteries, characterized in that the cathode contains the electrode active material of any one of claims 1 to 5 or the electrode active material prepared by the process of any one of claims 6 to 8.
  10. A battery, characterized in that the battery contains the cathode of claim 9.
PCT/CN2017/077300 2017-03-20 2017-03-20 Electrode active material, a process for preparing said electrode active material, and a cathode and a battery containing said electrode active material WO2018170679A1 (en)

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