CN110776019A - Synthesis of high-voltage anode material and preparation of high-voltage electrolyte for lithium ion battery - Google Patents

Synthesis of high-voltage anode material and preparation of high-voltage electrolyte for lithium ion battery Download PDF

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CN110776019A
CN110776019A CN201910674876.7A CN201910674876A CN110776019A CN 110776019 A CN110776019 A CN 110776019A CN 201910674876 A CN201910674876 A CN 201910674876A CN 110776019 A CN110776019 A CN 110776019A
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lithium
precursor
manganese
optionally
nickel oxide
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周颖瑜
舒时伟
禤施颖
辛见卓
何国强
李基凡
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Nano and Advanced Materials Institute Ltd
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    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
    • H01M4/52—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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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01P2006/16—Pore diameter
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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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

Abstract

The present invention relates to scalable methods for preparing lithium manganese nickel oxide positive electrode materials and formulations for high voltage electrolyte systems for use in lithium ion batteries. The lithium manganese nickel oxide was prepared by a continuous stirred tank reactor followed by calcination. The lithium ion battery applying the developed cathode material and the electrolyte can be charged to 5V, and has relatively high specific capacitance and long-term cycling stability.

Description

Synthesis of high-voltage anode material and preparation of high-voltage electrolyte for lithium ion battery
Reference to related applications
The present invention claims priority from U.S. provisional application No. 62/764,293 entitled "synthesis of high voltage cathode materials and preparation of high voltage electrolytes for lithium ion batteries," filed 2018, 7, 27, which is incorporated herein by reference in its entirety.
Technical Field
The present invention relates to the field of lithium ion batteries. In particular, the present invention relates to a method for manufacturing a positive electrode material suitable for a high voltage lithium ion battery, in particular, a lithium manganese nickel oxide material, and a novel high voltage positive electrode material prepared thereby. The invention also relates to a formula of the high-voltage electrolyte for the lithium ion battery.
Background
With the advent of a variety of new applications, the Lithium Ion Battery (LIB) industry is expected to appeal to the market. In order to cope with the development trend of the next generation Electric Vehicles (EVs) and electric power applications, the development of LIBs with higher energy density is urgently required. Therefore, a need has arisen for the research and development of new materials, particularly positive electrode materials for EVs and power batteries.
Much research has been devoted to developing new cathode materials for EV and power batteries that make the energy density, power density, cycle life and safety performance of the batteries more efficient than existing cathode materials. LiMn with spinel structure 1.5Ni 0.5O 4Lithium metal oxide material of (LMNO) has been proposed as one of the potential positive electrode materials for 5V batteries for EV and power battery applications due to its high nominal voltage of 4.6V (compared to graphite) and good specific capacitance of 130 mAh/g. Furthermore, since LMNO does not contain expensive and toxic cobalt elements, it is less costly than lithium nickel cobalt manganese oxide cathode materials.
However, spinel LMNO still suffers from capacitive decay during cycling due to the phase impurities of LMNO. Another key obstacle to commercialization of 5V cells is electrolyte decomposition, since the operating voltage window of LMNO/graphite full cells (5V) exceeds the electrochemical stability window of currently available commercial electrolytes of about 4.35V.
Therefore, in order to overcome some technical problems in the application of the existing high-voltage lithium ion battery, it is urgently needed to develop a positive electrode material with good cycle stability, which can be suitable for the high-voltage lithium ion battery, a preparation method thereof and an electrolyte formula for the high-voltage lithium ion battery.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a novel positive electrode material (especially a lithium manganese nickel oxide material) with good cycle stability for a high-voltage lithium ion battery, a preparation method thereof and an electrolyte formula for the high-voltage lithium ion battery.
A first aspect of the present invention provides a method for manufacturing lithium manganese nickel oxide, comprising the steps of:
(a) reacting metal salts (e.g., manganese metal salts and nickel metal salts) in a reactor to form a precursor; and
(b) the precursor is calcined (e.g., in a furnace) with a lithium salt to obtain a lithium manganese nickel oxide.
In some embodiments, the method of the present invention for making lithium manganese nickel oxide is performed in a CSTR system. In some embodiments, the method for manufacturing lithium manganese nickel oxide according to the present invention further comprises the step (c): modifying the obtained lithium manganese nickel oxide.
In some embodiments, the step (a) is performed in the presence of a precipitating agent selected from one or more of sodium carbonate, sodium hydroxide, ammonium bicarbonate and ammonium oxalate. In a preferred embodiment, the precipitating agent is sodium carbonate (e.g., sodium carbonate solution) and ammonium hydroxide (e.g., ammonium hydroxide solution).
In some embodiments, step (a) comprises reacting a manganese metal salt and a nickel metal salt in a reactor. In some embodiments, the manganese metal salt is selected from one or more of manganese sulfate, manganese nitrate, manganese acetate, and manganese chloride, for example, the manganese metal salt is manganese sulfate. In some embodiments, the nickel metal salt is selected from one or more of nickel sulfate, nickel nitrate, nickel acetate, and nickel chloride, for example the nickel metal salt is nickel sulfate. In further embodiments, step (a) further comprises dissolving the manganese metal salt and nickel metal salt in water to form a transition metal solution. The step (a) further comprises dissolving the precipitant in water to form a precipitant solution (e.g., an alkali solution and/or an ammonia solution). In a further embodiment, the water is deionized water. In a further embodiment, step (a) further comprises feeding the transition metal solution and precipitant solution (e.g., by peristaltic pump) into a reactor and mixing. In some embodiments, the ratio of manganese atoms to nickel atoms in the reactor is controlled to be about 3/1.
In some embodiments, step (a) further comprises controlling the pH in the reactor to be in the range of about 6-8, such as about 7.3-8.0, about 7.35-7.75, about 7.5-7.8, about 7.6-7.8, about 7.65-7.75, about 7.3, 7.35, 7.4, 7.5, 7.6, 7.65, 7.7, 7.75, 7.8, and the like, preferably about 7.6-7.8, about 7.65-7.75, such as about 7.65 or about 7.75. In some embodiments, step (a) further comprises controlling the reaction temperature in the range of about 30-60 ℃, e.g., about 35-55 ℃, about 40-50 ℃, about 35 ℃, 38 ℃, 40 ℃, 42 ℃, 45 ℃, 48 ℃, 50 ℃, 55 ℃, etc. In some embodiments, step (a) further comprises stirring the mixture in the reactor at a rate of about 200-.
In some embodiments, when the precipitant comprises one or more of ammonium hydroxide, ammonium bicarbonate, and ammonium oxalate, the step (a) further comprises controlling the ammonia concentration in the reactor to be about 0.1-4.0M, e.g., about 0.5-4.0M, about 1.0-4.0M, about 1.5-4.0M, about 2.0-4.0M, about 2.5-3.8M, about 2.8-3.3M, about 3.0-3.5M, about 0.7M, about 1.0M, about 2.8M, about 3.0M, about 3.2M, about 3.4M, preferably about 3.0M.
In some embodiments, step (a) further comprises collecting the precursor, washing and drying. In some embodiments, the precursor is spherical particles having a particle size distribution of about 5 to 50 μm and an average particle size of about 10 to 20 μm, preferably about 15 to 20 μm. Optionally, the precursor comprises pores having a pore size of about 10-500nm, preferably, the average pore size is about 100-200 nm.
In some embodiments, the lithium salt in step (b) is selected from one or more of lithium hydroxide, lithium carbonate, lithium acetate, lithium chloride and lithium nitrate, for example the lithium salt is lithium hydroxide or lithium carbonate.
In some embodiments, the calcining in step (b) comprises heating the precursor with a lithium salt to about 400-; then heated to about 800-1150 deg.C (e.g., about 850-1100 deg.C, about 900-1050 deg.C, about 925-975 deg.C, about 950-1000 deg.C, about 925 deg.C, about 950 deg.C, about 975 deg.C) and left for about 12-36 hours, e.g., about 24 hours.
In some embodiments, the lithium manganese nickel oxide is spherical particles having a particle size distribution of about 5 to 50 μm and an average particle size of about 10 to 20 μm, preferably about 15 to 20 μm. Optionally, the lithium manganese nickel oxide contains pores with a pore size of about 10-500nm, preferably, the average pore size is about 100-200 nm. In a preferred embodiment, the precursor is Mn 1.5Ni 0.5(CO 3) 2And the lithium manganese nickel oxide is LiMn 1.5Ni 0.5O 4(LMNO)。
In some embodiments, the modifying in step (c) is performed by doping, cladding, or a combination thereof. In some embodiments, step (c) comprises treating the substrate with, for example, MgO, Al 2O 3、Fe 2And carrying out doping modification on materials such as O and the like. In some embodiments, step (c) comprises treating the substrate with a compound selected from Al 2O 3、TiO 2Any one or more of LiPAA and 0.5-5% wt of carbon coats the lithium manganese nickel oxide.
In a further embodiment, said step (a) comprises: (a1) dissolving manganese sulfate and nickel sulfate in water to form a transition metal solution; (a2) respectively dissolving sodium carbonate and ammonium hydroxide in water to form an alkali solution and an ammonia solution; (a3) reacting the transition metal solution, the alkali solution and the ammonia solution in a reactor to form a precursor Mn 1.5Ni 0.5(CO 3) 2(ii) a And (a4) collecting the precursor. Optionally, the step (b) comprises: calcining the precursor obtained in step (a) together with lithium carbonate or lithium hydroxide in a furnace to obtain a lithium manganese nickel oxide LiMn 1.5Ni 0.5O 4Wherein the calcination profile comprises heating the precursor and lithium salt to about 400-600 ℃ for about 4-8 hours, followed by heating to about 800-1150 ℃ for about 12-36 hours, e.g., at a heating and cooling rate of 1-5 ℃/min. Optionally, the step (c) comprises: (c1) with elements selected from Al 2O 3、TiO 2Any one or more of LiPAA and 0.5-5% wt of carbon coats the lithium manganese nickel oxide.
A second aspect of the invention provides a lithium manganese nickel oxide material produced by any of the above methods of the invention.
In a third aspect, the invention provides a positive electrode material for a high-voltage lithium ion battery, wherein the positive electrode material comprises the lithium manganese nickel oxide material.
In a fourth aspect, the invention provides a high-voltage lithium ion battery, which comprises the cathode material.
In some embodiments, the high voltage lithium ion battery further comprises an electrolyte system comprising a solvent and an additive. In some embodiments, the solvent includes, but is not limited to, EC, EMC, DMC, nitrile, fluorinated solvent, and any combination thereof. In some embodiments, the additives include, but are not limited to, FEC, TMSP, TMSPi, LiFOB, LiBOB, PS, 13PCS, AMSL, DN-6-O, VC, and any combination thereof.
In some embodiments, the solvent comprises EC + DMC (e.g., EC: DMC at a 1:1v/v, 1:2v/v ratio) or EC + EMC (e.g., 3:7v/v), preferably comprises EC: DMC at 1:2 v/v. In some embodiments, the additive is selected from the following combinations: TMSP +13 PCS; TMSP + LiFOB; TMSP + PS; TMSPi + VC; and TMSPi +13 PCS. Preferably, the above combination comprises 1% TMSP + 1% 13 PCS; 1% TMSP + 1% LiFOB; 1% TMSP + 2% PS; 1% TMSPi + 0.09% VC; 1% TMSPi + 1% 13 PCS.
In some embodiments, the active material of the lithium ion battery negative electrode includes, but is not limited to, lithium titanium oxide, graphite, silicon carbon composite, silicon containing composite, and any combination thereof.
A fifth aspect of the invention provides a method of screening an electrolyte system for use in a high voltage lithium ion battery, the method comprising:
(1) selecting a proper electrolyte solvent system;
(2) screening single additives through simulation and testing; and
(3) appropriate additive combinations were screened.
In some embodiments, wherein said selecting in step (1) is by a test including, but not limited to, battery cycling tests, cyclic voltammetry, electrochemical impedance spectroscopy, and the like. In some embodiments, the modeling in step (2) comprises calculating different parameters of the additive, including, but not limited to, HOMO and LUMO energy, electron affinity, dipole moment, and chemical hardness. Preferably, the single additive test is performed based on the solvent system selected in step (1). And, performing step (3) based on the single additive selected in step (2).
In some embodiments, the electrolyte system is used in a high voltage lithium ion battery, wherein the high voltage lithium ion battery comprises a cathode material according to the present invention.
A sixth aspect of the invention provides an electrolyte system formulation obtainable by a method such as that described in the fifth aspect of the invention, the electrolyte system formulation comprising a solvent and an additive.
In some embodiments, the solvent of the electrolyte formulation includes, but is not limited to, EC, EMC, DMC, nitrile, fluorinated solvent, and any combination thereof, preferably 1:2v/v EC to DMC. In some embodiments, the additives of the electrolyte formulation include, but are not limited to, FEC, TMSP, TMSPi, LiFOB, LiBOB, PS, 13PCS, AMSL, DN-6-O, VC and any combination thereof, preferably, the weight percentage of each additive is about 0.05-2%. Preferably, the additive comprises any one or more of the following combinations: 1% TMSP + 1% 13 PCS; 1% TMSP + 1% LiFOB; 1% TMSP + 2% PS; 1% TMSPi + 0.09% VC; 1% TMSPi + 1% 13 PCS.
Compared with the prior art, the preparation method, the lithium manganese nickel oxide and the electrolyte formula have the following advantages:
1. the final lithium manganese nickel oxide is stoichiometric LiMn 1.5Ni 0.5O 4. The lithium metal oxide has an average particle size of about 15 to 20 μm. The average pore diameter is about 100-200 nm.
2. The lithium manganese nickel oxide may be coated with a conductive layer and a protective layer to improve its cycle stability in the full cell.
3. The formulation of the high voltage electrolyte with better performance is obtained by screening, which contains a combination of a carbonated solvent and several additives, including carbonate, borate, sulfite or phosphate.
4. Batteries made with lithium manganese nickel oxide positive electrodes and high voltage electrolyte formulations can be charged to 5V (vs Li). The initial specific capacitance of the positive electrode material at C/5 is greater than about 120 mAh/g. After 500 charge-discharge cycles under C/2, the capacity retention rate exceeds 80 percent and even can reach 100 percent.
Therefore, the method, the anode material and the electrolyte formula have great application value and development prospect.
Other aspects and advantages of the invention will be apparent to those skilled in the art from a reading of the following description.
Drawings
The above and other objects and features of the present invention will become apparent from the following description of the invention, taken in conjunction with the accompanying drawings, in which:
FIG. 1: preparation of LiMn according to embodiments of the invention 1.5Ni 0.5O 4The process flow of (1).
FIG. 2: capacity retention when LMNO prepared at different pH values (left panel) and ammonia concentrations (right panel) in a CSTR as a cathode material according to an embodiment of the present invention.
FIG. 3: according to the embodiments of the present invention, the capacity retention ratio when LMNO is calcined at different temperatures as a positive electrode material.
FIG. 4: comparison of specific capacitance of different carbonized solvent systems during 300 cycles according to an embodiment of the present invention.
FIG. 5: comparison of the carbonization solvent, nitrile solvent, and fluorinated solvent according to embodiments of the present invention: coulombic efficiency (left panel) and capacity retention (right panel).
FIG. 6: according to an embodiment of the invention, HOMO and LUMO of the different additives obtained by simulation.
FIG. 7: comparison of carbonization solvent systems containing different single additives according to embodiments of the present invention: coulombic efficiency (left panel) and capacity retention (right panel).
FIG. 8: comparison of carbonization solvent systems containing different dual additives according to embodiments of the present invention: coulombic efficiency (left panel) and capacity retention (right panel).
FIG. 9: LMNO-graphite full cells using different electrolyte systems, specific capacitance at 0.1C, according to embodiments of the present invention.
FIG. 10: SEM images of LMNO precursor (left panel) and LMNO (right panel) obtained according to example 1 of the present invention.
FIG. 11: LiMn according to example 3 of the invention 1.5Ni 0.5O 4Charge and discharge curves of the half-cell at 0.1C, 0.2C, 1C.
FIG. 12: LiMn according to example 3 of the invention 1.5Ni 0.5O 4Capacity retention of the half cell during 500 cycles.
FIG. 13: root of herbaceous plantLiMn according to the invention from example 4 1.5Ni 0.5O 4-Li 2TiO 3Performance of the full cell at 1C charge rate and 1C discharge rate: charge and discharge curves (left panel); capacity retention (right panel).
FIG. 14: LiMn according to invention example 5 1.5Ni 0.5O 4Performance of graphite full cells at 1C charge rate and 1C discharge rate.
FIG. 15: 3% lithium polyacrylate (LiPAA) coated LiMn according to example 6 of the invention 1.5Ni 0.5O 4Performance of graphite full cells at 1C charge rate and 1C discharge rate.
Detailed description of the preferred embodiments
The scope of the present invention is not limited to any particular embodiment described herein. The following examples are provided for illustration only.
1. Preparation method of lithium manganese nickel oxide
1.1 preparation of LMNO precursor in CSTR System
The lithium manganese nickel oxide is prepared using a CSTR and then subjected to a calcination process. The CSTR is widely applied to the preparation of industrial cathode materials. CSTRs have the advantages of good homogeneity (not only uniform material composition, but also uniform particle distribution), controllable particle size, and compatibility with industrial processes.
Preparation of Mn precursor from manganese sulfate, nickel sulfate, sodium carbonate and ammonium hydroxide 1.5Ni 0.5(CO 3) 2The raw materials of (1). FIG. 1 shows a schematic diagram of a water-jacketed (water-plugged) CSTR system that may be used with the present invention. 1M sodium carbonate and 0.72M ammonium hydroxide were dissolved in deionized water in an alkali vessel and an ammonia vessel, respectively. Nickel sulfate and manganese sulfate were dissolved in deionized water in a salt container to prepare a 0.85M transition metal solution (TM solution) in which the Mn/Ni atomic ratio was fixed at 3/1. The three feed tanks described above (base, ammonia and salt vessels) were connected to peristaltic pumps. During the preparation, the solutions in the salt and base containers are allowed to stand at about 1.5Lh -1Is pumped into the CSTR system while the solution in the ammonia vessel is maintained at about 0.14Lh -1Is pumped into the CSTR system. In thatThe reaction temperature is controlled during the reaction process. After 4 hours of experimental run, at about 3.34Lh -1The product, i.e. the precursor, is collected. The collected samples can also be washed several times with deionized water to remove residual sodium and sulfate ion species, then filtered and dried in a vacuum oven at 90 ℃ overnight.
The inventors investigated particle nucleation and growth during co-precipitation. During the first 1 hour of the experiment, the precursor particles had no defined shape. Some spherical agglomerates of different sizes then start to form. Samples taken at 3 hours of the experiment showed that the particles continued to grow into spheres. The surface of the finally collected particles (t ═ 6 hours) was smoother and denser. These spherical particles are secondary particles composed of nano-primary particles having the same chemical composition and nano-sized pores.
The inventors have discovered that several important factors need to be addressed in the preparation of lithium manganese nickel oxide using a CSTR system, two of the main factors that can affect the secondary particle size including reaction temperature and agitation speed. The secondary particle size decreases as the reaction temperature decreases and the stirring speed decreases. In one embodiment, the stirring speed may be controlled in the range of about 200 and 1000 rpm. The optimum average secondary particle size was found to be about 15-20 μm with an average pore diameter of 100-200 nm. The pH and ammonia concentration are also important influencing factors, as they can influence the distribution of Mn and Ni ions formed in the precursor. LMNO prepared at pH 7.75 and 3M ammonia was found to have better capacity retention (figure 2).
1.2 calcination of LMNO precursor
In an exemplary embodiment, the LMNO precursor is calcined with a lithium salt (e.g., Li) in a muffle or rotary furnace 2CO 3) To obtain the lithium manganese nickel oxide material. The inventors have found that the calcination temperature is the most important factor in this process. The calcination temperature should be controlled within a window that enables a balance between high specific capacitance and good retention to be obtained (fig. 3). The calcination time, another important factor affecting the process, should exceed the lower limit of the time during which good retention can be obtained.
1.3 modification of lithium manganese Nickel oxide Material as Positive electrode Material for lithium ion batteries
For example, a salt of the dopant may be added to the reactor along with other TM solutions to dope the anode material. First principle simulations (e.g. by Material studio CASSTEP) can be performed to evaluate different doping materials such as MgO, Al 2O 3、Fe 2O 3The effect of (1). The doping modification of the positive electrode material can be carried out using methods known to those skilled in the art.
Surface modification, e.g. coating of metal oxides (e.g. Al) on positive electrode materials 2O 3、TiO 2) LiPAA, or carbon, can reduce side reactions between the electrode and the electrolyte during charge and discharge, thereby protecting the positive electrode material at high voltage. After calcination of the precursor material, coating is performed by mixing the obtained LMNO with a material source for coating and heating again in a furnace.
2. High-voltage electrolyte system formula
2.1 solvent systems
In order to screen for better solvent systems, the present invention compares base electrolytes with different solvents, as shown in table 1 below. The Li-rich electrolyte was purchased from a supplier (Capchem). Base 0, base 1 and base 2 contain the solvents EC DMC 1:1v/v, EC EMC 3:7v/v and EC DMC 1:2v/v, respectively, and do not contain any additives. A button-type full cell was prepared using the NEI-LNMO positive electrode, Celgard 2325 separator, and BTR long-cycle graphite for evaluation of baseline electrolyte performance. The 1C long cycle capacitance results are shown in fig. 4. As is evident from fig. 4, the base 2 electrolyte has the best circulation capacity.
Table 1: composition of different solvent systems
Numbering Composition of
#1 Lithium-rich electrolyte
#2 (Foundation 0) EC DMC 1:1v/v, no additive, 1mol/L LiPF 6
#3 (Foundation 1) EC EMC 3:7v/v, no additive, 1mol/L LiPF 6
#4 (Foundation 2) EC DMC 1:2v/v, no additive, 1mol/L LiPF 6
EC is ethylene carbonate; EMC methyl ethyl carbonate; DMC, dimethyl carbonate; LiPF 6Lithium hexafluorophosphate
Further, base 2 was compared with a nitrile solvent and a fluorinated solvent, respectively, in a full cell. The cycling results at 0.1C are shown in figure 5. As can be seen from fig. 5, basis 2 (where EC: DMC ═ 1:2v/v) is still the best, with higher coulombic efficiency and capacity retention.
2.2 screening of Single additives
Based on the selected solvent system (base 2), 37 single additives as shown in table 2 below were screened. Simulations were performed (by Material Studio Dmol3) and the HOMO and LUMO of the energy of each additive were calculated and the results are plotted in fig. 6.
Table 2: the types of additives screened in the present invention
Figure BDA0002141597090000101
Using a cathode comprising NEI-LNMO, Celgard 2325 separator and BTR long-circulating graphiteThe button full cell of (1) was evaluated for various additives. The cycle was performed at C/10. The coulombic efficiency and the capacity retention were compared for 100 cycles. Some of the results are shown in fig. 7. The inventors have found that the following additives have better properties: FEC, TMSP, TMSPi, LiFOB, LiBOB, PS, 13PCS, AMSL, DN-6-O, VC, etc. LiPF contained in electrolyte 6During the recycling process, traces of HF can be decomposed and formed. This trace amount of HF may react with the electrode, resulting in performance degradation. It was found that LiBOB and LiFOB can suppress the generation of HF during charge/discharge. Based on the HOMO/LUMO calculation, TMSP and TMSPi may decompose earlier than the solvent, thus forming a stable positive electrolyte interface (CEI) on the positive electrode. The PS may be reduced to form a Solid Electrolyte Interface (SEI) on the anode. The HOMO/LUMO ratio of 13PCS is lower than PS, and thus the electrolyte performance can be further improved. VC can help form SEI on the graphite surface to protect the negative electrode. VC also suppresses the formation of resistive LiF, thereby reducing the interface resistance.
2.3 combination of additives
The combination of multiple additives is likely to be a better way to prepare electrolytes for LMNO/graphite full cells due to the synergistic effect. Based on the single additive selected, certain combinations of the various additives shown in table 3 below were tested at 0.1C using LMNO-graphite full cells. Combinations of additives have shown better performance, including: 1% TMSP + 1% LiFOB; 1% TMSPi + 1% 13 PCS; 1% TMSP + 1% 13 PCS; 1% TMSP + 2% PS; 1% TMSPi + 0.09% VC. Some of the results are shown in fig. 8 and 9.
Table 3: combinations of certain additives tested by the invention
Numbering Additive 1 Additive 2 Numbering Additive 1 Additive 2
1 TMSP LiFOB 8 TMSPi 13PCS
2 TMSP PS 9 TMSPi PS
3 TMPS 13PCS 10 LiFOB PS
4 TMSP AMSL 11 LiFOB 13PCS
5 TMSP LiBOB 12 LiBOB AMSL
6 TMSP DN-6-O 13 AMSL PS
7 TMSPi VC
Throughout the specification and claims, unless the context requires otherwise, the terms "comprise" or "comprises", "comprising" or "comprising" will be understood to imply the inclusion of a stated element, component or feature or group of elements, components or features but not the exclusion of any other element, component or feature or group of elements, components or features.
Unless defined otherwise, all other technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Unless otherwise stated, the cycling tests of all cells in the following examples were performed at a voltage of 3.5-5.0V.
Example 1: LiMn 1.5Ni 0.5O 4Preparation of
Preparation of precursor Mn using manganese sulfate, nickel sulfate, sodium carbonate and ammonium hydroxide as starting materials 1.5Ni 0.5(CO 3) 2. The preparation was carried out using a water jacketed CSTR system as shown in fig. 1. 1M sodium carbonate and 3.042M ammonium hydroxide were dissolved in deionized water in an alkali vessel and an ammonia vessel, respectively. Nickel sulfate and manganese sulfate were dissolved in deionized water in a salt container to prepare a 1M transition metal solution with a Mn/Ni atomic ratio fixed at 3/1. Three feed tanks were connected to peristaltic pumps. The solution in the salt and base containers is allowed to flow at about 1.5Lh -1Is pumped into a reactor (not shown) while the solution in the ammonia vessel is maintained at about 0.14Lh -1Pumped into the same reactor. During this time, the pH of the reaction mixture was controlled to 7.75 by a pH controller connected to the reactor, the reaction mixture was stirred at 300rpm, and the reaction temperature was controlled at 45 ℃. At 3.34Lh -1The reaction product was collected. After 4 hours of experiment run, the precursor was collected. The collected samples were washed several times with deionized water to remove residual sodium and sulfate ion species, then filtered and dried in a vacuum oven at 110 ℃ overnight.
After drying, the precursor Mn obtained 1.5Ni 0.5(CO 3) 2LiCO at a molar excess of 5% 3And (4) mixing. The mixture was calcined to 450 ℃ at a ramp rate of 2 ℃/min and held for 6 hours, then ramped to 950 ℃ at the same ramp rate and held for 24 hours. SEM images of the precursor and LMNO obtained are shown in fig. 10.
Example 2: LiPAA coated LiMn 1.5Ni 0.5O 4Preparation of
Positive electrode LiMn was prepared as described in example 3 below 1.5Ni 0.5O 4And an electrode. A quantity of polyacrylate (m.w.3000) was dissolved in deionized water. Slowly add 2.5mol L -1Until the pH of the resulting solution is 8. Then adding LiMn 1.5Ni 0.5O 4Added to the LiPAA solution. The mixture was evaporated under constant stirring and dried in a vacuum oven at 100 ℃ for 12h to give a LiPAA coated LiMn of 0.5% -5 wt% 1.5Ni 0.5O 4。
Example 3: LiMn 1.5Ni 0.5O 4Preparation of half-cells
Preparation of LiMn from a mixture of 84% active material, 4% Super-P (conductive carbon black), 4% KS6 (conductive graphite) and 8% PVDF (polyvinylidene fluoride) 1.5Ni 0.5O 4The slurry of (1). The solids content of the slurry was controlled at 38%. The slurry was coated onto an aluminum substrate. After preparation, the electrode was dried in vacuo at 90 ℃ overnight. Cutting LiMn with a cutter 1.5Ni 0.5O 4The geometric area of the electrode is punched to 1.13cm 2。LiMn 1.5Ni 0.5O 4The surface density of the positive electrode is fixed at 5-7mg/cm 2。
Electrochemical coin cells were assembled in a Braun glove box under a high purity argon atmosphere. The electrolyte solution contained DMC and EC in a ratio of 2:1v/v, 1M LiPF 6And 5 vol% FEC. Including LiMn 1.5Ni 0.5O 4A two-electrode cell of working electrode, lithium foil counter electrode and PE separator was used to cycle at charge and discharge rates of 0.1C, 0.2C and 1C. With LiMn 1.5Ni 0.5O 4The charge and discharge curves of the half cell, which is a positive electrode material, are shown in fig. 11. LiMn 1.5Ni 0.5O 4The capacity retention of the half cell is shown in fig. 12. As shown in fig. 12, the capacity retention rate after 500 cycles was close to 100% at a charge/discharge rate of 1C.
Example 4: LiMn 1.5Ni 0.5O 4–Li 2TiO 3Preparation of full cell
Positive electrode LiMn 1.5Ni 0.5O 4The electrode was prepared as in example 3. Preparation of Li with a mixture of 84% active Material, 4% Super-P, 4% KS6 and 8% PVDF 2TiO 3And (3) slurry. The solids content of the slurry was controlled at 38%. The slurry is coated onto a copper substrate. After preparation, the electrode was dried in vacuo at 90 ℃ overnight. Cutting LiMn with a cutter 1.5Ni 0.5O 4Electrode and Li 2TiO 3Is punched to 9cm 2. The N/P ratio (negative/positive ratio) was set to 1.05.
Assembling the electrochemical soft package battery in a Braun glove box under the atmosphere of high-purity argon. The electrolyte solution contained DMC and EC in a ratio of 2:1v/v, and 1M LiPF 6A mixture of (a). Including LiMn 1.5Ni 0.5O 4Positive electrode and Li 2TiO 3A two-electrode cell (16 mAh capacity) of negative electrode and PE separator was used to cycle at a charge rate and discharge rate of 1C. LiMn 1.5Ni 0.5O 4-Li 2TiO 3The performance of the full cell at 1C charge rate and 1C discharge rate is shown in fig. 13. As can be seen from fig. 13, the capacity retention rate after 500 cycles was as high as 100%.
Example 5: LiMn 1.5Ni 0.5O 4Preparation of graphite full cell
Positive electrode LiMn 1.5Ni 0.5O 4The electrode was prepared as in example 3. A graphite slurry was prepared with a mixture of 94% active material, 2% Super-P, 2% CMC (sodium carboxymethylcellulose) and 2% SBR (styrene butadiene rubber). The solids content of the slurry was controlled at 40%. The slurry is coated onto a copper substrate. After preparation, the electrode was dried in vacuo at 90 ℃ overnight. Cutting LiMn with a cutter 1.5Ni 0.5O 4The geometric area of the electrode and graphite is punched to 9cm 2. The N/P ratio was set to 1.4.
Assembling the electrochemical soft package battery in a Braun glove box under the atmosphere of high-purity argon. The electrolyte solution contained DMC and EC in a ratio of 2:1v/v, and 1M LiPF 6A mixture of (a). Including LiMn 1.5Ni 0.5O 4A two-electrode cell (capacity of 80mAh) of positive electrode, graphite negative electrode and PE separator was used to cycle at a charge rate and discharge rate of 1C. LiMn 1.5Ni 0.5O 4The performance of the graphite full cell at 1C charge rate and 1C discharge rate is shown in fig. 14. As shown in fig. 14, the capacity retention rate was as high as 83% after 300 cycles.
Example 6: LiPAA coated LiMn 1.5Ni 0.5O 4Preparation of graphite full cell
Positive electrode LiMn 1.5Ni 0.5O 4The electrode was prepared as in example 3. A graphite slurry was prepared with a mixture of 94% active material, 2% Super-P, 2% CMC, and 2% S BR. The solids content of the slurry was controlled at 40%. The slurry is coated onto a copper substrate. After preparation was complete, the electrode was dried in vacuo at 90 ℃ overnight. Cutting LiMn with a cutter 1.5Ni 0.5O 4The geometric area of the electrode and graphite is punched to 9cm 2. The N/P ratio was set to 1.05.
Assembling the electrochemical soft package battery in a Braun glove box under the atmosphere of high-purity argon. The electrolyte solution contained DMC and EC in a ratio of 2:1v/v, and 1.5m LiPF 6A mixture of (a). Including LiPAA coated LiMn 1.5Ni 0.5O 4A two-electrode cell (capacity of 80mAh) of positive electrode, graphite negative electrode and PE separator was used to cycle at a charge rate and discharge rate of 1C. FIG. 15 shows 3% LiPAA coated LiMn 1.5Ni 0.5O 4Performance of graphite full cells at 1C charge rate and 1C discharge rate. According to fig. 15, the capacity retention after 300 cycles was as high as 85%.
The embodiments described above are presented to facilitate one of ordinary skill in the art to understand and practice the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, it is intended that the present invention not be limited to the particular embodiments disclosed herein, but that modifications and variations can be made by those skilled in the art in light of the above teachings without departing from the scope of the invention.

Claims (15)

1. A method of making lithium manganese nickel oxide comprising the steps of:
(a) reacting a manganese metal salt and a nickel metal salt in a reactor in a CSTR system to form a precursor;
(b) calcining the precursor and lithium salt together in a furnace to obtain lithium manganese nickel oxide; and optionally also (c) a second set of one or more of,
(c) modifying the obtained lithium manganese nickel oxide.
2. The method of claim 1, wherein,
performing said step (a) in the presence of a precipitating agent selected from one or more of sodium carbonate, sodium hydroxide, ammonium bicarbonate and ammonium oxalate;
optionally, the manganese metal salt is selected from one or more of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride;
optionally, the nickel metal salt is selected from one or more of nickel sulfate, nickel nitrate, nickel acetate and nickel chloride;
optionally, the lithium salt is selected from one or more of lithium hydroxide, lithium carbonate, lithium acetate, lithium chloride and lithium nitrate; and
optionally, the modification is by means of doping or cladding or a combination thereof.
3. The method of claim 2, wherein the precipitant comprises one or more of ammonium hydroxide, ammonium bicarbonate, and ammonium oxalate, and the concentration of ammonia in the reactor is about 0.1-4.0M.
4. The process of claim 1 or 3, wherein step (a) further comprises controlling the reaction temperature to about 30-60 ℃.
5. The method of claim 4, wherein step (a) further comprises controlling the pH in the reactor to about 6-8.
6. The method as claimed in claim 1, wherein the calcining in step (b) comprises heating the precursor together with the lithium salt to about 400-600 ℃ for about 4-8 hours, and then further heating to about 800-1150 ℃ for about 12-36 hours.
7. The method of any one of claims 2-6, wherein the precipitating agent comprises sodium carbonate and hydrogenOxidizing ammonium; optionally, the precursor is Mn 1.5Ni 0.5(CO 3) 2And the lithium manganese nickel oxide is LiMn 1.5Ni 0.5O 4。
8. The method of claim 7, wherein the precursor is spherical particles having a particle size distribution of about 5-50 μm and an average particle size of about 10-20 μm; and optionally, the precursor comprises pores having a pore size of about 10-500 nm.
9. The method of claim 7, wherein the lithium manganese nickel oxide is spherical particles having a particle size distribution of about 5-50 μm and an average particle size of about 10-20 μm; and optionally, the lithium manganese nickel oxide contains pores having a pore diameter of about 10-500 nm.
10. The method of claim 2, wherein,
the step (a) includes: (a1) dissolving manganese sulfate and nickel sulfate in water to form a transition metal solution; (a2) respectively dissolving sodium carbonate and ammonium hydroxide in water to form an alkali solution and an ammonia solution; (a3) reacting the transition metal solution, the alkali solution and the ammonia solution in a reactor to form a precursor Mn 1.5Ni 0.5(CO 3) 2(ii) a And (a4) collecting the precursor;
optionally, the step (b) comprises: calcining the precursor obtained in step (a) together with lithium carbonate or lithium hydroxide in a furnace to obtain a lithium manganese nickel oxide LiMn 1.5Ni 0.5O 4Wherein the calcination profile comprises heating the precursor and lithium salt to about 400-600 ℃ for about 4-8 hours, and then to about 800-1150 ℃ for about 12-36 hours; and
optionally, the step (c) comprises: (c1) with elements selected from Al 2O 3、TiO 2Any one or more of LiPAA and 0.5-5% wt of carbon coats the lithium manganese nickel oxide.
11. A lithium manganese nickel oxide material produced by the method of any one of claims 1-10.
12. A positive electrode material for a high voltage lithium ion battery, the positive electrode material comprising the lithium manganese nickel oxide material of claim 11.
13. A high voltage lithium ion battery comprising the positive electrode material of claim 12.
14. The high voltage lithium ion battery of claim 13 further comprising an electrolyte system comprising a solvent and an additive, wherein the solvent includes, but is not limited to, EC, EMC, DMC, nitrile, fluorinated solvent and any combination thereof; and optionally, the additives include, but are not limited to, FEC, TMSP, TMSPi, LiFOB, LiBOB, PS, 13PCS, AMSL, DN-6-O, VC, and any combination thereof.
15. The high voltage lithium ion battery of claim 14, wherein the solvent comprises 1:2v/v EC: DMC; and optionally, the additive is selected from: TMSP +13 PCS; TMSP + LiFOB; TMSP + PS; TMSPi + VC; and TMSPi +13 PCS.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113185543A (en) * 2021-04-26 2021-07-30 苏州华赢新能源材料科技有限公司 Silicon-oxygen-based compound, electrolyte prepared from silicon-oxygen-based compound and lithium ion battery

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005194106A (en) * 2003-12-12 2005-07-21 Nippon Chem Ind Co Ltd Method of manufacturing lithium manganese nickel multiple oxide
CN103107325A (en) * 2011-11-11 2013-05-15 Skc株式会社 Cathode active material for a lithium secondary battery containing phosphate fluoride and preparation method thereof
CN106025254A (en) * 2016-06-24 2016-10-12 常熟理工学院 Surface coating modification method of LiNi0.5Mn1.5O4 cathode material
CN103456946B (en) * 2013-09-12 2017-07-11 湖南立方新能源科技有限责任公司 Anode material for lithium-ion batteries
CN107565124A (en) * 2017-08-22 2018-01-09 山东精工电子科技有限公司 A kind of precursor of nickel-cobalt-lithium-manganese-oxide and preparation method thereof
CN107799747A (en) * 2017-10-20 2018-03-13 江苏容汇通用锂业股份有限公司 A kind of preparation method of ion doping rich lithium manganese base solid solution/network combined positive electrode of carbonaceous conductive
CN108025926A (en) * 2015-09-17 2018-05-11 巴登-符腾堡州太阳能和氢能公益基金研究中心 Lithium-nickel-manganese base transition metal oxide particle, its production and its purposes as electrode material

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005194106A (en) * 2003-12-12 2005-07-21 Nippon Chem Ind Co Ltd Method of manufacturing lithium manganese nickel multiple oxide
CN103107325A (en) * 2011-11-11 2013-05-15 Skc株式会社 Cathode active material for a lithium secondary battery containing phosphate fluoride and preparation method thereof
CN103456946B (en) * 2013-09-12 2017-07-11 湖南立方新能源科技有限责任公司 Anode material for lithium-ion batteries
CN108025926A (en) * 2015-09-17 2018-05-11 巴登-符腾堡州太阳能和氢能公益基金研究中心 Lithium-nickel-manganese base transition metal oxide particle, its production and its purposes as electrode material
CN106025254A (en) * 2016-06-24 2016-10-12 常熟理工学院 Surface coating modification method of LiNi0.5Mn1.5O4 cathode material
CN107565124A (en) * 2017-08-22 2018-01-09 山东精工电子科技有限公司 A kind of precursor of nickel-cobalt-lithium-manganese-oxide and preparation method thereof
CN107799747A (en) * 2017-10-20 2018-03-13 江苏容汇通用锂业股份有限公司 A kind of preparation method of ion doping rich lithium manganese base solid solution/network combined positive electrode of carbonaceous conductive

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113185543A (en) * 2021-04-26 2021-07-30 苏州华赢新能源材料科技有限公司 Silicon-oxygen-based compound, electrolyte prepared from silicon-oxygen-based compound and lithium ion battery

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