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EP2973790A1 - Matériaux composites de cathode ayant une durée de vie de cycle améliorée - Google Patents

Matériaux composites de cathode ayant une durée de vie de cycle améliorée

Info

Publication number
EP2973790A1
EP2973790A1 EP13877477.3A EP13877477A EP2973790A1 EP 2973790 A1 EP2973790 A1 EP 2973790A1 EP 13877477 A EP13877477 A EP 13877477A EP 2973790 A1 EP2973790 A1 EP 2973790A1
Authority
EP
European Patent Office
Prior art keywords
lithium storage
nickel content
lithiated
capacity
dopant
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP13877477.3A
Other languages
German (de)
English (en)
Inventor
Benjamin Reichman
William Mays
Diana Wong
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ovonic Battery Co Inc
Original Assignee
Ovonic Battery Co Inc
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 Ovonic Battery Co Inc filed Critical Ovonic Battery Co Inc
Publication of EP2973790A1 publication Critical patent/EP2973790A1/fr
Withdrawn legal-status Critical Current

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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
    • H01M10/052—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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • H01M4/48—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
    • 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

  • This invention relates to composite materials and methods for their fabrication.
  • the invention relates to composite lithium storage materials that are capable of absorbing and desorbing lithium.
  • the invention relates to a composite of a high nickel content material and a transition metal oxide or sulfide, the combination of which provides a lithium storage material with high capacity over an extended cycle life.
  • a generalized lithium battery includes an anode and a cathode that are disposed in a volume of a nonaqueous electrolyte material typically including one or more lithium salts and a solvent such as an organic carbonate material.
  • the anode and cathode have a body of separator material interposed therebetween.
  • lithium ions travel from the cathode to the anode and are intercalated therein.
  • discharge of the battery the process reverses.
  • Nickel containing mixed oxide materials offer a solution to the disadvantages of L1C0O 2 . These materials offer high capacities, often with a specific capacity of 200 mAh/g or greater.
  • Ni02 or compositions where some of the nickel is replaced with cobalt show excellent capacities, but suffer from sub-optimal cycle life as a result of their high oxidation power and oxygen release. For example, after only 5 and 10 cycles the capacity of Ni0 2 or Ni9 2 Co 8 drops from >200 mAh/g to ⁇ 160 mAh/g.
  • Novel lithiated composite materials are disclosed that are useful as an electrode material, optionally in a cathode for inclusion in a rechargeable lithium ion electrochemical cell. These materials are characterized by high capacity maintained over an unexpectedly long cycle life, particularly relative to the high nickel content lithium storage material when used alone.
  • the novel lithiated composite materials include: a non-lithiated high nickel content lithium storage material characterized by greater than 63 weight percent nickel; a non-lithiated transition metal dopant material; and a lithium source; and where the resulting molecular structure of the materials is imparted by intermixing the lithium storage materials and the lithium source followed by sintering to form the final lithiated composite material.
  • the high nickel content lithium storage material is present as a predominant by weight relative to the non- lithiated transition metal dopant material, and the composite material is characterized by not only high capacity but also by longer cycle life than that of the high nickel content lithium storage material when lithiated and used alone.
  • the performance characteristics of the lithiated composite materials include the ability to maintain a capacity in excess of 170 mAh/g at 30 cycles, optionally a capacity in excess of 160 mAh/g per gram at 40 cycles.
  • the electrode materials include the dopant material at 10 atomic percent or less, optionally from 0.1 to 4 atomic percent, relative to the high nickel content lithium storage material.
  • the high nickel content lithium storage material includes Ni0 2 , N192C0 8 O2, or combinations thereof.
  • a high nickel content lithium storage material also includes Mn at an atomic percentage of 10% or less.
  • the dopant used in the lithiated composite materials is optionally an oxide of a transition metal, optionally oxides of Ti, W, Mo, or combinations thereof.
  • the dopant used in the lithiated composite materials is a sulfide of a transition metal, optionally a sulfide of W, Mo, or combinations thereof.
  • both an oxide of a transition metal and a sulfide of a transition metal are employed.
  • the lithium source may be present at greater than stoichiometric ratio.
  • Methods are also provided for making a high capacity, long cycle life lithiated composite material useful in an electrode for a rechargeable lithium ion electrochemical cell that addressed the long felt need for a high capacity, long cycle life battery.
  • Methods include: providing a non-lithiated high nickel content lithium storage material characterized by greater than 63 weight percent nickel; providing a non-lithiated transition metal dopant; mixing the lithium storage material and the dopant with a lithium source to form a lithiated composite material, wherein the high nickel content lithium storage material is present as a predominant by weight relative to the dopant; and sintering the lithiated composite material to produce a lithiated composite material characterized by not only high capacity but also by a longer cycle life than that of the high nickel content lithium storage material when lithiated and used in the absence of the dopant.
  • the performance characteristics of the lithiated composite materials produced by the methods include the ability to maintain a capacity in excess of 170 mAh/g at 30 cycles, optionally a capacity in excess of mAh/g at 40 cycles.
  • the methods provide the dopant material at 5 weight percent or less, optionally from 0.1 to 4 atomic percent, relative to the high nickel content lithium storage material.
  • the high nickel content lithium storage material includes Ni0 2 , Ni 92 Cos0 2 , or combinations thereof.
  • a high nickel content lithium storage material also includes Mn at an atomic percentage of 10% or less.
  • the dopant provided in the methods is optionally an oxide of a transition metal, optionally oxides of Ti, W, Mo, or combinations thereof.
  • the dopant used in the methods is a sulfide of a transition metal, optionally a sulfide of W, Mo, or combinations thereof.
  • the lithium source may be provided at greater than stoichiometric ratio.
  • the methods may be used to make the lithium storage materials also provided.
  • the materials are significant advances in improving cycle life of high capacity electrodes useful in lithium ion electrochemical cells.
  • FIG. 1 is an ECD spectra illustrating an overall surface profile of a lithiated composite material of Ni 92 Co 8 0 2 with Nio .5 Co 0.2 Mn 0 .3 at a ratio of 80/20 (A) and 90/10 (B) respectively;
  • FIG. 2 is an SEM image illustrating an overall surface profile of a lithiated composite material of Ni 92 Co 8 0 2 with Ni 0.5 Co 0.2 Mn 0 .3 at a ratio of 80/20 (A) and 90/10 (B) respectively;
  • FIG. 3 illustrates the cycleability and capacities of a lithiated composite material of Ni 92 Co 8 0 2 with Nio .5 Co 0.2 Mn 0 .3 at a ratio of 80/20 and 90/10;
  • FIG. 4 illustrates the cycleability and capacities of a lithiated composite material of Ni0 2 with Ni 0 .5Coo. 2 Mn 0 .3 at a ratio of 80/20 and 90/10;
  • FIG. 5 illustrates the effect of different mixing methods on the cycleability and capacities of a lithiated composite material of Ni9 2 Co 8 0 2 with Nio . sCoo .2 Mno.3 at a ratio of 80/20 (A) and Ni0 2 with Nio.5Co 0 . 2 Mn 0 .3 at a ratio of 80/20 (B);
  • FIG. 6 illustrates the cycleability and capacities of a lithiated composite material of Ni 92 Co 8 0 2 doped with different oxides including Ti0 2 (3%), W0 3 (1%), and Mo0 2 (0.5%);
  • FIG. 7 illustrates the cycleability and capacities of a lithiated composite material of Ni0 2 doped with different oxides including Ti0 2 (3.5%) and W0 3 (1%).
  • batteries and “cells” will be used interchangeably when referring to one electrochemical cell, although the term “battery” can also be used to refer to a plurality of electrically interconnected cells.
  • the present invention is directed to composite materials and methods of their manufacture for use in a lithium ion cell.
  • the composite materials manifest high capacity over a long cycle life.
  • the composite materials have particular utility as a cathode material for use in a lithium ion cell.
  • a high capacity, long cycle life lithiated storage material for a rechargeable lithium and electrochemical cell is provided.
  • a lithiated storage material includes a non-lithiated high nickel content lithium storage material that is characterized by greater than 63 weight percent nickel.
  • the high nickel content lithium storage material is intermixed with either a transition metal oxide lithium storage material that is characterized by less than 55 weight percent nickel, a dopant, or both, as well as with a lithium source.
  • the lithium storage materials and the lithium source are intermixed and sintered so as to form a lithiated composite material.
  • the composite material includes the high nickel content lithium storage material present as a predominate by weight relative to the transition metal oxide lithium storage material such that the composite material has not only high-capacity but is also characterized by longer cycle life than that of the high nickel content lithium storage material alone.
  • the inventors discovered that by adding a non-lithiated transition metal oxide lithium storage material, a non-lithiated dopant, or both at a relatively low weight percent compared to the non-lithiated high nickel content lithium storage material prior to sintering with a lithium source, that the high-capacity characteristics of the high nickel content lithium storage material could be maintained over a long cycle life. This was particularly unexpected given that prior attempts to bolster cycle life by combining such materials resulted in an unacceptable decrease in the overall capacity of the high nickel content material.
  • the resulting lithiated composite materials arranged as a result of particular manufacturing processes such as those described herein possess excellent capacity and greatly extended cycle life relative to the high nickel content lithium storage material alone. It is known that typical high nickel content lithium storage materials possess a high oxidation power leading to the release of oxygen, which may react with the non-aqueous electrolyte of the cell in exothermic reaction. This leads to poor cycle life with typical nickel oxide, for example, operating for 5 cycles or less before it's capacity drops below 160 mAh/g, which is a typical capacity of lower nickel content materials (e.g. less than 63 weight percent nickel).
  • the presence of a dopant at relatively low levels compared to the high nickel content lithium storage material allows maintenance of a capacity in excess of 160 mAh/g for 20 or more cycles. Many embodiments of the invention maintain a capacity in excess of 160 mAh/g for 100 or more cycles.
  • the inventive lithiated composite materials typically maintain a capacity in excess of 160 mAh/g for 20 cycles. More typically the materials maintain a capacity in excess of 170 mAh/g for 80 or more cycles. In some embodiments, the resulting lithiated composite material is capable of maintaining a capacity in excess of 180 mAh/gram after cycling of 40 or more cycles.
  • a lithiated composite material includes a high nickel content lithium storage material.
  • High nickel content is defined herein to include 63 weight percent nickel or greater.
  • a high nickel content lithium storage material includes 63 weight percent nickel or greater relative to other transition metals included in the material.
  • a high nickel content lithium storage material optionally includes between 63 and 100 atomic percent nickel, or any value or range therebetween, relative to other transition metals included the material.
  • the amount of nickel in a high nickel content lithium storage material is in excess of 64% nickel, optionally in excess of 65% nickel, optionally in excess of 70% nickel, optionally in excess of 75% nickel.
  • the amount of nickel in a high nickel content lithium storage material is in excess of 80%, 85%, 90%, 95%, or 99% relative to other transition metal components of the high nickel content lithium storage material.
  • a is from 80 to 100 atomic percent.
  • a is 80, 81, 82, 83, 84, 85, 86, 87, 80, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 and, atomic percent relative to Co.
  • a is 100.
  • a is 92.
  • b ranges from 0 to 20 atomic percent or any value or range therebetween.
  • b is 0.
  • b is zero, one, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 atomic percent.
  • the high nickel content lithium storage material when lithiated in the absence of the transition metal oxide lithium storage material additive optionally has a capacity of 170 mAh/g or greater.
  • the capacity of the high nickel content lithium storage material is in excess of 170, 175, 180, 185, 190, 195, 200, 205, 210, 211, 212, 213, 214, or greater mAh/g.
  • a high nickel content lithium storage material also includes Mn.
  • Mn when present is optionally at 10 atomic percent or less.
  • a composite material in some embodiments, optionally includes a transition metal oxide lithium storage material.
  • the transition metal oxide lithium storage material is optionally characterized by less than 55 weight percent nickel.
  • the amount of nickel present in a transition metal oxide lithium storage material is between 30 atomic percent and 50 atomic percent, or any value or range therebetween.
  • nickel is present at 30%, 35%, 40%, 45%, 50%, or 55%.
  • the transition metal oxide lithium storage material is optionally present at 20 weight percent or less relative to the high nickel content lithium storage material.
  • the transition metal oxide lithium storage material is present at from 1 to 20 weight percent relative to the high nickel content lithium storage material, or any value or range there between.
  • the transition metal oxide lithium storage material is present at 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 weight percent relative to the high nickel content lithium storage material.
  • x is optionally from 0 to 0.5, or any value or range therebetween.
  • x is from 0.3 to 0.5.
  • x is 0, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, or 0.50.
  • y is optionally from 0 to 0.4, or any value or range therebetween.
  • y is from 0.2 to 0.4.
  • y is 0, 0.03, 0.1, 0.20, 0.21, 0.22, 3.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, or 0.40.
  • z is optionally from 0 to 0.4, or any value or range therebetween.
  • z is from 0.3 to 0.4.
  • z is 0, 0.03, 0.1, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, or 0.40.
  • Some embodiments include Ni, Co, and Mn at any value or range listed above.
  • a composite material optionally includes a dopant in place of the transition metal oxide lithium storage material or in addition thereto.
  • a dopant is optionally an oxide or sulfide of a transition metal, where the dopant is capable of intercalating lithium.
  • Illustrative examples of a dopant include oxides or sulfides of Ti, Mo, W, Al, Mg, Zr, Cr, V, Zn, Co, or Mn.
  • Specific examples of a dopant include Ti0 2 , W0 3 , Mo0 2 , MoS 2 , WS 2 , A1203, MgO, Zr02,V205,Cr02, Nb205, ZnO, CoO, MnO among others, or combinations thereof.
  • a dopant is not an oxide or sulfide of manganese.
  • a dopant when present, is included in the composite material at an amount of 10 atomic percent or less relative to the high nickel content lithium storage material.
  • a dopant it is present from between 0.5 weight percent to 4 weight percent.
  • a dopant is optionally present at 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0 weight percent relative to the high nickel content lithium storage material.
  • the lithiated composite materials further include a lithium source.
  • a lithium source is present in the lithiated composite materials at stoichiometric amounts or amounts that are moderately in excess of stoichiometric amounts.
  • lithium is present at an amount of 0.1% to 5% in excess of a stoichiometric amount, or any value or range therebetween. This lithium amount allows formation of a lithiated composite material whereby both the high nickel content lithium storage material and the transition metal oxide lithium storage material or dopant are sufficiently lithiated so as to be useful as a cathode material.
  • Preferred methods include the mechanical intermixing of non- lithiated lithium storage materials along with a lithium source and sintering. These methods are in direct contrast to typical art practiced methods of intermixing a pre-lithiated lithium ion source with one or more dopants or other materials so as to form a composite material.
  • a method include mechanically mixing a non-lithiated high nickel content lithium storage material with a non-lithiated transition metal material or a dopant, as well as with a lithium source where the lithium source is present at a stoichiometric amount or greater.
  • the components are subjected to a mechanical alloying processes such as ball milling, impact milling, attritor milling, and the like, which may be utilized to at least partially alloy the particles mechanically.
  • ball milling results in a material with significantly greater capacity relative to simple hand mixing. Ball milling the materials together prior to sintering will produce between 5 to 15 mAh/g of additional capacity relative to hand mixing. As such, typical embodiments of the methods include mechanical ball milling of the materials prior to sintering.
  • the milled materials are then subjected to a sintering process.
  • Typical sintering processes as known in the art are operable.
  • the materials are sintered together at a temperature in excess of 700°C and less than 950°C.
  • the materials are sintered together at a temperature of 725°C.
  • Sintering times are typically from 1 to 10 hours. This is optionally followed by exposure to high temperatures such as that of about 1000°C for an additional period of time to help stabilize the composite.
  • the processes of intermixing non-lithiated materials with the lithium source at the relative ratios and amounts of the invention creates a lithiated composite material as described herein with excellent cycle life and high capacity that is greatly superior to materials previously known in the art.
  • the lithiated composite materials are optionally used as a cathode active component in an electrochemical cell.
  • a cathode is typically formed of the lithiated composite material along with any selected or preferred additives such as binders, conductive diluents, fillers, adhesion promoters, thickening agents or other additives.
  • additives are known in the art and can be found described in part in U.S. Patent No. 8,012,624.
  • the materials may be placed in a solution or dispersion in an appropriate solvent(s) so as to form a coating mixture.
  • the coating mixture may then be applied to an electrically conductive substrate by techniques known in the art.
  • Common conductive substrates include copper, aluminum, stainless steel, or nickel foils.
  • An electrochemical cell is formed by including a cathode, an anode, an electrolyte, along with other necessary elements as known in the art to form a lithium-ion electrochemical cell.
  • An anode is optionally formed from materials including lithium, carbonaceous materials, silicon alloys, or lithium alloys, among others.
  • Electrolytes are optionally liquid, gel, or solid depending on the application and desired characteristics of the cell. Electrolytes optionally include a lithium salt such as LiPF 6 , LiBF 4 , LiC10 4 , lithium bis(oxalato)borate, LiN(CF 3 S02) 2 , LiN(C2F 5 S02) 2 , LiAsF 6 , LiC(CF 3 S0 2 ) 3 , among many others known in the art, and combinations thereof.
  • a lithium salt such as LiPF 6 , LiBF 4 , LiC10 4 , lithium bis(oxalato)borate, LiN(CF 3 S02) 2 , LiN(C2F 5 S02) 2 , LiAsF 6 , LiC(CF 3 S0 2 ) 3 , among many others known in the art, and combinations thereof.
  • the resulting lithium-ion electrochemical cells incorporating a lithiated composite material component in a cathode exhibit both high capacity and long cycle life so as to be particularly useful in many applications including portable devices and automobiles.
  • Example 1 Lithiated composite materials of Ni 92 Co 8 0 2 with Nio .5 Co 0.2 Mn 0 .3 (NCM 523) at ratios of 80/20 and 90/10 are prepared.
  • NCM 523 4 grams of Ni9 2 Co 8 0 2 is added to a mixing chamber along with 1 gram of NCM 523 and 1.4 grams of LiOH.
  • a 90/10 material 4.5 grams of Ni 92 Cos0 2 is added to a mixing chamber along with 0.5 grams of NCM 523 and 1.4 grams of LiOH.
  • the materials are mechanically mixed by ball milling for a period of 1 minute.
  • the resulting powdered mixture is then sintered at 725 °C for 5 hours.
  • the resulting lithiated composite material is then cooled to 25 °C and stored for further analyses.
  • FIG. 1A illustrates the 80/20 material and FIG. IB illustrates the 90/10 material.
  • Table 1 The quantitative average amounts of each element in the respective materials are illustrated in Table 1.
  • Table 2 Atomic composition of 80/20 material.
  • Table 3 Atomic composition of 90/10 material.
  • the lithiated composite materials are studied for capacity levels and cycle life in CR2032 coin cells using lithium metal as counter electrode.
  • the lithiated composite materials are formed into a cathode powder for testing by mixing with carbon Super 65 from Timcal (7.5w ), graphite KS10 from Timcal (7.5%) and 6% PVDF (Kynar) binder.
  • Anhydrous solvent l-methyl-2pyrrolidinone was then added to the powder mix to form a slurry.
  • the slurry was then coated on an aluminum substrate. The coating was dried at 85 °C for several hours and calendared to the final thickness (-60 ⁇ ).
  • the cathode and anode materials are separated by a microporous polypropylene separator (MTI corporation) that was wetted with electrolyte consisting of a 1M solution of LiPF 6 dissolved in a 1:1:1 volume mixture of ethylene carbonate (EC), Dimethyl Carbonate (DMC), and diethyl carbonate (DEC) from Novolyte Corporation.
  • electrolyte consisting of a 1M solution of LiPF 6 dissolved in a 1:1:1 volume mixture of ethylene carbonate (EC), Dimethyl Carbonate (DMC), and diethyl carbonate (DEC) from Novolyte Corporation.
  • EC ethylene carbonate
  • DMC Dimethyl Carbonate
  • DEC diethyl carbonate
  • Lithiated composite materials of Ni0 2 with Nio.5Co 0 . 2 Mn 0 .3 (NCM 523) at ratios of 80/20 and 90/10 are prepared substantially as described in Example 1.
  • NCM 523 and 1.4 grams of LiOH For an 80/20 material, 4 grams of Ni0 2 is added to a mixing chamber along with 1 gram of NCM 523 and 1.4 grams of LiOH.
  • For a 90/10 material 4.5 grams of Ni0 2 is added to a mixing chamber along with 0.5 grams of NCM 523 and 1.4 grams of LiOH.
  • the materials are mechanically mixed by ball milling for a period of 1 minute.
  • the resulting powdered mixture is then sintered at 725 °C for 5 hours.
  • the resulting lithiated composite material is then cooled to 25 °C and stored for further analyses.
  • the lithiated composite material of Ni0 2 and NCM 523 is studied for capacity levels and cycle life as a cathode material used to form coin cells substantially as described in Example 1.
  • the coin cells were charged and discharged at a voltage between 4.3V and 3.0V.
  • the cycling performance test was performed with a charge and discharge current each at 18 mA/g.
  • both the 80/20 and the 90/10 cathodes exhibited peak capacity well in excess of 190 mAh/g with the 90/10 composite material demonstrating peak capacity virtually identical to the Ni0 2 material alone.
  • the 80/20 composite material demonstrated higher capacity for much greater cycling than the 90/10 material with an excess of 170 mAh/g capacity present well beyond 80 cycles.
  • the 90/10 composite material was capable of capacity in excess of 170 mAh/g for greater than 20 cycles representing a significant improvement relative to the Ni0 2 alone.
  • Example 1 The lithiated composite materials of Examples 1 and 2 were formed as in Examples 1 or 2, with the exception that mixing was done using conventional hand mixing by mortar and pestle prior to sintering. The hand mixed materials were then compared to the material formed as in Examples 1 and 2 using ball mill mixing for capacity levels and cycle life using coin cells formed and tested substantially as described in Example 1.
  • FIG. 5A The results of different mixing processes of the predominantly Ni 92 Cos0 2 material are illustrated in FIG. 5A.
  • the results of different mixing processes of the predominantly Ni0 2 material are illustrated in FIG. 5B.
  • ball mill mixing produced much greater capacity that was maintained for many additional cycles.
  • Ball mill mixing of the Ni 92 Cos0 2 material provided nearly 10 mAh/g improved capacity that was maintained above 170 mAh/g for nearly 80 cycles. Ball milling of the Ni0 2 material showed similar results.
  • Lithiated composite materials of Ni 92 Co 8 0 2 with a dopant at various relative amounts between 1 atomic % and 5 atomic % are prepared.
  • dopant materials including Ti0 2 (3.5%), W0 3 (1%), Mo0 2 (0.5%) at a dopant amount relative to the Ni 92 Co 8 0 2 as indicated.
  • 5 grams of Ni 92 Cos0 2 is added to a mixing chamber along with the appropriate amount of dopant and 1.4 grams of LiOH. The materials are milled by pestle until thoroughly intermixed. The resulting powdered mixture is then sintered at 725°C for 5 hours.
  • the lithiated composite materials are used to form electrodes and tested in coin cells substantially as described in Example 1.
  • the presence of each dopant material reduces the peak capacity of the material relative to the predominant component (Ni 92 Cos0 2 ).
  • the cycle life is significantly improved, however, as reflected by the slope of the capacity vs. cycle number.
  • the presence of 3 atomic % Ti0 2 demonstrated a capacity of 170 mAh/g attained out to nearly 40 cycles.
  • the 1% WO 3 dopant including composite material was capable of maintaining a capacity in excess of 160 mAh/g in excess of 30 cycles. Both materials are significantly better than the predominant Ni 92 Co 8 0 2 material alone.
  • the inclusion of 0.5% Mo0 2 resulted in the lowest maximum capacity and dropped below 160 mAh/g by 12 cycles.
  • Overall, Ti0 2 and WO 3 at levels less than 5% produce excellent cycle life to the predominant Ni 92 Cos0 2 material.
  • Example 5 Example 5:
  • Lithiated composite materials of Ni0 2 with a dopant at various relative amounts between 1 atomic % and 5 atomic % are prepared. Preparation procedures are substantially as described in Example 1. Several dopant materials are investigated including Ti0 2 (3.5%), WO 3 (1%), Mo0 2 (0.5%) at a dopant amount relative to the Ni0 2 as indicated. Approximately 5 grams of Ni0 2 is added to a mixing chamber along with the appropriate amount of dopant and 1.4 grams of LiOH. The materials are milled by pestle until thoroughly intermixed. The resulting powdered mixture is then sintered at 725 °C for 5 hours.
  • the lithiated composite materials are used to form electrodes and tested in coin cells substantially as described in Example 1.
  • the presence of each dopant material reduces the peak capacity relative to the predominant component (Ni0 2 ) alone.
  • the cycle life is significantly improved, however, with the presence of 3.5% Ti0 2 providing capacity of 160 mAh/g out to over 40 cycles.
  • the 1% WO 3 dopant including composite material showed much greater peak capacity and was capable of maintaining a capacity in excess of 160 mAh/g in excess of 40 cycles. Both materials possess significantly greater cycle life than the predominant Ni0 2 material alone, as well as possessing excellent capacities over this cycle life.
  • Patents, publications, and applications mentioned in the specification are indicative of the levels of those skilled in the art to which the invention pertains. These patents, publications, and applications are incorporated herein by reference to the same extent as if each individual patent, publication, or application was specifically and individually incorporated herein by reference.

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Abstract

L'invention concerne des matériaux composites au lithium et des procédés de fabrication qui sont aptes à fournir une excellente capacité et une durée de vie de cycle grandement améliorée de cellules secondaires au lithium-ion. Par ajout d'un matériau de stockage au lithium à teneur élevée en nickel avec un matériau de stockage au lithium/oxyde de métal de transition ou un dopant à de relativement faibles niveaux, la capacité des matériaux de stockage au lithium à teneur élevée en nickel est maintenue alors que la durée de vie de cycle est fortement augmentée. Ces caractéristiques sont fournies par des procédés de fabrication des matériaux qui mélangent des matériaux de précurseur sans lithium avec une source de lithium et de frittage des matériaux ensemble selon une réaction de frittage unique. Les matériaux composites au lithium résultants fournissent pour la première fois à la fois une capacité élevée et une durée de vie de cycle excellente à des électrodes à teneur élevée en nickel de manière prédominante.
EP13877477.3A 2013-03-15 2013-03-15 Matériaux composites de cathode ayant une durée de vie de cycle améliorée Withdrawn EP2973790A1 (fr)

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CN111268748B (zh) * 2020-02-21 2023-04-07 桂林理工大学 一种优化α-Ni(OH)2材料储锂性能的方法

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JP5132048B2 (ja) * 2005-08-11 2013-01-30 三洋電機株式会社 非水電解質二次電池
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