US20040241547A1 - Metal oxide containing multiple dopants and methods of preparing same - Google Patents
Metal oxide containing multiple dopants and methods of preparing same Download PDFInfo
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- 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
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- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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
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- 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
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- 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 metal oxide compounds and to preparation methods thereof. More specifically, this invention relates to doped metal oxide insertion compounds for use in lithium and lithium-ion batteries.
- Metal oxides such as lithium metal oxides have found utility in various applications.
- lithium metal oxides have been used as cathode materials in lithium secondary batteries.
- Lithium and lithium ion batteries can be used for large power applications such as for electric vehicles.
- lithium or lithium ion cells are put in series to form a module. In the event that one or more of the cells in the module fails, the rest of the cells become overcharged resulting possibly in explosion of the cells. Therefore, it is important that each cell is individually monitored and protected against overcharging.
- LiCoO 2 and LiNiO 2 have additional disadvantages when used in lithium ion batteries. Specifically, LiNiO 2 raises safety concerns because it has a sharper exothermic reaction at a lower temperature than LiCoO 2 . As a result, the charged end product, NiO 2 , is unstable and can undergo an exothermic decomposition reaction releasing O 2 (Dahn et al, Solid State Ionics, Vol. 69, 265 (1994)). Accordingly, pure LiNiO 2 is generally not selected for use in commercial lithium-ion batteries. Additionally, cobalt is a relatively rare and expensive transition metal, which makes the positive electrode expensive.
- LiMn 2 O 4 spinel is believed to be overcharge safe and is a desirable cathode material for that reason. Nevertheless, although cycling over the full capacity range for pure LiMn 2 O 4 can be done safely, the specific capacity of LiMn 2 O 4 is low. Specifically, the theoretical capacity of LiMn 2 O 4 is only 148 mA ⁇ hr/g and typically no more than about 115-120 mA ⁇ hr/g can be obtained with good cycleability.
- the orthorhombic LiMnO 2 and the tetragonally distorted spinel Li 2 Mn 2 O 4 have the potential for larger capacities than is obtained with the LiMn 2 O 4 spinel. However, cycling over the full capacity range for LiMnO 2 and Li 2 Mn 2 O 4 results in a rapid capacity fade.
- the dopant ion has to have the right electron configuration in addition to having the right valency.
- Co 3+ , Al 3+ , and Ga 3+ all have the same valency but Co 3+ can be oxidized to Co 4+ while Al 3+ , and Ga 3+ cannot. Therefore doping LiNiO 2 with Al or Ga can produce overcharge protection while doping with cobalt does not have the same effect.
- the dopant ions also have to reside at the correct sites in the structure. Rossen et al (Solid State Ionics Vol.
- the present invention uses multiple dopants to replace the transition metal M in lithium metal oxides and metal oxides having the formula LiM y O z or M y O z to have a collective effect on these intercalation compounds.
- the choice of dopants is not limited to elements having the same valency or site preference in the structure as the transition metal M, to elements having only a desired electron configuration, and to elements having the ability to diffuse into LiM y O z or M y O z under practical conditions.
- the use of a carefully chosen combination of multiple dopants widens the choices of dopants which can be used in the intercalation compounds and also can bring about more beneficial effects than a single dopant.
- the doped intercalation compounds of the invention can be used as cathode materials in electrochemical cells for lithium and lithium-ion batteries.
- the doped lithium metal oxides and doped metal oxides of the invention have the formula:
- E i the oxidation state of the replaced transition metal M ⁇ 0.5
- E i is the oxidation state of dopant B i in the final product LiM y-x [A] x O z or M y-x [A] x O z
- the dopant elements B i are cations in the intercalation compound, and the ratio of Li to O in the doped intercalation compound is not smaller than the ratio of Li to O in the undoped compound LiM y O z or M y O z .
- M is selected from Co, Ni, Mn, Ti, Fe, V and Mo and the dopant elements B i are any elements other than M having a Pauling's electronegativity not greater than 2.05 or Mo.
- the intercalation compound has a formula LiM y-x [A] x O z wherein M is Ni or Co and the dopant elements B i include Ti 4+ and Mg 2+ .
- the present invention also includes a method of preparing a doped intercalation compound having the formula LiM y-x [A] x O z or M y-x [A] x O z .
- E i the oxidation state of the replaced transition metal M ⁇ 0.5
- E i is the oxidation state of dopant B i in the final product LiM y-x [A] x O z or M y-x [A] x O z , the dopant elements B; are selected to be cations in the intercalation compound, and the ratio of Li to O in the doped intercalation compound is not smaller than the ratio of Li to O in the undoped compound LiM 4 O 2 or M y O z .
- the cations for the intercalation compound can each be supplied from separate source compounds or two or more of the cations can be supplied from the same source compounds.
- the mixture of source compounds is fired at a temperature between 500° C. and 1000° C. in the presence of oxygen to produce the intercalation compound and preferably cooled in a controlled manner to produce a doped intercalation compound suitable for use as a cathode material for electrochemical cells for lithium and lithium-ion batteries.
- FIG. 1 is an x-ray diffraction pattern study for four different intercalation compounds produced according to the present invention.
- FIG. 2 is an x-ray diffraction pattern study for two different intercalation compounds produced according to the invention and demonstrating the desirability of maintaining valency in the intercalation compound.
- FIG. 3 is a voltage profile for three slow cycles between 3.0 V to 5.0 V for a fresh electrochemical cell containing an intercalation compound produced according to a preferred embodiment of the present invention.
- FIG. 4 is a voltage profile between 3.0 V and 4.5 V for the compound of FIG. 3 after the three slow cycles and demonstrating the cycleability of the compound.
- FIG. 5 is a graph of discharge capacity versus cycle number for the same compound as FIG. 4 and following the same cycling pattern as FIG. 4.
- FIG. 6 is a graph of discharge capacity versus cycle number for an electrochemical cell containing the same intercalation compound tested in FIGS. 3-5 and following the same cycling pattern as in FIGS. 3-5.
- FIG. 7 is a differential scanning calorimetry (DSC) scan of three of the intercalation compounds tested in FIG. 1 and of LiNiO 2 .
- FIG. 8 is an x-ray diffraction pattern for an intercalation compound produced in accordance with the present invention both before and after acid treatment of the intercalation compound.
- FIG. 9 is an x-ray diffraction pattern for an intercalation compound produced according to another preferred embodiment of the present invention.
- FIG. 10 is an x-ray diffraction pattern for an intercalation compound produced according to yet another preferred embodiment of the present invention.
- the present invention should not be limited thereto and can be used with various intercalation compounds including a wide range of lithium metal oxides and metal oxides including, e.g., LiMnO 2 , LiCoO 2 , Li 2 Mn 2 O 4 , LiMn 2 O 4 , MnO 2 , and V 2 O 5 .
- the doped lithium metal oxides and doped metal oxides of the invention have the formula:
- M is a transition metal
- w i E i the oxidation state of the replaced transition metal M ⁇ 0.5
- Es is the oxidation state of dopant B i in the final product LiM y-x [A] x O z or M y-x [A] x O z
- the dopant elements B i are cations in the intercalation compound
- the ratio of Li to O in the intercalation compound is not smaller than the ratio of Li to O in the undoped compound LiM y O z or M y O z .
- the doped lithium metal oxide and doped metal oxide compounds of the invention can be described as intercalation or insertion compounds.
- the preferred doped metal oxide compound is a lithium metal oxide intercalation compound having the formula LiM y-x [A] x O z .
- M is typically selected from Co, Ni, Mn, Ti, Fe, V and Mo.
- the dopant elements B i are any elements other than M having a Pauling's electronegativity not greater than 2.05 or Mo (i.e., if M is not Mo). In other words, the dopant elements B i are elements other than M selected to be cations in the intercalation compound.
- w i E i preferably approaches the oxidation state of the transition metal M and more preferably is equal to the oxidation state of the transition metal M in the undoped metal oxide LiM y O z or M y O z .
- the molar quantity of oxygen, z, in the intercalation compounds of the invention is such that the metal oxide is a stable, single phase metal oxide compound. Furthermore, as described above, the molar quantity of oxygen is such that the ratio of Li to O in the doped intercalation compound is not smaller than the ratio of Li to O in the undoped compound LiM y O z or M y O z . Accordingly, the transition metal M is replaced with the dopant ions and the lithium is not substituted to maximize the specific capacity of the intercalation compound.
- Various combinations of multiple dopants can be used according to the present invention in place of single dopants used in conventional intercalation compounds having the formula LiM y-x A x O z or M y-z A x O z .
- the dopants Al 3+ and Ga 3+ conventionally described to replace Ni 3+ can be replaced with 0.5Ti 4+ +0.5Mg 2+ and still maintain the same charge balance in the compound.
- LiNi 1-x 3+ Alx 3+ O 2 one has LiNi 1-x 3+ Ti x/2 4+ Mg x/2 2+ O 2 .
- Ni 3+ can only be oxidized to Ni 4+
- (1-x) Li per formula unit can be removed.
- both Ti 4+ and Mg 2+ have no remaining valence electrons. Therefore, when the material composition reaches Li x Ni 1-x 4+ Ti x/2 4+ Mg x/2 2+ O 2 no more lithium can be removed and the voltage will simply increase sharply. Thus overcharge protection is achieved.
- Ti 4+ and Mg 2+ bind with oxygen more strongly than Ni 4+ and therefore LixNi is more stable than NiO 2 .
- single dopant Al 3+ or Ga 3+ or Ni 3+ itself in LiNiO 2 can be replaced by [0.5Mg 2+ +0.5Ti 4+ ] or even [0.667 Mg 2+ +0.333 V 5+ ] and other combinations of cations to achieve the overcharge protection and at the same time taking the benefit of the latter's larger binding energy with oxygen to achieve better material stability.
- LiCoO 2 can be doped in the manner described above with respect to LiNiO 2 .
- the intercalation compound has a formula LiM y-x [A] x O z wherein M is Ni or Co and the dopant elements B i include Ti 4+ and Mg 2+ .
- the formulas LiNi 1-x Ti a Mg b O 2 and LiCo 1-x Ti a Mg b O 2 wherein x a+b and x is preferably in the range from greater than 0 to about 0.5, can also be used to describe these intercalation compounds which have a hexagonal layered crystal structure. More preferably, a is approximately equal to b and b is no smaller than a for these intercalation compounds.
- Ti and Mg have the form Ti 4+ and Mg 2+ in LiNi 1-x Ti y Mg z O 2 because the energies of Mg 2s electrons are higher than Ti 3d electrons which in turn are higher than Ni 3d electrons (Yeh et al, Atomic Data and Nuclear Data Tables Vol. 32, 1-155 (1985)).
- the ratio of b:a is preferably between about 1 and about 1/x.
- the dopant elements B i can further include other cations such as cobalt cations.
- Li + ions can be used as a dopant with other dopants such as Ti 4+ , either alone or in combination with Mg 2+ .
- the [0.5 Ti 4+ +0.5 Mg 2+ ] described in the preferred embodiment above can be replaced by [0.667 Ti 4+ +0.333 Li+].
- the [0.5 Ti 4+ +0.5 Mg 2+ ] described in the preferred embodiment above can be replaced by [0.6 Ti 4+ +0.2 Mg 2+ +0.2 Li + ].
- LiM y-x Ti 0.6x Mg 0.2x Li 0.2x O z can also be written as Li 1+0.2 M y-x Ti 0.6x Mg 0.2x O z for the latter example.
- the present invention can also be applied to many other types of lithium metal oxide and metal oxide cathode materials. For instance, one can replace Mn 4+ with 0.4Li++0.6Mo 6+ or 0.25Li++0.75V 5+ in LiMn 2 O 4 so that more Li + ions can be introduced into the octahedral 16d sites to improve the structural stability without causing significant capacity decrease.
- the present invention also includes a method of preparing a doped intercalation compound having the formula LiM y-x [A] x O z or M y-x [A] x O z .
- B i is an element used to replace the transition metal M and w i is the fractional amount of element B i in the total dopant combination
- n is the total number of dopant elements used and is a positive integer of two or more
- E i is the oxidation state of dopant B i in the final product LiM y-x [A] x O z or M y-x [A] x O z
- the dopant elements B i are selected to be cations in the doped intercalation compound
- the ratio of Li to O in the doped intercalation compound is not smaller than the ratio of Li to O in the undoped compound LiM y O z or M y O z
- the source compounds (raw materials) can be the pure elements but are typically compounds containing the elements such as oxides or salts thereof.
- the cations for the intercalation compound can each be supplied from separate source compounds or two or more of the cations can be supplied from the same source compounds. In addition, the source compounds can be mixed in any desirable order.
- the intercalation compounds are preferably prepared by a solid state reactions, it can be advantageous to react the raw materials using wet chemistry such as sol-gel type reactions, alone or in combination with solid state reactions.
- the source compounds comprising M and [A] can be prepared as a solution in a solvent such as water and the M and [A] precipitated out of solution to produce an intimately mixed hydroxide.
- the mixed hydroxide can then be blended with a lithium source compound.
- the selection of reaction methods will vary depending on the raw materials used and the desired end product.
- the mixture once prepared can be reacted to form the lithium metal oxide or metal oxide.
- the mixture is reacted by firing the mixture at an elevated temperature between 500° C. and 1000° C. in the presence of oxygen, e.g., between about 700° C. and 900° C., in a solid state reaction to produce the intercalation compounds.
- the intercalation compound is preferably cooled in a controlled manner to produce an intercalation compound suitable for use as a cathode material for electrochemical cells for lithium and lithium-ion batteries.
- a single phase can be obtained by the following steps. First, stoichiometric amounts of a lithium source compound, a nickel or cobalt source compound, a titanium source compound and a magnesium source compound are mixed in any desired order to give the desired molar ratio according to the formula LiNi 1-x Ti y Mg z O 2 or LiCo 1-x Ti a Mg b O 2 . As described above, the lithium, nickel (or cobalt), titanium and magnesium can be supplied by separate source compounds or two or more of these cations can be supplied by a single source compound.
- TiMgO 3 and Ni 0.75 Ti 0.25 O are commercially available compounds which can supply two cations for use in the intercalation compounds of the invention.
- the mixture is then fired at a temperature between 700° C. and 900° C., preferably between 750° C. and 850° C., in an atmosphere with a partial pressure of oxygen of at least 20 kPa, preferably about 100 kPa.
- the fired mixture is then cooled in a controlled manner, preferably at a rate of 50C/min or less.
- the firing temperature and the soak times are chosen depending on x and the oxygen partial pressure so that the lithium to Ni 1-x Ti y Mg z ratio in the structure preferably approximates 1:1 and no significant cation mixing between lithium and the other metals occurs in the layers.
- Suitable compounds for the invention include a lithium source compound comprising one or any combination of the following: LiOH, LiNO 3 , Li 2 CO 3 , LiCl and LiF; a nickel source compound comprising one or any combination of the following: NiO, Ni(NO 3 ) 2 , Ni(OH) 2 and NiCO 3 ; a cobalt source compound comprising one or any combination of the following: CO 3 O 4 , Co(OH) 2 , CoCO 3 , Co(NO 3 ) 2 , CoO, and CO 2 O 3 ; a titanium source compound comprising one or any combination of the following: a titanium source compound comprising TiO 2 in one or any combination of the following forms: anatase, rutile and brookite; and a magnesium source compound comprising one or any combination of the following: Mg(OH) 2 , Mg(NO) 3 , MgCO 3 , MgCl and MgO.
- TiMgO 3 and Ni 0.75 Ti 0.25 O can be used as source compounds as
- these compounds can also be made by wet chemistry methods.
- Ni, Ti and Mg can be precipitated simultaneously from a solution containing the three resulting in an intimately mixed hydroxide.
- the mixed hydroxide having the desired molar ratio according to the formula LiNi 1-x Ti a Mg b O 2 can then be blended with a lithium source compound and fired at a temperature of between 700° C. and 900° C. in an oxygen-containing atmosphere.
- FIG. 1 shows the x-ray diffraction (XRD) patterns for 4 samples having the following formulas: LiNi 0.9 Ti 0.05 Mg 0.05 O 2 , LiNi 0.8 Ti 0.1 Mg 0.1 O 2 , LiNi 0.75 Ti 0.125 Mg 0.125 O 2 , and LiNi 0.7 Ti 0.15 Mg 0.15 O 2 .
- XRD x-ray diffraction
- a intercalation compound having the formula LiNi 0.75 Ti 0.15 Mg 0.10 O 2 was prepared according to the method described in Example 1.
- the x-ray diffraction pattern for this sample is illustrated in FIG. 2 along with the x-ray diffraction pattern of the LiNi 0.75 Ti 0.125 Mg 0.125 O 2 prepared in Example 1.
- the smaller peak ratio between the 003 peak and the 104 peak for LiNi 0.75 Ti 0.15 Mg 0.10 O 2 as compared to LiNi 0.75 Ti 0.125 Mg 0.125 O 2 there is a greater amount of cation mixing in the LiNi 0.75 Tio. 15 Mg 0.100 2 sample than in the LiNi 0.75 Ti 0.125 Mg 0.125 O 2 sample. Therefore, it is important to maintain the amount of Mg 2+ greater than equal to the amount of Ti 4+ and preferably equal to the amount of Ti 4+ .
- Electrochemical cells with lithium metal as the anode and cathodes with LiNi 0.75 Ti 0.125 Mg 0.125 0 2 (prepared according to Example 1) as the active material were made and tested.
- the electrolyte was IM LiPF 6 in a 50/50 volume percent mixture of ethylene carbonate and dimethyl carbonate solvents.
- Celgard 3501 separators and NRC 2325 coin cell hardware were used.
- the cathode consisted of 85% active material (by weight), 10% super STM carbon black (available from Chemetals) and 5% polyvinylidene fluoride (PVDF) as a binder polymer, coated on aluminum foil. Preliminary test results are shown in FIGS. 3-6.
- the cathode of test cell 1 contains 9.1 mg active mass of LiNi 0.75 Ti 0.125 Mg 0.125 O 2 .
- the cell was first cycled with 0.075 mA from 3.0 V to 5.0 V three times. The results of this cycling are illustrated in the voltage (V) to specific capacity (mA-hr/g) graph of FIG. 3.
- the current corresponds to a rate close to C/20 or 8.2 mA/g of active mass.
- the voltage curve of the subsequent cycles shows very reversible characteristics. As further shown in FIG. 3, most of the capacity is contained between 3.6 V and 4.4 V versus Li. Above 4.4 V, the voltage increases sharply to 5 V which shows very good overcharge characteristics.
- the reversible capacity is about 190 mA-hr/g.
- the cell was cycled between 3.0 V and 4.5 V at a larger current of 0.6 mA. This current corresponds to a faster rate of C/3, or 66 mA/g of active material.
- V voltage
- hr time
- the discharge capacity versus cycle number for the 3.0-4.5 V cycling in FIG. 4 is shown in FIG. 5 which demonstrates the excellent cycleability of the material.
- test cell 2 A second test cell (test cell 2 ) containing 16.2 mg active mass of LiNi 0.75 Ti 0.125 Mg 0.125 O 2 was prepared. The cell was first cycled between 3.0 and 5.0 V for 11 cycles, and was then switched to 3.0-4.5 V cycling. The current for charge and discharge was 0.6 mA. As shown in the graph of discharge capacity versus cycle number in FIG. 6, the cycleability of the material was excellent.
- the LiNi 0.9 Ti 0.05 Mg 0.05 O 2 , LiNi 0.8 Ti 0.1 Mg 0.1 O 2 and LiNi 0.75 Ti 0.125 Mg 0.125 O 2 prepared in Example 1 were each used as the active cathode material for electrochemical cells prepared in the manner described in Example 3 using between 10 mg and 20 mg active material for each cell.
- the cells were first conditioning charged to 5.0 V and discharged to 3.0 V, and then float charged to 4.5 V with 0.2 mA current for 40 hours to ensure equilibrium conditions. The charged cells were then transferred to a glove box filled with argon and opened. Between 0.1 mg and 1.0 mg of the cathode material from the cells was removed and hermetically sealed into DSC cells.
- FIG. 7 illustrates the DSC results for the LiNi 0.9 Ti 0.05 Mg 0.05 O 2 , LiNi 0.8 Ti 0.1 Mg 0.1 O 2 and LiNi 0.75 Ti 0.125 Mg 0.125 O 2 with the area of interest magnified in the inset.
- the positive heat flow in FIG. 7 represent heat flowing out of the sample.
- LiNi 0.75 Ti 0.125 MgO 125 O 2 prepared as described in Example I was tested for acid resistance. Twenty grams of LiNi 0.75 Ti 0.125 Mg 0.125 O 2 was placed in 400 ml deionized water. HCl was added until the pH of the solution reached 2 and the solution was stirred for 1 hour. The LiNi 0.75 Ti 0.125 Mg 0.125 O 2 was filtered and washed with deionized water until the wash reached a pH of 7. The first liter of the wash was analyzed with inductively coupled plasma (ICP) spectroscopy. About 25% of the total lithium and less than 0.5% of the total Ni in the sample was detected in the wash. No Ti and Mg were detected in the wash.
- ICP inductively coupled plasma
- the washed and filtered LiNi 0.75 Ti 0.125 Mg 0.125 O 2 was vacuum dried and an x-ray diffraction of this compound was performed.
- the acid treated sample has the same XRD pattern as an untreated sample and the peaks are still sharp. Therefore, although there is partial delithiation (lithium leaching) under acidic conditions, the basic structural integrity of the material is still maintained as evidenced by the minimal loss of the transition metals and the XRD pattern showing the same structure and crystallinity of the intercalation compound.
- a doped intercalation compound having the formula iNi 0.75 Ti 0.15 Mg 0.05 Li 0.05 O 2 was prepared by firing a stoichiometric mixture of LiOH, NiO, TiO 2 and Mg(OH) 2 at 800° C. for 20 hours in air, followed by a 1° C./min controlled cooling to 500° C. and natural cooling to room temperature.
- FIG. 9 illustrates an x-ray diffraction pattern for this compound. As demonstrated in FIG. 9, the intercalation compound was a single phase compound and as evidenced by the peak ratio between the 003 peak and 104 peak, there was no cation mixing in the metal layers.
- a doped intercalation compound having the formula LiNi 0.7 Co 0.1 Ti 0.1 Mg 0.1 O 2 was prepared by firing a stoichiometric mixture of LiOH, NiO, CO 3 O 4 , TiO 2 and Mg(OH) 2 at 800° C. for 20 hours in air, followed by a 1° C./min controlled cooling to 500° C. and natural cooling to room temperature. As shown in FIG. 10, this intercalation compound was predominantly single phase.
- the doped lithium metal oxide or metal oxide intercalation compounds can be used in the positive electrode (cathode) of lithium or lithium-ion electrochemical cells and are typically combined with a carbonaceous material and a binder polymer to form a cathode.
- the negative electrode can be lithium metal or alloys, or any material capable of reversibly lithiating and delithiating at an electrochemical potential relative to lithium metal between about 0.0 V and 0.7 V, and is separated from the positive electrode material in the cell using an electronic insulating separator.
- negative electrode materials are carbonaceous materials including carbonaceous materials containing H, B, Si and Sn, and tin oxides or tin-silicon oxides.
- the electrochemical cells further include an electrolyte.
- the electrolyte can be non-aqueous liquid, gel or solid and preferably comprises a lithium salt. Electrochemical cells using the intercalation compounds of the invention as positive electrode material can be combined for use in large power applications such as for electric vehicles.
- a combination of multiple dopants can be selected to replace the transition metal M in intercalation compounds of the formula LiM y O z or M y O z to achieve the same result as a single dopant.
- the limits on the choice of single dopants can be avoided and, at the same time, more beneficial effects can be achieved by using a combination of two or more dopants.
- the use of multiple dopants can result in better specific capacity, cycleability, stability, handling properties and/or cost than has been achieved in single dopant metal oxides.
- the multiple doped intercalation compounds demonstrate good heat and acid stability and therefore are safe for use as cathode materials in electrochemical cells for lithium and lithium ion batteries.
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Abstract
The present invention relates to metal oxides containing multiple dopants. The metal oxides have the formula:
LiMy-x[A]xOz or My-x[A]xOz,
wiBi wherein Bi is an element used to replace the transition metal M and wi is the fractional amount of element Bi in the total dopant combination such that
wi =1, n is the total number of dopant elements used and is a positive integer of two or more, wherein the fractional amount wi of dopant element Bi is determined by the relationship
wiEi=the oxidation state of the transition metal M±0.5, Ei is the oxidation state of dopant Bi in the final product LiMy-x[A]xOz or My-x[A]xOz the dopant elements Bi are cations in the intercalation compound, and the ratio of Li to O in the intercalation compound is not smaller than the ratio of Li to O in the undoped compound LiMyOz or MyOz. The present invention also includes methods of preparing same and specific embodiments of same.
Description
- This application is a divisional application of allowed U.S. application Ser. No. 10/165,023, filed Jun. 7, 2002, which is a continuation application of abandoned U.S. application Ser. No. 08/954,372, filed Oct. 20, 1997, which is related to commonly owned copending provisional application Ser. No. 60/046,570, filed May 15, 1997, and copending provisional application Ser. No. 60/046,571, filed May 15, 1997. The benefit of the earlier filing dates of each of these applications is claimed under 35 U.S.C. § 119(e) and each of the applications and patents issuing therefrom are incorporated herein in their entireties by reference.
- This invention relates to metal oxide compounds and to preparation methods thereof. More specifically, this invention relates to doped metal oxide insertion compounds for use in lithium and lithium-ion batteries.
- Metal oxides such as lithium metal oxides have found utility in various applications. For example, lithium metal oxides have been used as cathode materials in lithium secondary batteries. Lithium and lithium ion batteries can be used for large power applications such as for electric vehicles. In this specific application, lithium or lithium ion cells are put in series to form a module. In the event that one or more of the cells in the module fails, the rest of the cells become overcharged resulting possibly in explosion of the cells. Therefore, it is important that each cell is individually monitored and protected against overcharging.
- The most attractive materials for use as cathode materials for lithium ion secondary batteries have been LiCoO2, LiNiO2, and LiMn2O4. However, although these cathode materials are attractive for use in lithium ion secondary batteries, there are definite drawbacks associated with these materials. One of the apparent benefits for using LiNiO2 and LiCoO2 as cathode materials is that those lithium metal oxides have a theoretical capacity of 275 mA·hr/g. Nevertheless, the full capacity of these materials cannot be achieved in practice. In fact, for pure LiNiO2 and LiCoO2, only about 140-150 mA·hr/g can be used. The further removal of lithium by further charging (overcharging) the LiNiO2 and LiCoO2 material degrades the cycleability of these materials by moving nickel or cobalt into the lithium layers. Furthermore, the further removal of lithium causes exothermic decomposition of the oxide in contact with the organic electrolyte under heated conditions which poses safety hazards. Therefore, lithium ion cells using LiCoO2 or LiNiO2 are typically overcharge protected.
- LiCoO2 and LiNiO2 have additional disadvantages when used in lithium ion batteries. Specifically, LiNiO2 raises safety concerns because it has a sharper exothermic reaction at a lower temperature than LiCoO2. As a result, the charged end product, NiO2, is unstable and can undergo an exothermic decomposition reaction releasing O2 (Dahn et al, Solid State Ionics, Vol. 69, 265 (1994)). Accordingly, pure LiNiO2 is generally not selected for use in commercial lithium-ion batteries. Additionally, cobalt is a relatively rare and expensive transition metal, which makes the positive electrode expensive.
- Unlike LiCoO2 and LiNiO2, LiMn2O4 spinel is believed to be overcharge safe and is a desirable cathode material for that reason. Nevertheless, although cycling over the full capacity range for pure LiMn2O4 can be done safely, the specific capacity of LiMn2O4 is low. Specifically, the theoretical capacity of LiMn2O4 is only 148 mA·hr/g and typically no more than about 115-120 mA·hr/g can be obtained with good cycleability. The orthorhombic LiMnO2 and the tetragonally distorted spinel Li2Mn2O4 have the potential for larger capacities than is obtained with the LiMn2O4 spinel. However, cycling over the full capacity range for LiMnO2 and Li2Mn2O4 results in a rapid capacity fade.
- Various attempts have been made to either improve the specific capacity or safety of the lithium metal oxides used in secondary lithium batteries. For example, in an attempt to improve the safety and/or specific capacity of these lithium metal oxides, these lithium metal oxides have been doped with other cations. For example, lithium and cobalt cations have been used in combination in lithium metal oxides. Nevertheless, although the resulting solid solution LiNi1-xCoxO2 (0×1) may have somewhat improved safety characteristics over LiNiO2 and larger useful capacity below 4.2 V versus Li than LiCoO2, this solid solution still has to be overcharge protected just as LiCoO2 and LiNiO2.
- One alternative has been to dope LiNiO2 with ions that have no remaining valence electrons thereby forcing the material into an insulator state at a certain point of charge, and therefore protecting the material from overcharge. For example, Ohzuku et al (Journal of Electrochemical Soc., Vol. 142, 4033 (1995)) describe that the use of Al3+ +s a dopant for lithium nickelates (LiNi0.75Al0.25O4) can produce improved overcharge protection and thermal stability in the fully charged state as compared to LiNiO2. However, the cycle life performance of this material is unknown. Alternatively, U.S. Pat. No. 5,595,842 to Nakare et al. demonstrates the use of Ga3+ instead of Al3+. In another example, Davidson et al (U.S. Pat. No. 5,370,949) demonstrates that introducing chromium cations into LiMnO2 can produce a tetragonally distorted spinel type of structure which is air stable and has good reversibility on cycling in lithium cells.
- Although doping lithium metal oxides with single dopants has been successful in improving these materials, the choice of single dopants which can be used to replace the metal in the lithium metal oxide is limited by many factors. For example, the dopant ion has to have the right electron configuration in addition to having the right valency. For example, Co3+, Al3+, and Ga3+ all have the same valency but Co3+ can be oxidized to Co4+ while Al3+, and Ga3+ cannot. Therefore doping LiNiO2 with Al or Ga can produce overcharge protection while doping with cobalt does not have the same effect. The dopant ions also have to reside at the correct sites in the structure. Rossen et al (Solid State Ionics Vol. 57, 311 (1992)) shows that introducing Mn into LiNiO2 promotes cation mixing and therefore has a detrimental effect on performance. Furthermore, one has to consider the ease at which the doping reaction can be carried out, the cost of the dopants, and the toxicity of the dopants. All of these factors further limit the choice of single dopants.
- The present invention uses multiple dopants to replace the transition metal M in lithium metal oxides and metal oxides having the formula LiMyOz or MyOz to have a collective effect on these intercalation compounds. As a result, the choice of dopants is not limited to elements having the same valency or site preference in the structure as the transition metal M, to elements having only a desired electron configuration, and to elements having the ability to diffuse into LiMyOz or MyOz under practical conditions. The use of a carefully chosen combination of multiple dopants widens the choices of dopants which can be used in the intercalation compounds and also can bring about more beneficial effects than a single dopant. For example, the use of multiple dopants can result in better specific capacity, cycleability, stability, handling properties and/or cost than has been achieved in single dopant metal oxides. The doped intercalation compounds of the invention can be used as cathode materials in electrochemical cells for lithium and lithium-ion batteries.
- The doped lithium metal oxides and doped metal oxides of the invention have the formula:
- LiMy-x[A]xOz or My-x[A]xOz,
-
-
-
- wiEi=the oxidation state of the replaced transition metal M±0.5, Ei is the oxidation state of dopant Bi in the final product LiMy-x[A]xOz or My-x[A]xOz the dopant elements Bi are cations in the intercalation compound, and the ratio of Li to O in the doped intercalation compound is not smaller than the ratio of Li to O in the undoped compound LiMyOz or MyOz. Typically, M is selected from Co, Ni, Mn, Ti, Fe, V and Mo and the dopant elements Bi are any elements other than M having a Pauling's electronegativity not greater than 2.05 or Mo.
- In one preferred embodiment of the invention, the intercalation compound has a formula LiMy-x[A]xOz wherein M is Ni or Co and the dopant elements Bi include Ti4+ and Mg2+. The formulas LiNi1-xTiaMgbO2 and LiCo1-xTiaMgbO2 can also be used to describe these intercalation compounds wherein x=a+b and x is preferably in the range from greater than 0 to about 0.5. More preferably, a is approximately equal to b and b is no smaller than a for these intercalation compounds. The dopant elements Bi can further include other cations or have the formula LiMy-x[A]xOz wherein M is Ni or Co, y=1, z=2, and the dopant elements Bi include Ti4+, Mg2+ and Li+ cations.
-
-
- wiEi=the oxidation state of the replaced transition metal M±0.5, Ei is the oxidation state of dopant Bi in the final product LiMy-x[A]xOz or My-x[A]xOz, the dopant elements B; are selected to be cations in the intercalation compound, and the ratio of Li to O in the doped intercalation compound is not smaller than the ratio of Li to O in the undoped compound LiM4O2 or MyOz. The cations for the intercalation compound can each be supplied from separate source compounds or two or more of the cations can be supplied from the same source compounds. The mixture of source compounds is fired at a temperature between 500° C. and 1000° C. in the presence of oxygen to produce the intercalation compound and preferably cooled in a controlled manner to produce a doped intercalation compound suitable for use as a cathode material for electrochemical cells for lithium and lithium-ion batteries.
- These and other features and advantages of the present invention will become more readily apparent to those skilled in the art upon consideration of the following detailed description which describes both the preferred and alternative embodiments of the present invention.
- FIG. 1 is an x-ray diffraction pattern study for four different intercalation compounds produced according to the present invention.
- FIG. 2 is an x-ray diffraction pattern study for two different intercalation compounds produced according to the invention and demonstrating the desirability of maintaining valency in the intercalation compound.
- FIG. 3 is a voltage profile for three slow cycles between 3.0 V to 5.0 V for a fresh electrochemical cell containing an intercalation compound produced according to a preferred embodiment of the present invention.
- FIG. 4 is a voltage profile between 3.0 V and 4.5 V for the compound of FIG. 3 after the three slow cycles and demonstrating the cycleability of the compound.
- FIG. 5 is a graph of discharge capacity versus cycle number for the same compound as FIG. 4 and following the same cycling pattern as FIG. 4.
- FIG. 6 is a graph of discharge capacity versus cycle number for an electrochemical cell containing the same intercalation compound tested in FIGS. 3-5 and following the same cycling pattern as in FIGS. 3-5.
- FIG. 7 is a differential scanning calorimetry (DSC) scan of three of the intercalation compounds tested in FIG. 1 and of LiNiO2.
- FIG. 8 is an x-ray diffraction pattern for an intercalation compound produced in accordance with the present invention both before and after acid treatment of the intercalation compound.
- FIG. 9 is an x-ray diffraction pattern for an intercalation compound produced according to another preferred embodiment of the present invention.
- FIG. 10 is an x-ray diffraction pattern for an intercalation compound produced according to yet another preferred embodiment of the present invention.
- The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments of the invention are shown. This invention can, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the following description, the invention is described primarily with respect to LiNiO2. Nevertheless, the present invention should not be limited thereto and can be used with various intercalation compounds including a wide range of lithium metal oxides and metal oxides including, e.g., LiMnO2, LiCoO2, Li2Mn2O4, LiMn2O4, MnO2, and V2O5.
- The doped lithium metal oxides and doped metal oxides of the invention have the formula:
- LiMy-x[A]xOz or My-x[A]xOz,
- wherein M is a transition metal,
-
-
-
- wiEi=the oxidation state of the replaced transition metal M±0.5, Es is the oxidation state of dopant Bi in the final product LiMy-x[A]xOz or My-x[A]xOz, the dopant elements Bi are cations in the intercalation compound, and the ratio of Li to O in the intercalation compound is not smaller than the ratio of Li to O in the undoped compound LiMyOz or MyOz.
-
- wiEi preferably approaches the oxidation state of the transition metal M and more preferably is equal to the oxidation state of the transition metal M in the undoped metal oxide LiMyOz or MyOz.
- The molar quantity of oxygen, z, in the intercalation compounds of the invention is such that the metal oxide is a stable, single phase metal oxide compound. Furthermore, as described above, the molar quantity of oxygen is such that the ratio of Li to O in the doped intercalation compound is not smaller than the ratio of Li to O in the undoped compound LiMyOz or MyOz. Accordingly, the transition metal M is replaced with the dopant ions and the lithium is not substituted to maximize the specific capacity of the intercalation compound.
- Various combinations of multiple dopants can be used according to the present invention in place of single dopants used in conventional intercalation compounds having the formula LiMy-xAxOz or My-zAxOz. For example, in LiNi1-xAxO2 intercalation compounds, the dopants Al3+ and Ga3+ conventionally described to replace Ni3+, can be replaced with 0.5Ti4++0.5Mg2+ and still maintain the same charge balance in the compound. Instead of having LiNi1-x 3+Alx3+O2, one has LiNi1-x 3+Tix/2 4+Mgx/2 2+O2. Since it is believed that Ni3+ can only be oxidized to Ni4+, only (1-x) Li per formula unit can be removed. Like Al3+ and Ga3+, both Ti4+ and Mg2+ have no remaining valence electrons. Therefore, when the material composition reaches LixNi1-x 4+Tix/2 4+Mgx/2 2+O2 no more lithium can be removed and the voltage will simply increase sharply. Thus overcharge protection is achieved. In addition, Ti4+ and Mg2+ bind with oxygen more strongly than Ni4+ and therefore LixNi is more stable than NiO2. Accordingly, single dopant Al3+ or Ga3+ or Ni3+ itself in LiNiO2 can be replaced by [0.5Mg2++0.5Ti4+] or even [0.667 Mg2++0.333 V5+] and other combinations of cations to achieve the overcharge protection and at the same time taking the benefit of the latter's larger binding energy with oxygen to achieve better material stability. Furthermore, LiCoO2 can be doped in the manner described above with respect to LiNiO2.
- In one preferred embodiment of the invention, the intercalation compound has a formula LiMy-x[A]xOz wherein M is Ni or Co and the dopant elements Bi include Ti4+ and Mg2+. The formulas LiNi1-xTiaMgbO2 and LiCo1-xTiaMgbO2 wherein x=a+b and x is preferably in the range from greater than 0 to about 0.5, can also be used to describe these intercalation compounds which have a hexagonal layered crystal structure. More preferably, a is approximately equal to b and b is no smaller than a for these intercalation compounds. It has been discovered that these materials, when used as the positive electrodes in lithium secondary electrochemical cells, have large specific capacities, are safer than LiNiO2, and have good cycleabilities. The balance between having a large capacity and a thermally benign material can be achieved by adjusting x.
- The use of Ti and Mg at the same time imposes intrinsic overcharge protection on the intercalation compounds and improves the safety of the material while maintaining good cycleability at large capacities. For example, it is believed that Ti and Mg have the form Ti4+ and Mg2+ in LiNi1-xTiyMgzO2 because the energies of Mg 2s electrons are higher than Ti 3d electrons which in turn are higher than Ni 3d electrons (Yeh et al, Atomic Data and Nuclear Data Tables Vol. 32, 1-155 (1985)). It can be shown that the oxidation state of nickel equals 3 when a=b so that the material can be written as Li+Ni1-x 3+(Ti)y 4+Mgy 2+O2 where y=a/2. Since there are no remaining valence electrons in either Ti4+ or Mg2+, only (1-x) Li per formula unit can be removed and therefore overcharge protection is achieved intrinsically. In other words, the charge will stop when all the Ni3+ are oxidized to Ni4+ and the fully charged material is Lix +Ni1-x 4+Tiy 4+Mgy 2+O2. Also, the material is believed to be more stable against decomposition in the fully charged state than LiNiO2. This is because Ti4+ and Mg2+ bind oxygen more strongly than Ni4+, as evidenced by the fact that TiO2 and MgO are very stable oxides and NiO2 is not. This stability improves the safety of the material under overcharge conditions in lithium ion electrochemical cells. Because the average oxidation state of nickel is less than 3 in LiNi1-xTiaMgbO2 when b<a, it is preferred that b≧a because Ni2+ ions tend to migrate to the lithium layers, causing diffusion problems for lithium during electrochemical charge and discharge. Furthermore, it is preferred that b is not much greater than a because the oxidation state of nickel will approach 4 which makes it difficult to formulate single phase intercalation compounds. Therefore, the ratio of b:a is preferably between about 1 and about 1/x.
- In the preferred embodiment described above, wherein M is Ni, the dopant elements Bi can further include other cations such as cobalt cations. In addition, Li+ ions can be used as a dopant with other dopants such as Ti4+, either alone or in combination with Mg2+. In other words, intercalation compounds can have the formula LiMy-x[A]xOz wherein M is Ni, y=1, z=2, and the dopant elements Bi include Ti4+ and Li+ cations. In such an embodiment, the [0.5 Ti4++0.5 Mg2+] described in the preferred embodiment above can be replaced by [0.667 Ti4++0.333 Li+]. Alternatively, the intercalation compound can also include Mg2+ as a dopant such that the intercalation compound has a formula LiMy-x[A]xOz wherein M is Ni, y=1, z=2, and the dopant elements Bi include Ti4+, Mg2+ and Li+ cations. In such an embodiment, the [0.5 Ti4++0.5 Mg2+] described in the preferred embodiment above can be replaced by [0.6 Ti4++0.2 Mg2++0.2 Li+]. As will be recognized by those skilled in the art, the above formulas can be altered when Li+ is used as a dopant, e.g., LiMy-xTi0.6xMg0.2xLi0.2xOz can also be written as Li1+0.2My-xTi0.6xMg0.2xOz for the latter example.
- The present invention can also be applied to many other types of lithium metal oxide and metal oxide cathode materials. For instance, one can replace Mn4+ with 0.4Li++0.6Mo6+ or 0.25Li++0.75V5+ in LiMn2O4 so that more Li+ ions can be introduced into the octahedral 16d sites to improve the structural stability without causing significant capacity decrease.
-
-
- the oxidation state of the transition metal M±0.5, Ei is the oxidation state of dopant Bi in the final product LiMy-x[A]xOz or My-x[A]xOz, the dopant elements Bi are selected to be cations in the doped intercalation compound, and the ratio of Li to O in the doped intercalation compound is not smaller than the ratio of Li to O in the undoped compound LiMyOz or MyOz. The source compounds (raw materials) can be the pure elements but are typically compounds containing the elements such as oxides or salts thereof. The cations for the intercalation compound can each be supplied from separate source compounds or two or more of the cations can be supplied from the same source compounds. In addition, the source compounds can be mixed in any desirable order.
- Although the intercalation compounds are preferably prepared by a solid state reactions, it can be advantageous to react the raw materials using wet chemistry such as sol-gel type reactions, alone or in combination with solid state reactions. For example, the source compounds comprising M and [A] can be prepared as a solution in a solvent such as water and the M and [A] precipitated out of solution to produce an intimately mixed hydroxide. The mixed hydroxide can then be blended with a lithium source compound. Typically, the selection of reaction methods will vary depending on the raw materials used and the desired end product.
- The mixture once prepared can be reacted to form the lithium metal oxide or metal oxide. Preferably, the mixture is reacted by firing the mixture at an elevated temperature between 500° C. and 1000° C. in the presence of oxygen, e.g., between about 700° C. and 900° C., in a solid state reaction to produce the intercalation compounds. Once the mixture has been fired to form the doped lithium metal oxide or metal oxide intercalation compound, the intercalation compound is preferably cooled in a controlled manner to produce an intercalation compound suitable for use as a cathode material for electrochemical cells for lithium and lithium-ion batteries.
- In the preferred embodiment described above having the formula LiNi1-xTiaMgbO2 or LiCo1-xTiaMgbO2, a single phase can be obtained by the following steps. First, stoichiometric amounts of a lithium source compound, a nickel or cobalt source compound, a titanium source compound and a magnesium source compound are mixed in any desired order to give the desired molar ratio according to the formula LiNi1-xTiyMgzO2 or LiCo1-xTiaMgbO2. As described above, the lithium, nickel (or cobalt), titanium and magnesium can be supplied by separate source compounds or two or more of these cations can be supplied by a single source compound. For example, TiMgO3 and Ni0.75Ti0.25O are commercially available compounds which can supply two cations for use in the intercalation compounds of the invention. The mixture is then fired at a temperature between 700° C. and 900° C., preferably between 750° C. and 850° C., in an atmosphere with a partial pressure of oxygen of at least 20 kPa, preferably about 100 kPa. The fired mixture is then cooled in a controlled manner, preferably at a rate of 50C/min or less. The firing temperature and the soak times are chosen depending on x and the oxygen partial pressure so that the lithium to Ni1-xTiyMgz ratio in the structure preferably approximates 1:1 and no significant cation mixing between lithium and the other metals occurs in the layers. Suitable compounds for the invention include a lithium source compound comprising one or any combination of the following: LiOH, LiNO3, Li2CO3, LiCl and LiF; a nickel source compound comprising one or any combination of the following: NiO, Ni(NO3)2, Ni(OH)2 and NiCO3; a cobalt source compound comprising one or any combination of the following: CO3O4, Co(OH)2, CoCO3, Co(NO3)2, CoO, and CO2O3; a titanium source compound comprising one or any combination of the following: a titanium source compound comprising TiO2 in one or any combination of the following forms: anatase, rutile and brookite; and a magnesium source compound comprising one or any combination of the following: Mg(OH)2, Mg(NO)3, MgCO3, MgCl and MgO. Also, TiMgO3 and Ni0.75Ti0.25O can be used as source compounds as described above.
- As mentioned above, in addition to producing the intercalation compounds of the invention by solid state methods, these compounds can also be made by wet chemistry methods. For example, Ni, Ti and Mg can be precipitated simultaneously from a solution containing the three resulting in an intimately mixed hydroxide. The mixed hydroxide having the desired molar ratio according to the formula LiNi1-xTiaMgbO2 can then be blended with a lithium source compound and fired at a temperature of between 700° C. and 900° C. in an oxygen-containing atmosphere. In such wet chemistry reactions, it is not necessary to stay at high temperatures for extended periods of time in order for the Ti and Mg to diffuse uniformly with Ni.
- The present invention will now be described according to the following non-limiting examples.
- Stoichiometric amounts of LiOH, NiO, TiO2, and Mg(OH)2 are mixed and fired at a temperature of 800° C. for 20 hours in an atmosphere with the oxygen partial pressure close to 100 kPa. The cooling was controlled at 1 D C/min down to 500° C. followed by natural cooling to room temperature. FIG. 1 shows the x-ray diffraction (XRD) patterns for 4 samples having the following formulas: LiNi0.9Ti0.05Mg0.05O2, LiNi0.8Ti0.1Mg0.1O2, LiNi0.75Ti0.125Mg0.125O2, and LiNi0.7Ti0.15Mg0.15O2. As shown in FIG. 1, each of these samples are in a single phase having a hexagonal layered structure. Samples were also made with nitrate precursors instead of hydroxides. The same single phase materials were obtained.
- A intercalation compound having the formula LiNi0.75Ti0.15Mg0.10O2 was prepared according to the method described in Example 1. The x-ray diffraction pattern for this sample is illustrated in FIG. 2 along with the x-ray diffraction pattern of the LiNi0.75Ti0.125Mg 0.125O2 prepared in Example 1. As evidenced by the smaller peak ratio between the 003 peak and the 104 peak for LiNi0.75Ti0.15Mg0.10O2 as compared to LiNi0.75Ti0.125Mg0.125O2, there is a greater amount of cation mixing in the LiNi0.75Tio. 15Mg0.100 2 sample than in the LiNi0.75Ti0.125Mg0.125O2 sample. Therefore, it is important to maintain the amount of Mg2+ greater than equal to the amount of Ti4+ and preferably equal to the amount of Ti4+.
- Electrochemical cells with lithium metal as the anode and cathodes with LiNi0.75Ti0.125Mg0.125 0 2 (prepared according to Example 1) as the active material were made and tested. The electrolyte was IM LiPF6 in a 50/50 volume percent mixture of ethylene carbonate and dimethyl carbonate solvents. Celgard 3501 separators and NRC 2325 coin cell hardware were used. The cathode consisted of 85% active material (by weight), 10% super S™ carbon black (available from Chemetals) and 5% polyvinylidene fluoride (PVDF) as a binder polymer, coated on aluminum foil. Preliminary test results are shown in FIGS. 3-6. The cathode of
test cell 1 contains 9.1 mg active mass of LiNi0.75Ti0.125Mg0.125O2. The cell was first cycled with 0.075 mA from 3.0 V to 5.0 V three times. The results of this cycling are illustrated in the voltage (V) to specific capacity (mA-hr/g) graph of FIG. 3. The current corresponds to a rate close to C/20 or 8.2 mA/g of active mass. After the first conditioning charge, the voltage curve of the subsequent cycles shows very reversible characteristics. As further shown in FIG. 3, most of the capacity is contained between 3.6 V and 4.4 V versus Li. Above 4.4 V, the voltage increases sharply to 5 V which shows very good overcharge characteristics. The reversible capacity is about 190 mA-hr/g. After the three slow cycles, the cell was cycled between 3.0 V and 4.5 V at a larger current of 0.6 mA. This current corresponds to a faster rate of C/3, or 66 mA/g of active material. As shown in the voltage (V) to time (hr) graph of FIG. 4, very good reversibility was maintained and the polarization remained small at the higher charge/discharge rates. The discharge capacity versus cycle number for the 3.0-4.5 V cycling in FIG. 4 is shown in FIG. 5 which demonstrates the excellent cycleability of the material. - A second test cell (test cell2) containing 16.2 mg active mass of LiNi0.75Ti0.125Mg0.125O2 was prepared. The cell was first cycled between 3.0 and 5.0 V for 11 cycles, and was then switched to 3.0-4.5 V cycling. The current for charge and discharge was 0.6 mA. As shown in the graph of discharge capacity versus cycle number in FIG. 6, the cycleability of the material was excellent.
- The LiNi0.9Ti0.05Mg0.05O2, LiNi0.8Ti0.1Mg0.1O2 and LiNi0.75Ti0.125Mg0.125O2 prepared in Example 1 were each used as the active cathode material for electrochemical cells prepared in the manner described in Example 3 using between 10 mg and 20 mg active material for each cell. The cells were first conditioning charged to 5.0 V and discharged to 3.0 V, and then float charged to 4.5 V with 0.2 mA current for 40 hours to ensure equilibrium conditions. The charged cells were then transferred to a glove box filled with argon and opened. Between 0.1 mg and 1.0 mg of the cathode material from the cells was removed and hermetically sealed into DSC cells. Each of cells contained 10-15% of the electrolyte described in Example 3. FIG. 7 illustrates the DSC results for the LiNi0.9Ti0.05Mg0.05O2, LiNi0.8Ti0.1Mg0.1O2 and LiNi0.75Ti0.125Mg0.125O2 with the area of interest magnified in the inset. The positive heat flow in FIG. 7 represent heat flowing out of the sample. As demonstrated in FIG. 7, the sharp exothermic peak at 220° C. decreases with increasing x for the formula LiNil-xTiaMgbO2 (x=a+b) demonstrating the thermal stability and safety advantage associated with the doped intercalation compounds.
- LiNi0.75Ti0.125MgO125O2 prepared as described in Example I was tested for acid resistance. Twenty grams of LiNi0.75Ti0.125Mg0.125O2 was placed in 400 ml deionized water. HCl was added until the pH of the solution reached 2 and the solution was stirred for 1 hour. The LiNi0.75Ti0.125Mg0.125O2 was filtered and washed with deionized water until the wash reached a pH of 7. The first liter of the wash was analyzed with inductively coupled plasma (ICP) spectroscopy. About 25% of the total lithium and less than 0.5% of the total Ni in the sample was detected in the wash. No Ti and Mg were detected in the wash. The washed and filtered LiNi0.75Ti0.125Mg0.125O2 was vacuum dried and an x-ray diffraction of this compound was performed. As shown in FIG. 8, the acid treated sample has the same XRD pattern as an untreated sample and the peaks are still sharp. Therefore, although there is partial delithiation (lithium leaching) under acidic conditions, the basic structural integrity of the material is still maintained as evidenced by the minimal loss of the transition metals and the XRD pattern showing the same structure and crystallinity of the intercalation compound.
- A doped intercalation compound having the formula iNi0.75Ti0.15Mg0.05Li0.05O2 was prepared by firing a stoichiometric mixture of LiOH, NiO, TiO2 and Mg(OH)2 at 800° C. for 20 hours in air, followed by a 1° C./min controlled cooling to 500° C. and natural cooling to room temperature. FIG. 9 illustrates an x-ray diffraction pattern for this compound. As demonstrated in FIG. 9, the intercalation compound was a single phase compound and as evidenced by the peak ratio between the 003 peak and 104 peak, there was no cation mixing in the metal layers. Accordingly, although not wishing to be bound by theory, it is believed that for lithium metal oxides having the formula LiNi1-xTiaMgbO2 (x=a+b), if a>b then deficiencies in Mg can be compensated by excess Li as long as the average oxidation state of the Ti—Mg—Li dopant combination is still maintained at about 3.
- A doped intercalation compound having the formula LiNi0.7Co0.1Ti0.1Mg0.1O2 was prepared by firing a stoichiometric mixture of LiOH, NiO, CO3O4, TiO2 and Mg(OH)2 at 800° C. for 20 hours in air, followed by a 1° C./min controlled cooling to 500° C. and natural cooling to room temperature. As shown in FIG. 10, this intercalation compound was predominantly single phase.
- As shown in the examples, the doped lithium metal oxide or metal oxide intercalation compounds can be used in the positive electrode (cathode) of lithium or lithium-ion electrochemical cells and are typically combined with a carbonaceous material and a binder polymer to form a cathode. The negative electrode can be lithium metal or alloys, or any material capable of reversibly lithiating and delithiating at an electrochemical potential relative to lithium metal between about 0.0 V and 0.7 V, and is separated from the positive electrode material in the cell using an electronic insulating separator. Examples of negative electrode materials are carbonaceous materials including carbonaceous materials containing H, B, Si and Sn, and tin oxides or tin-silicon oxides. The electrochemical cells further include an electrolyte. The electrolyte can be non-aqueous liquid, gel or solid and preferably comprises a lithium salt. Electrochemical cells using the intercalation compounds of the invention as positive electrode material can be combined for use in large power applications such as for electric vehicles.
- In the present invention, a combination of multiple dopants can be selected to replace the transition metal M in intercalation compounds of the formula LiMyOz or MyOz to achieve the same result as a single dopant. As a result, the limits on the choice of single dopants can be avoided and, at the same time, more beneficial effects can be achieved by using a combination of two or more dopants. Specifically, the use of multiple dopants can result in better specific capacity, cycleability, stability, handling properties and/or cost than has been achieved in single dopant metal oxides. Furthermore, the multiple doped intercalation compounds demonstrate good heat and acid stability and therefore are safe for use as cathode materials in electrochemical cells for lithium and lithium ion batteries.
- Many modifications and other embodiments of the invention will come to the mind of one skilled in the art to which this invention pertains having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the invention is not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (17)
1. A doped intercalation compound having the formula:
LiMy-x[A]xOz or My-x[A]xOz,
wherein M=a transition metal,
wherein Bi is an element used to replace the transition metal M and wi is the fractional amount of element Bi in the total dopant combination such that
and n=total number of dopant elements Bi and is a positive integer of two or more;
wherein the fractional amount wi of dopant element Bi is determined by the following relation:
oxidation state of the replaced transition metal ion M±0.5;
wherein Ei is the oxidation state of dopant Bi in the final product LiMy-x{A}xOz or My-x{A}xOz;
wherein the dopant elements Bi are cations in the intercalation compound and at least two of the dopant elements Bi have a different oxidation state than the oxidation state of M in the LiMy-x{A}xOz or My-x{A}xOz; compound;
wherein the dopant elements Bi include Ti4+ and Mg2+;
wherein y and z are values that provide a stable metal oxide compound; and
wherein the ratio of Li to O in the doped intercalation compound is not smaller than the ratio of Li to O in the undoped compound LiMyOz or MyOz.
2. The intercalation compound of claim 1 , wherein the dopant elements Bi are any elements other than M having a Pauling's electronegativity not greater than 2.05 or Mo.
3. The intercalation compound of claim 1 , wherein the dopant elements Bi include no more than one element from Groups IIIB and IVB.
4. The intercalation compound of claim 1 , wherein the fractional amount of Ti4+ is approximately equal to the fractional amount of Mg2+.
5. The intercalation compound of claim 1 , wherein the fractional amount of Mg2+ is no smaller than the fractional amount of Ti4+.
6. A positive electrode for lithium and lithium ions cells comprising an intercalation compound having the formula:
LiMy-x[A]xOz or My-x[A]xOz,
wherein M=a transition metal,
wherein wi is the fractional amount of element Bi in the total dopant combination such that
and n=total number of dopant elements used and is a positive integer of two or more;
wherein the fractional amount wi of dopant element Bi is determined by the following relation:
oxidation state of the replaced transition metal ion M±0.5;
wherein Ei is the oxidation state of dopant Bi in the final product LiMy-x{A}xOz or LiMy-x{A}xOz;
wherein the dopant elements Bi are cations in the intercalation compound and at least two of the dopant elements Bi have a different oxidation state than the oxidation state of M in the LiMy-x{A}xOz or My-x{A}xOz; compound;
wherein the dopant elements Bi include Ti4+ and Mg2+;
wherein y and z are values that provide a stable metal oxide compound; and
wherein the ratio of Li to O in the doped intercalation compound is not smaller than the ratio of Li to O in the undoped compound LiMyOz or MyOz.
7. The positive electrode of claim 6 , wherein the dopant elements Bi are any elements other than M having a Pauling's electronegativity not greater than 2.05 or Mo.
8. The positive electrode of claim 6 , wherein the dopant elements Bi include no more than one element from Groups 111B and IVB.
9. The positive electrode of claim 6 , wherein the fractional amount of Ti4+ is approximately equal to the fractional amount of Mg2+.
10. The positive electrode of claim 6 , wherein the fractional amount of Mg2+ is no smaller than the fractional amount of Ti4+.
11. A method of preparing a doped intercalation compound of the formula LiMy-x{A}xOz or My-x{A}xOz, comprising the steps of:
mixing source compounds containing M, {A} and optionally Li to provide a stoichiometric relationship between M, {A} and Li corresponding to the formula LiMy-x{A}xOz or My-x{A}xOz, wherein M is a transition metal,
wherein Bi is an element i=1 used to replace the transition metal M and wi is the fractional amount of element Bi in the total dopant combination, n is the total number of dopant elements and is a positive integer of two or more, the fractional amount wi of dopant element Bi is determined by the relationship:
Ei is the oxidation state of dopant Bi in the final product LiMy-x{A}xOz or LiMy-x{A}xOz, the dopant elements Bi are selected to be cations in the intercalation compound, at least two of the dopant elements Bi have a different oxidation state than the oxidation state of M in the LiMy-x{A}xOz or My-x{A}xOz compound, the dopant elements Bi include Ti4+ and Mg2+, y and z are values that provide a stable metal oxide compound; and the ratio of Li to O in the doped intercalation compound is not smaller than the ratio of Li to O in the undoped compound LiMyOz or MyOz;
firing the mixture at a temperature between 500° C. and 1000° C. in the presence of oxygen to produce the doped intercalation compound; and
cooling the doped intercalation compound.
12. The method of claim 11 , wherein the step of mixing source compounds comprising mixing source compounds containing a transition metal M selected from Co, Ni, Mn, Fe, V and Mo.
13. The method of claim 11 , wherein the step of mixing source compounds comprising mixing source compounds containing dopant elements Bi other than M having a Pauling's electronegativity not greater than 2.05 or Mo.
14. The method of claim 11 , wherein the step of mixing source compounds comprising mixing source compounds containing dopant elements Bi wherein the dopant elements Bi include no more than one element from Groups 111B and IVB.
15. The method of claim 11 , wherein the step of mixing source compounds comprising mixing source compounds containing Ni or Co as the transition metal M to form an intercalation compound having the formula LiMY-X{A}xOz.
16. The method of claim 15 , wherein the step of mixing source compounds comprising mixing source compounds containing Ni as the transition metal M.
17. The method of claim 11 , wherein the step of mixing source compounds comprises preparing a solution comprising M and {A} from source compounds comprising M and {A}, precipitating the M and {A} out of solution to produce an intimately mixed hydroxide, and blending the mixed hydroxide with a lithium source compound.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040223905A1 (en) * | 2003-05-06 | 2004-11-11 | Inco Limited | Low temperature lithiation of mixed hydroxides |
Families Citing this family (66)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4326041B2 (en) * | 1997-05-15 | 2009-09-02 | エフエムシー・コーポレイション | Doped intercalation compound and method for producing the same |
KR100473413B1 (en) | 1998-11-13 | 2005-03-08 | 에프엠씨 코포레이션 | Layered lithium metal oxides free of localized cubic spinel-like structural phases and methods of making same |
JP4960561B2 (en) * | 1999-12-10 | 2012-06-27 | エフエムシー・コーポレイション | Lithium cobalt oxide and method for producing the same |
JP4678457B2 (en) * | 2000-10-24 | 2011-04-27 | 株式会社豊田中央研究所 | Lithium transition metal composite oxide for positive electrode active material of lithium secondary battery and lithium secondary battery using the same |
JP4592931B2 (en) * | 2000-11-30 | 2010-12-08 | Jx日鉱日石金属株式会社 | Positive electrode material for lithium secondary battery and method for producing the same |
US6964828B2 (en) | 2001-04-27 | 2005-11-15 | 3M Innovative Properties Company | Cathode compositions for lithium-ion batteries |
KR100406816B1 (en) * | 2001-06-05 | 2003-11-21 | 삼성에스디아이 주식회사 | Method of preparing positive active material for rechargeable lithium battery |
US6921609B2 (en) | 2001-06-15 | 2005-07-26 | Kureha Chemical Industry Co., Ltd. | Gradient cathode material for lithium rechargeable batteries |
US6855461B2 (en) * | 2001-06-15 | 2005-02-15 | Kureha Chemical Industry Co., Ltd. | Cathode material for lithium rechargeable batteries |
US20030108793A1 (en) * | 2001-08-07 | 2003-06-12 | 3M Innovative Properties Company | Cathode compositions for lithium ion batteries |
US6878490B2 (en) * | 2001-08-20 | 2005-04-12 | Fmc Corporation | Positive electrode active materials for secondary batteries and methods of preparing same |
JP4836371B2 (en) * | 2001-09-13 | 2011-12-14 | パナソニック株式会社 | Positive electrode active material and non-aqueous electrolyte secondary battery including the same |
JP4197237B2 (en) | 2002-03-01 | 2008-12-17 | パナソニック株式会社 | Method for producing positive electrode active material |
US9391325B2 (en) | 2002-03-01 | 2016-07-12 | Panasonic Corporation | Positive electrode active material, production method thereof and non-aqueous electrolyte secondary battery |
US8394522B2 (en) | 2002-08-09 | 2013-03-12 | Infinite Power Solutions, Inc. | Robust metal film encapsulation |
US7993773B2 (en) * | 2002-08-09 | 2011-08-09 | Infinite Power Solutions, Inc. | Electrochemical apparatus with barrier layer protected substrate |
US8431264B2 (en) | 2002-08-09 | 2013-04-30 | Infinite Power Solutions, Inc. | Hybrid thin-film battery |
US8404376B2 (en) | 2002-08-09 | 2013-03-26 | Infinite Power Solutions, Inc. | Metal film encapsulation |
US8021778B2 (en) | 2002-08-09 | 2011-09-20 | Infinite Power Solutions, Inc. | Electrochemical apparatus with barrier layer protected substrate |
US20070264564A1 (en) | 2006-03-16 | 2007-11-15 | Infinite Power Solutions, Inc. | Thin film battery on an integrated circuit or circuit board and method thereof |
US8236443B2 (en) | 2002-08-09 | 2012-08-07 | Infinite Power Solutions, Inc. | Metal film encapsulation |
US8445130B2 (en) * | 2002-08-09 | 2013-05-21 | Infinite Power Solutions, Inc. | Hybrid thin-film battery |
US20040121234A1 (en) * | 2002-12-23 | 2004-06-24 | 3M Innovative Properties Company | Cathode composition for rechargeable lithium battery |
CN100342571C (en) * | 2003-02-03 | 2007-10-10 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery |
JP4307962B2 (en) * | 2003-02-03 | 2009-08-05 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
US8728285B2 (en) | 2003-05-23 | 2014-05-20 | Demaray, Llc | Transparent conductive oxides |
JP4737952B2 (en) * | 2003-07-24 | 2011-08-03 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery |
JP4497899B2 (en) * | 2003-11-19 | 2010-07-07 | 三洋電機株式会社 | Lithium secondary battery |
US7211237B2 (en) * | 2003-11-26 | 2007-05-01 | 3M Innovative Properties Company | Solid state synthesis of lithium ion battery cathode material |
KR101065307B1 (en) * | 2004-01-19 | 2011-09-16 | 삼성에스디아이 주식회사 | Cathode active material for lithium secondary battery and lithium secondary battery using the same |
US7968233B2 (en) | 2004-02-18 | 2011-06-28 | Solicore, Inc. | Lithium inks and electrodes and batteries made therefrom |
JP4502664B2 (en) * | 2004-02-24 | 2010-07-14 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery |
JP4291195B2 (en) * | 2004-03-30 | 2009-07-08 | 宇部興産株式会社 | Nonaqueous electrolyte secondary battery |
US7381496B2 (en) * | 2004-05-21 | 2008-06-03 | Tiax Llc | Lithium metal oxide materials and methods of synthesis and use |
JP4721729B2 (en) | 2004-11-12 | 2011-07-13 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
JP4841133B2 (en) | 2004-11-16 | 2011-12-21 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
US7959769B2 (en) | 2004-12-08 | 2011-06-14 | Infinite Power Solutions, Inc. | Deposition of LiCoO2 |
CN101931097B (en) | 2004-12-08 | 2012-11-21 | 希莫菲克斯公司 | Deposition of LiCoO2 |
WO2008039808A2 (en) | 2006-09-25 | 2008-04-03 | Board Of Regents, The University Of Texas System | Cation-substituted spinel oxide and oxyfluoride cathodes for lithium ion batteries |
US8062708B2 (en) | 2006-09-29 | 2011-11-22 | Infinite Power Solutions, Inc. | Masking of and material constraint for depositing battery layers on flexible substrates |
US8197781B2 (en) | 2006-11-07 | 2012-06-12 | Infinite Power Solutions, Inc. | Sputtering target of Li3PO4 and method for producing same |
JP2008123972A (en) * | 2006-11-16 | 2008-05-29 | Sanyo Electric Co Ltd | Non-aqueous electrolyte secondary cell |
JP2009032656A (en) * | 2007-02-28 | 2009-02-12 | Sanyo Electric Co Ltd | Method of manufacturing active material for lithium secondary battery, method of manufacturing electrode for lithium secondary battery, method of manufacturing lithium secondary battery, and method of monitoring quality of active material for lithium secondary battery |
JP2008251218A (en) * | 2007-03-29 | 2008-10-16 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
US8268488B2 (en) * | 2007-12-21 | 2012-09-18 | Infinite Power Solutions, Inc. | Thin film electrolyte for thin film batteries |
KR20100102180A (en) | 2007-12-21 | 2010-09-20 | 인피니트 파워 솔루션스, 인크. | Method for sputter targets for electrolyte films |
JP5705549B2 (en) * | 2008-01-11 | 2015-04-22 | インフィニット パワー ソリューションズ, インコーポレイテッド | Thin film encapsulation for thin film batteries and other devices |
EP2269251A4 (en) | 2008-03-04 | 2012-09-26 | Enerdel Inc | Anode for lithium-ion cell and method of making the same |
CN101960655A (en) * | 2008-03-04 | 2011-01-26 | 埃纳德尔公司 | Anode for lithium-ion cell and method of making the same |
US8350519B2 (en) | 2008-04-02 | 2013-01-08 | Infinite Power Solutions, Inc | Passive over/under voltage control and protection for energy storage devices associated with energy harvesting |
US8906523B2 (en) | 2008-08-11 | 2014-12-09 | Infinite Power Solutions, Inc. | Energy device with integral collector surface for electromagnetic energy harvesting and method thereof |
EP2332127A4 (en) | 2008-09-12 | 2011-11-09 | Infinite Power Solutions Inc | Energy device with integral conductive surface for data communication via electromagnetic energy and method thereof |
EP2345145B1 (en) * | 2008-10-08 | 2016-05-25 | Sapurast Research LLC | Foot-powered footwear-embedded sensor-transceiver |
WO2010042594A1 (en) * | 2008-10-08 | 2010-04-15 | Infinite Power Solutions, Inc. | Environmentally-powered wireless sensor module |
EP2474056B1 (en) | 2009-09-01 | 2016-05-04 | Sapurast Research LLC | Printed circuit board with integrated thin film battery |
JP2013528912A (en) | 2010-06-07 | 2013-07-11 | インフィニット パワー ソリューションズ, インコーポレイテッド | Rechargeable high density electrochemical device |
JPWO2012067102A1 (en) * | 2010-11-16 | 2014-05-12 | 日立マクセル株式会社 | Non-aqueous secondary battery |
KR101320391B1 (en) | 2011-07-18 | 2013-10-23 | 삼성에스디아이 주식회사 | Positive active material for lithium secondary battery, preparing method thereof, positive electrode including the same, and lithium secondary battery employing the same |
KR101666879B1 (en) | 2012-08-14 | 2016-10-17 | 삼성에스디아이 주식회사 | Cathode active material for lithium secondary battery, method for preparing cathode active material for lithium secondary battery and lithium secondary battery including cathode active material |
CN104241679A (en) * | 2013-06-14 | 2014-12-24 | 上海绿孚新能源科技有限公司 | Secondary battery |
US9627722B1 (en) | 2013-09-16 | 2017-04-18 | American Lithium Energy Corporation | Positive temperature coefficient film, positive temperature coefficient electrode, positive temperature coefficient separator, and battery comprising the same |
EP3155680B1 (en) | 2014-06-10 | 2019-08-07 | Umicore | Positive electrode materials having a superior hardness strength |
CN115603009A (en) | 2014-11-25 | 2023-01-13 | 美国锂能源公司(Us) | Protective layer for use in rechargeable battery, rechargeable battery and method |
KR101826612B1 (en) | 2017-06-07 | 2018-02-07 | 주식회사 엘 앤 에프 | Positive active material, and rechargeable lithium battery including the same |
WO2019023683A1 (en) * | 2017-07-28 | 2019-01-31 | American Lithium Energy Corporation | Anti-corrosion coating for battery current collector |
KR102313226B1 (en) * | 2017-11-24 | 2021-10-14 | 주식회사 엘지화학 | Positive electrode material for lithium secondary battery and method for preparing the same |
Citations (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4366215A (en) * | 1979-11-06 | 1982-12-28 | South African Inventions Development Corp. | Electrochemical cell |
US4465747A (en) * | 1983-06-29 | 1984-08-14 | Union Carbide Corporation | Alkali metal or alkaline earth metal compound additive for manganese dioxide-containing nonaqueous cells |
US4507371A (en) * | 1982-06-02 | 1985-03-26 | South African Inventions Development Corporation | Solid state cell wherein an anode, solid electrolyte and cathode each comprise a cubic-close-packed framework structure |
US4668595A (en) * | 1985-05-10 | 1987-05-26 | Asahi Kasei Kogyo Kabushiki Kaisha | Secondary battery |
US4925752A (en) * | 1989-03-03 | 1990-05-15 | Fauteux Denis G | Solid state electrochemical cell having porous cathode current collector |
US4980251A (en) * | 1988-07-12 | 1990-12-25 | Csir | Method of synthesizing a lithium manganese oxide |
US5147738A (en) * | 1989-10-06 | 1992-09-15 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery |
US5153081A (en) * | 1989-07-28 | 1992-10-06 | Csir | Lithium manganese oxide compound |
US5160712A (en) * | 1990-04-12 | 1992-11-03 | Technology Finance Corporation (Prop.) Ltd | Lithium transition metal oxide |
US5169736A (en) * | 1990-08-09 | 1992-12-08 | Varta Batterie Aktiengesellschaft | Electrochemical secondary element |
US5240794A (en) * | 1990-12-20 | 1993-08-31 | Technology Finance Corporation (Proprietary) Limited | Electrochemical cell |
US5264201A (en) * | 1990-07-23 | 1993-11-23 | Her Majesty The Queen In Right Of The Province Of British Columbia | Lithiated nickel dioxide and secondary cells prepared therefrom |
US5316877A (en) * | 1992-08-28 | 1994-05-31 | Technology Finance Corporation (Proprietary) Limited | Electrochemical cell |
US5370949A (en) * | 1993-07-09 | 1994-12-06 | National Research Council Of Canada | Materials for use as cathodes in lithium electrochemical cells |
US5425932A (en) * | 1993-05-19 | 1995-06-20 | Bell Communications Research, Inc. | Method for synthesis of high capacity Lix Mn2 O4 secondary battery electrode compounds |
US5429890A (en) * | 1994-02-09 | 1995-07-04 | Valence Technology, Inc. | Cathode-active material blends of Lix Mn2 O4 |
US5478671A (en) * | 1992-04-24 | 1995-12-26 | Fuji Photo Film Co., Ltd. | Nonaqueous secondary battery |
US5478675A (en) * | 1993-12-27 | 1995-12-26 | Hival Ltd. | Secondary battery |
US5478672A (en) * | 1993-12-24 | 1995-12-26 | Sharp Kabushiki Kaisha | Nonaqueous secondary battery, positive-electrode active material |
US5478674A (en) * | 1993-04-28 | 1995-12-26 | Fuji Photo Film Co., Ltd. | Nonaqueous electrolyte-secondary battery |
US5515842A (en) * | 1993-08-09 | 1996-05-14 | Disetronic Ag | Inhalation device |
US5609975A (en) * | 1994-05-13 | 1997-03-11 | Matsushita Electric Industrial Co., Ltd. | Positive electrode for non-aqueous electrolyte lithium secondary battery and method of manufacturing the same |
US5620812A (en) * | 1994-08-04 | 1997-04-15 | Seiko Instruments Inc. | Non-aqueous electrolyte secondary battery |
US5626635A (en) * | 1994-12-16 | 1997-05-06 | Matsushita Electric Industrial Co., Ltd. | Processes for making positive active material for lithium secondary batteries and secondary batteries therefor |
US5631105A (en) * | 1995-05-26 | 1997-05-20 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte lithium secondary battery |
US5658693A (en) * | 1991-06-17 | 1997-08-19 | Technology Finance Corporation (Proprietary) Limited | Manganese dioxide-based material |
US5672329A (en) * | 1992-07-29 | 1997-09-30 | Tosoh Corporation | Manganese oxides production thereof, and use thereof |
US5674645A (en) * | 1996-09-06 | 1997-10-07 | Bell Communications Research, Inc. | Lithium manganese oxy-fluorides for li-ion rechargeable battery electrodes |
US5677087A (en) * | 1995-04-26 | 1997-10-14 | Japan Storage Battery Co., Ltd. | Method for manufacturing positive electrode material for a lithium battery |
US5686203A (en) * | 1994-12-01 | 1997-11-11 | Fuji Photo Film Co., Ltd. | Non-aqueous secondary battery |
US5718989A (en) * | 1995-12-29 | 1998-02-17 | Japan Storage Battery Co., Ltd. | Positive electrode active material for lithium secondary battery |
US5750288A (en) * | 1995-10-03 | 1998-05-12 | Rayovac Corporation | Modified lithium nickel oxide compounds for electrochemical cathodes and cells |
US5783333A (en) * | 1996-11-27 | 1998-07-21 | Polystor Corporation | Lithium nickel cobalt oxides for positive electrodes |
US5866279A (en) * | 1996-03-19 | 1999-02-02 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte secondary cell |
US6017654A (en) * | 1997-08-04 | 2000-01-25 | Carnegie Mellon University | Cathode materials for lithium-ion secondary cells |
US6071645A (en) * | 1996-07-12 | 2000-06-06 | Saft | Lithium electrode for a rechargeable electrochemical cell |
US6277521B1 (en) * | 1997-05-15 | 2001-08-21 | Fmc Corporation | Lithium metal oxide containing multiple dopants and method of preparing same |
Family Cites Families (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2547992B2 (en) | 1986-11-08 | 1996-10-30 | 旭化成工業株式会社 | Non-aqueous secondary battery |
JPH0821382B2 (en) | 1988-11-17 | 1996-03-04 | 松下電器産業株式会社 | Non-aqueous electrolyte secondary battery |
JP2798991B2 (en) | 1989-08-11 | 1998-09-17 | 富士電気化学株式会社 | Manufacturing method of non-aqueous electrolyte secondary battery |
GB2244701B (en) | 1990-05-17 | 1994-01-12 | Technology Finance Corp | Manganese oxide compound |
JPH04162356A (en) | 1990-10-24 | 1992-06-05 | Furukawa Battery Co Ltd:The | Positive electrode activated material and manufacture thereof for lithium secondary battery |
JP2586747B2 (en) | 1991-01-29 | 1997-03-05 | 株式会社ユアサコーポレーション | Lithium secondary battery |
JP3086297B2 (en) | 1991-05-21 | 2000-09-11 | 東芝電池株式会社 | Non-aqueous solvent secondary battery |
JP3232790B2 (en) | 1992-07-29 | 2001-11-26 | 東ソー株式会社 | Novel manganese oxide, its production method and its use |
JPH06124707A (en) | 1992-10-14 | 1994-05-06 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolytic battery |
JPH07114915A (en) | 1993-10-15 | 1995-05-02 | Fuji Photo Film Co Ltd | Nonaqueous secondary battery |
CA2102738C (en) | 1993-11-09 | 1999-01-12 | George T. Fey | Inverse spinel compounds as cathodes for lithium batteries |
JP3197763B2 (en) | 1993-11-18 | 2001-08-13 | 三洋電機株式会社 | Non-aqueous battery |
TW284922B (en) | 1994-05-10 | 1996-09-01 | Sumitomo Chemical Co | |
JPH0878004A (en) | 1994-09-05 | 1996-03-22 | Hitachi Ltd | Lithium secondary battery |
JPH08138669A (en) | 1994-11-02 | 1996-05-31 | Toray Ind Inc | Cathode active material, manufacture thereof, and non-aqueous solvent secondary battery using the same |
JPH08138649A (en) | 1994-11-09 | 1996-05-31 | Toray Ind Inc | Non-aqueous secondary battery |
CA2162456C (en) | 1994-11-09 | 2008-07-08 | Keijiro Takanishi | Cathode material, method of preparing it and nonaqueous solvent type secondary battery having a cathode comprising it |
JP3232943B2 (en) | 1994-12-16 | 2001-11-26 | 松下電器産業株式会社 | Manufacturing method of positive electrode active material for lithium secondary battery |
JPH08250120A (en) | 1995-03-08 | 1996-09-27 | Sanyo Electric Co Ltd | Lithium secondary battery |
JP3197779B2 (en) | 1995-03-27 | 2001-08-13 | 三洋電機株式会社 | Lithium battery |
JP3506397B2 (en) | 1995-03-28 | 2004-03-15 | 三井金属鉱業株式会社 | Positive electrode material for lithium secondary battery, method for producing the same, and lithium secondary battery using the same |
JPH08287914A (en) | 1995-04-18 | 1996-11-01 | Nippon Telegr & Teleph Corp <Ntt> | Lithium battery |
DE19519044A1 (en) | 1995-05-24 | 1996-11-28 | Basf Magnetics Gmbh | Spinels containing lithium and manganese (III / IV) |
US5769815A (en) | 1995-05-25 | 1998-06-23 | Medisystems Technology Corporation | Blood chamber with integral projections |
JP3260282B2 (en) | 1995-05-26 | 2002-02-25 | 松下電器産業株式会社 | Non-aqueous electrolyte lithium secondary battery |
JPH097638A (en) | 1995-06-22 | 1997-01-10 | Seiko Instr Inc | Nonaqueous electrolytic secondary battery |
JPH09306490A (en) | 1996-05-15 | 1997-11-28 | Mitsubishi Chem Corp | Nonaqueous electrolyte secondary battery |
US6159636A (en) * | 1996-04-08 | 2000-12-12 | The Gillette Company | Mixtures of lithium manganese oxide spinel as cathode active material |
JPH101316A (en) | 1996-06-10 | 1998-01-06 | Sakai Chem Ind Co Ltd | Lithium-cobalt multiple oxide and production thereof, and lithium ion secondary battery |
JP3290355B2 (en) | 1996-07-12 | 2002-06-10 | 株式会社田中化学研究所 | Lithium-containing composite oxide for lithium ion secondary battery and method for producing the same |
JP3609229B2 (en) | 1997-01-29 | 2005-01-12 | 株式会社田中化学研究所 | Method for producing positive electrode active material for non-aqueous secondary battery and lithium secondary battery using the same |
JP4022937B2 (en) * | 1997-04-24 | 2007-12-19 | 宇部興産株式会社 | Lithium ion non-aqueous electrolyte secondary battery |
JP4326041B2 (en) * | 1997-05-15 | 2009-09-02 | エフエムシー・コーポレイション | Doped intercalation compound and method for producing the same |
-
1998
- 1998-05-15 JP JP15215298A patent/JP4326041B2/en not_active Expired - Lifetime
- 1998-05-15 JP JP10171998A patent/JP3045998B2/en not_active Expired - Lifetime
-
2000
- 2000-05-30 US US09/580,088 patent/US6582852B1/en not_active Expired - Lifetime
-
2002
- 2002-06-07 US US10/165,023 patent/US6794085B2/en not_active Expired - Lifetime
-
2004
- 2004-06-30 US US10/880,890 patent/US20040241547A1/en not_active Abandoned
Patent Citations (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4366215A (en) * | 1979-11-06 | 1982-12-28 | South African Inventions Development Corp. | Electrochemical cell |
US4507371A (en) * | 1982-06-02 | 1985-03-26 | South African Inventions Development Corporation | Solid state cell wherein an anode, solid electrolyte and cathode each comprise a cubic-close-packed framework structure |
US4465747A (en) * | 1983-06-29 | 1984-08-14 | Union Carbide Corporation | Alkali metal or alkaline earth metal compound additive for manganese dioxide-containing nonaqueous cells |
US4668595A (en) * | 1985-05-10 | 1987-05-26 | Asahi Kasei Kogyo Kabushiki Kaisha | Secondary battery |
US4980251A (en) * | 1988-07-12 | 1990-12-25 | Csir | Method of synthesizing a lithium manganese oxide |
US4925752A (en) * | 1989-03-03 | 1990-05-15 | Fauteux Denis G | Solid state electrochemical cell having porous cathode current collector |
US5153081A (en) * | 1989-07-28 | 1992-10-06 | Csir | Lithium manganese oxide compound |
US5147738A (en) * | 1989-10-06 | 1992-09-15 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery |
US5160712A (en) * | 1990-04-12 | 1992-11-03 | Technology Finance Corporation (Prop.) Ltd | Lithium transition metal oxide |
US5264201A (en) * | 1990-07-23 | 1993-11-23 | Her Majesty The Queen In Right Of The Province Of British Columbia | Lithiated nickel dioxide and secondary cells prepared therefrom |
US5169736A (en) * | 1990-08-09 | 1992-12-08 | Varta Batterie Aktiengesellschaft | Electrochemical secondary element |
US5240794A (en) * | 1990-12-20 | 1993-08-31 | Technology Finance Corporation (Proprietary) Limited | Electrochemical cell |
US5658693A (en) * | 1991-06-17 | 1997-08-19 | Technology Finance Corporation (Proprietary) Limited | Manganese dioxide-based material |
US5478671A (en) * | 1992-04-24 | 1995-12-26 | Fuji Photo Film Co., Ltd. | Nonaqueous secondary battery |
US5672329A (en) * | 1992-07-29 | 1997-09-30 | Tosoh Corporation | Manganese oxides production thereof, and use thereof |
US5316877A (en) * | 1992-08-28 | 1994-05-31 | Technology Finance Corporation (Proprietary) Limited | Electrochemical cell |
US5478674A (en) * | 1993-04-28 | 1995-12-26 | Fuji Photo Film Co., Ltd. | Nonaqueous electrolyte-secondary battery |
US5425932A (en) * | 1993-05-19 | 1995-06-20 | Bell Communications Research, Inc. | Method for synthesis of high capacity Lix Mn2 O4 secondary battery electrode compounds |
US5370949A (en) * | 1993-07-09 | 1994-12-06 | National Research Council Of Canada | Materials for use as cathodes in lithium electrochemical cells |
US5515842A (en) * | 1993-08-09 | 1996-05-14 | Disetronic Ag | Inhalation device |
US5478672A (en) * | 1993-12-24 | 1995-12-26 | Sharp Kabushiki Kaisha | Nonaqueous secondary battery, positive-electrode active material |
US5478675A (en) * | 1993-12-27 | 1995-12-26 | Hival Ltd. | Secondary battery |
US5429890A (en) * | 1994-02-09 | 1995-07-04 | Valence Technology, Inc. | Cathode-active material blends of Lix Mn2 O4 |
US5609975A (en) * | 1994-05-13 | 1997-03-11 | Matsushita Electric Industrial Co., Ltd. | Positive electrode for non-aqueous electrolyte lithium secondary battery and method of manufacturing the same |
US5620812A (en) * | 1994-08-04 | 1997-04-15 | Seiko Instruments Inc. | Non-aqueous electrolyte secondary battery |
US5686203A (en) * | 1994-12-01 | 1997-11-11 | Fuji Photo Film Co., Ltd. | Non-aqueous secondary battery |
US5626635A (en) * | 1994-12-16 | 1997-05-06 | Matsushita Electric Industrial Co., Ltd. | Processes for making positive active material for lithium secondary batteries and secondary batteries therefor |
US5677087A (en) * | 1995-04-26 | 1997-10-14 | Japan Storage Battery Co., Ltd. | Method for manufacturing positive electrode material for a lithium battery |
US5631105A (en) * | 1995-05-26 | 1997-05-20 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte lithium secondary battery |
US5750288A (en) * | 1995-10-03 | 1998-05-12 | Rayovac Corporation | Modified lithium nickel oxide compounds for electrochemical cathodes and cells |
US5718989A (en) * | 1995-12-29 | 1998-02-17 | Japan Storage Battery Co., Ltd. | Positive electrode active material for lithium secondary battery |
US5795558A (en) * | 1995-12-29 | 1998-08-18 | Japan Storage Battery Co., Ltd. | Positive electrode active material for lithium secondary battery method of producing |
US5866279A (en) * | 1996-03-19 | 1999-02-02 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte secondary cell |
US6071645A (en) * | 1996-07-12 | 2000-06-06 | Saft | Lithium electrode for a rechargeable electrochemical cell |
US5674645A (en) * | 1996-09-06 | 1997-10-07 | Bell Communications Research, Inc. | Lithium manganese oxy-fluorides for li-ion rechargeable battery electrodes |
US5783333A (en) * | 1996-11-27 | 1998-07-21 | Polystor Corporation | Lithium nickel cobalt oxides for positive electrodes |
US6277521B1 (en) * | 1997-05-15 | 2001-08-21 | Fmc Corporation | Lithium metal oxide containing multiple dopants and method of preparing same |
US6017654A (en) * | 1997-08-04 | 2000-01-25 | Carnegie Mellon University | Cathode materials for lithium-ion secondary cells |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040223905A1 (en) * | 2003-05-06 | 2004-11-11 | Inco Limited | Low temperature lithiation of mixed hydroxides |
US7033555B2 (en) * | 2003-05-06 | 2006-04-25 | Inco Limited | Low temperature lithiation of mixed hydroxides |
Also Published As
Publication number | Publication date |
---|---|
JP3045998B2 (en) | 2000-05-29 |
US6582852B1 (en) | 2003-06-24 |
JP4326041B2 (en) | 2009-09-02 |
US6794085B2 (en) | 2004-09-21 |
JPH1179750A (en) | 1999-03-23 |
US20020197533A1 (en) | 2002-12-26 |
JPH1192149A (en) | 1999-04-06 |
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