CN114314689B - Lithium battery anode material and preparation method thereof - Google Patents
Lithium battery anode material and preparation method thereof Download PDFInfo
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- CN114314689B CN114314689B CN202111501290.4A CN202111501290A CN114314689B CN 114314689 B CN114314689 B CN 114314689B CN 202111501290 A CN202111501290 A CN 202111501290A CN 114314689 B CN114314689 B CN 114314689B
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Abstract
The application discloses a lithium battery anode material and a preparation method thereof, and the preparation method comprises the following steps: preparing soluble nickel salt, cobalt salt and manganese/aluminum salt into mixed salt solution, performing coprecipitation reaction with a complexing agent and a precipitator, and controlling reaction conditions to obtain spherical hydroxide precursors with obvious porous surface limit, which are formed by nano sheet stacking; uniformly mixing the prepared hydroxide precursor with a fusing inhibitor, pre-sintering the oxide precursor, mixing the pre-sintered oxide precursor with lithium salt, and sintering to obtain the nano-sized single-crystal anode material; preparing conductive polymer glue solution, and compounding the conductive polymer glue solution with a positive electrode material to form a film and sintering the film to obtain a three-dimensional self-supporting lithium battery positive electrode composite material; according to the application, the ternary material is nano-crystallized by adopting an innovative sintering method, and is also manufactured into the self-supporting electrode with the three-dimensional structure by a simple and effective means, so that the agglomeration of nano particles in the post-processing process can be prevented, and the self-supporting electrode has excellent comprehensive performance.
Description
Technical Field
The application relates to the technical field of lithium batteries, in particular to a lithium battery anode material and a preparation method thereof.
Background
In order to cope with the increasingly outstanding contradiction between fuel supply and demand and environmental pollution, the world major automobile production state is speeded up for deployment, new energy automobiles are developed as national strategy, and development and industrialization of propulsion technology are speeded up. As a member of the new energy automobile industry chain, lithium batteries have also proposed corresponding carbon emission targets and carbon emission reduction implementation routes. The lithium battery anode material is a core part of a power battery of a new energy automobile, and directly determines the power density, the energy density and the cost of the battery. Compared with materials such as lithium iron phosphate and lithium manganate, the high-nickel ternary anode material with the layered structure has high energy density and power density, and is becoming the main choice of the power battery of the new energy automobile.
The restriction point for the continuous improvement of the performance and the safety of the current layered structure ternary positive electrode material is the microstructure and the morphology of the current layered structure ternary positive electrode material. At present, manufacturers at home and abroad use traditional technology to prepare ternary material microcosmic morphology which is secondary spheroid polycrystalline particles formed by agglomeration and sintering of nanoscale primary particles, and the special microstructure causes the following problems: smaller non-crystal boundary gaps are usually arranged among primary particles in the polycrystalline secondary spherical particles, so that lithium ions cannot pass through; the skeleton has poor firmness and low mechanical strength, primary particles are easy to generate interfacial pulverization and even cracking, so that the secondary sphere structure collapses, more side reactions with electrolyte are initiated, the potential safety hazard of increasing gas production and the electrochemical performance decay are caused; the structure and morphology of the secondary spheres lead to coating difficulties, particularly the inability of the internal particles to coat, and once the secondary sphere structure collapses due to mechanical or electrochemical causes, severe side reactions can occur between the exposed internal particles and the electrolyte, resulting in performance degradation.
Disclosure of Invention
The application aims to provide a lithium battery anode material and a preparation method thereof, which solve the problem of defects of secondary spheroidic polycrystalline particles formed by agglomeration and sintering of nanoscale primary particles in the ternary anode material in the prior art.
The application is realized in such a way that the lithium battery anode material is nano-sized single-crystal nickel cobalt lithium manganate or nickel cobalt lithium aluminate anode material, and is a self-supporting electrode anode composite material with a three-dimensional structure,
the molecular formula of the positive electrode material is Li 1+n Ni x Co y M z O 2 Wherein M is Mn or Al, x+y+z= 1,0.6 is less than or equal to x and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.4, and n is more than or equal to 0.1 and less than or equal to 0.5.
The preparation method of the lithium battery anode material comprises the following steps:
step one: weighing soluble nickel salt, cobalt salt and manganese salt or nickel salt, cobalt salt and aluminum salt in proportion and deionized water to prepare a mixed salt solution A with a certain concentration; mixing a complexing agent and a precipitator to obtain a premix B; the solution obtained by filtering the mixed salt solution A and the premixed solution B is sequentially added into a reaction kettle which is communicated with a protective atmosphere for reaction, and the reaction conditions are controlled to generate precursor crystal nucleus and grow up gradually; aging for a certain time, filtering, washing and drying the reaction slurry after the granularity reaches a preset value to obtain a spherical nickel cobalt manganese or nickel cobalt aluminum hydroxide precursor with obvious porous surface limit formed by nano sheet stacking; the molecular formula of the precursor is Ni x Co y M z (OH) 2 Wherein M is Mn or Al, x+y+z= 1,0.6 is less than or equal to x and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 0.4, and z is more than or equal to 0 and less than or equal to 0.4.
Step two: uniformly mixing the prepared hydroxide precursor with a flux, obtaining a mixture A, presintering for 2-10 h at 200-700 ℃ in an oxygen-containing atmosphere, and annealing to obtain a presintered nickel-cobalt-manganese or nickel-cobalt-aluminum oxide precursor;
step three: and uniformly mixing the prepared presintered nickel cobalt manganese or nickel cobalt aluminum oxide precursor with lithium salt to obtain a mixture B, sintering the mixture B at 500-1000 ℃ for 1-20 h in an oxygen-containing atmosphere, and annealing to obtain the nano-sized single-crystalline nickel cobalt lithium manganate or nickel cobalt lithium aluminate anode material.
The application further adopts the technical scheme that: nickel salt, cobalt salt and manganese salt or nickel salt, cobalt salt and aluminum salt solution, wherein the molar ratio of nickel ions to cobalt ions is 1:1-5:1; the molar ratio of nickel ions to aluminum ions is 1.5:1-15:1; specifically, the concentration of nickel ions is 0.90mol/L to 1.50mol/L; the concentration of cobalt ions is 0.30mol/L to 0.90mol/L; the concentration of manganese ions is 0.30mol/L to 0.90mol/L; the concentration of aluminum ions is 0.10mol/L to 0.60mol/L.
The complexing agent is ammonia water solution, and further, the molar concentration of the complexing agent is 1.0 mol/L-12.0 mol/L;
the precipitant is sodium hydroxide solution, and further, the molar concentration of the precipitant is 3.0 mol/L-12.0 mol/L.
The protective atmosphere in the first step is nitrogen or argon, and the temperature of the reaction slurry in the reaction condition is 35-65 ℃; the pH value is 8-13; the rotating speed of the reaction kettle is 500-1000 r/min.
The application further adopts the technical scheme that: the aging time is 2-48 hours; the drying step is specifically as follows: drying at 60-150 deg.c for 8-24 hr; in particular, the drying apparatus should be provided with evacuation and protection of the breather.
The application further adopts the technical scheme that: the nano-flake is piled to form spherical nickel cobalt manganese or nickel cobalt aluminum hydroxide precursor with obvious porous surface limit, the median particle diameter is 1.0-5.0 mu m, and the specific surface area is 5.0-20.0 m 2 Per gram, the tap density is 1.0-2.5 g/cm 3 。
The morphology of the precursor has a certain influence on the subsequent nano-sized monocrystal, and the loose porous structure is beneficial to adsorbing the flux; the particle size of the precursor is controlled to be smaller in micron order, which is favorable for forming single crystals and is not easy to generate agglomeration.
The application further adopts the technical scheme that: uniformly mixing the prepared spherical nickel cobalt manganese or nickel cobalt aluminum hydroxide precursor with a flux to obtain a mixture A, pre-sintering the mixture A for 2-10 hours at 200-700 ℃ in an oxygen (or air) atmosphere, and annealing to obtain a presintered nickel cobalt manganese or nickel cobalt aluminum oxide precursor;
the application further adopts the technical scheme that: the said solvent is selected from CaO and CaF 2 、CaCO 3 、H 2 BO 3 、B 2 O 3 At least one of (a) and (b); the purpose of presintering the fusing inhibitor and the precursor hydroxide is to uniformly coat and firmly attach the fusing inhibitor and the precursor hydroxide on the surfaces of the spherical particles of the precursor and in gaps among the primary particles; the action mechanism of the fusing inhibitor is that lithium oxide generated by lithium salt decomposition under the high temperature condition and the fusing inhibitor generate unsaturated composite oxide, the reaction interface is blocked, and primary particles are prevented from fusing; the doping mass proportion of the fusing inhibitor is 500 ppm-4000 ppm.
The median particle diameter of the nano-sized single-crystal nickel cobalt lithium manganate or nickel cobalt lithium aluminate anode material is less than 1 mu m; after the sintering step, the method further comprises a step of crushing, and further, the median particle diameter of the positive electrode material is 100-900 nm.
The application further adopts the technical scheme that: the lithium source is at least one selected from lithium hydroxide, lithium oxide, lithium fluoride, lithium carbonate, lithium nitrate and lithium acetate, and the molar ratio of the lithium source to the presintered nickel cobalt manganese or nickel cobalt aluminum oxide precursor is 0.95:1-1.5:1.
The application further adopts the technical scheme that: the mixture is subjected to sintering annealing treatment at 500-1000 ℃, wherein the sintering atmosphere of the materials according to different element proportions can be pure oxygen (volume concentration is more than 80%), air, mixed gas of oxygen and air with different volume concentrations; wherein, in the step of sintering the mixture at 500-1000 ℃, the sintering time is 1-20 h; specifically, the sintering equipment is a tunnel kiln or a rotary kiln with ventilation, exhaust, heat dissipation and precise temperature control.
The application further adopts the technical scheme that: the preparation method also comprises the following steps: dissolving a sulfur source and polyacrylonitrile in an organic solvent for crosslinking and combining reaction to obtain a glue solution precursor with a certain concentration, uniformly mixing the glue solution precursor with the prepared nano-sized single-crystal nickel cobalt lithium manganate or nickel cobalt lithium aluminate positive electrode material, spin-coating on a flat plate, vacuum drying at 60-120 ℃ for 2-24 h to obtain a precursor film on the flat plate, annealing the precursor film in an atmosphere environment at 300-500 ℃ for 5-24 h, cooling to 150-250 ℃, annealing in an air environment for 2-8 h, and cooling to obtain the three-dimensional self-supporting lithium battery positive electrode composite material.
The application further adopts the technical scheme that: the sulfur source is at least one of sulfur, sodium thiosulfate or sodium sulfide; the organic solvent is at least one of dimethyl sulfoxide, DMF, acetone or DMAC;
dissolving polyacrylonitrile in an organic solution, heating and stirring for 10-100 min to form a solution with the mass fraction of 1-12 wt%; adding a sulfur source into the solution, and stirring for 10-100 min, wherein the mass ratio of the sulfur source to the polyacrylonitrile is 0.5-5; placing the dispersed solution into an oil bath at 150-300 ℃ for heating reaction for 5-24 hours to form a homogeneous solution, and filtering out unreacted sulfur sources from the homogeneous solution cooled to room temperature to obtain a glue solution precursor; the glue solution can be changed into conductive polymer through drying and heating annealing treatment, and plays roles of conducting and bonding in the subsequent three-dimensional self-supporting composite material.
The application further adopts the technical scheme that: the spin coating process requires a planar carrier; the precursor films with different quality and area density can be obtained by changing the concentration and thickness of the spin-coated mixed glue solution, and rolling treatment with different compaction can be performed subsequently.
The three-dimensional self-supporting lithium battery anode composite material is film-shaped as a whole and is microscopically in a three-dimensional porous dendrite crosslinking shape.
The lithium battery anode material is prepared by adopting the preparation method of the lithium battery anode material.
The lithium ion electrode adopts the positive electrode material prepared by the preparation method of the lithium battery positive electrode material.
A lithium ion battery is provided, and the positive electrode material of the lithium ion battery is prepared by adopting the preparation method of the positive electrode material of the lithium ion battery.
The application has the beneficial effects that:
(1) The method effectively combines the characteristics of single crystal, nanometer and the like, and the prepared material has the advantages of high mechanical strength, good processability, strong chemical stability, good conductivity, excellent electrochemical performance, long cycle life, large energy density, higher capacity, and improved power performance, high-rate rapid charge and discharge performance and low-temperature electrochemical performance;
(2) The application relates to a method for preparing nano-sized single-crystal nickel cobalt lithium manganate or nickel cobalt lithium aluminate positive electrode material, which adopts spherical nickel cobalt manganese or nickel cobalt aluminum hydroxide precursors with obvious loose porous surface limit formed by nano-sheet stacking, and the loose porous structure is favorable for adsorbing a fusing agent; the particle size of the precursor is controlled to be smaller in micron order, which is favorable for forming single crystals and is not easy to agglomerate nano particles in the synthesis process;
(3) In the preparation method, the pre-sintering is carried out by adopting the fusing inhibitor and the precursor hydroxide, and the fusing inhibitor can be uniformly coated and firmly attached on the surfaces of the precursor spherical particles and in gaps among the primary particles; the action mechanism of the flux is that lithium oxide generated by decomposition of lithium salt and the flux generate unsaturated composite oxide under the high temperature condition, the reaction interface is blocked, primary particles are prevented from fusing, single crystal formation is facilitated, and meanwhile, agglomeration of nano particles is not easy in the synthesis process;
(4) According to the application, an innovative sintering method is adopted to perform nano single crystallization on ternary materials, a sulfur source and polyacrylonitrile are dissolved in an organic solvent to perform a crosslinking combination reaction to obtain a glue solution precursor, the glue solution precursor and the prepared nano-sized single-crystal nickel cobalt lithium manganate or nickel cobalt lithium aluminate positive electrode material are uniformly mixed and then spin-coated on a flat plate, and after drying and sintering, a self-supporting electrode with a three-dimensional structure is prepared, so that the problem of agglomeration of nano single crystal particles in the subsequent processing process can be prevented;
(5) The three-dimensional structure of the application increases the active material load per unit foot area, shortens the lithium ion diffusion path of the internal particle nano structure, increases the contact area of the electrode/electrolyte membrane, and improves the utilization rate of the anode material, thereby improving the capacity and the charge-discharge rate of the battery and obtaining high energy density and high power density; meanwhile, the self-supporting electrode can discard the conductive agent and the binder, so that the manufacturing cost is greatly reduced, and meanwhile, the non-conductive binder is removed, so that the utilization rate of the active material and the dynamic rate of electrode reaction can be improved, and the electrochemical performance is improved;
(6) The three-dimensional self-supporting electrode thin film has immeasurable application prospect in the field of all-solid-state lithium batteries, and can possibly become the development direction of new generation new energy batteries.
Drawings
FIG. 1 is a SEM image at 10000 times of magnification of a hydroxide precursor obtained in example 1;
FIG. 2 is a SEM image at 10000 times of magnification of a pre-sintered oxide precursor obtained in example 1;
FIG. 3 is an SEM image at 10000 times of magnification of the nano-sized single crystal positive electrode material obtained in example 1;
FIG. 4 is an SEM image at a magnification of 3300 times of the three-dimensional self-supporting positive electrode composite material obtained in example 1;
FIG. 5 is a physical view of the three-dimensional self-supporting positive electrode composite material obtained in example 1;
FIG. 6 is a graph showing the initial charge and discharge at room temperature current density of 0.1C and 3.0V to 4.3V for a 2032 button cell made of the three-dimensional self-supporting positive electrode composite material obtained in example 1 and the conventional positive electrode material of comparative example 1, respectively;
FIG. 7 is a graph of the initial charge and discharge at ambient temperature current density of 0.1C and 3.0V to 4.3V for a 2032 button cell made of the three-dimensional self-supporting positive electrode composite material obtained in example 2;
FIG. 8 is a graph of the initial charge and discharge at room temperature current density of 0.1C and voltage of 3.0V to 4.3V for a 2032 button cell made of the three-dimensional self-supporting positive electrode composite material obtained in example 3;
FIG. 9 is a graph showing that 2032 button cell fabricated by the three-dimensional self-supporting positive electrode composite material obtained in example 1 and the conventional positive electrode material of comparative example 1, respectively, circulates for 97 weeks at a current density of 1C and a voltage of 3.0V to 4.3V;
FIG. 10 is a graph showing that 2032 button cell fabricated from the three-dimensional self-supporting positive electrode composite material obtained in example 2 circulates for 97 weeks at a current density of 1C and a voltage of 3.0V to 4.3V;
fig. 11 is a graph showing that 2032 button cell fabricated with the three-dimensional self-supporting positive electrode composite material obtained in example 3 circulates for 97 weeks at a current density of 1C and a voltage of 3.0V to 4.3V.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1-5" is disclosed, the described range should be interpreted to include the ranges of "1-4", "1-3", "1-2 and 4-5", "1-3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
In order that the application may be readily understood, a more complete description of the application will be rendered by reference to the appended drawings. Preferred embodiments of the present application are shown in the drawings. This application may, 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.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The positive electrode material of this example was prepared as follows:
(1) Respectively dissolving nickel sulfate, cobalt sulfate and manganese sulfate with deionized water, uniformly mixing the three solutions to obtain a nickel-cobalt-manganese mixed salt solution, wherein the molar ratio of nickel ions to cobalt ions to manganese ions in the nickel-cobalt-manganese mixed salt solution is 0.80:0.1:0.1, preparing 8.0mol/L ammonia water solution and 12.0mol/L sodium hydroxide solution, and mixing the solution to obtain a premix;
(2) Adding the two filtered solutions into a reaction kettle with the rotating speed of 500r/min in parallel, regulating the flow rate of the solution of the premixed solution to control the pH value in the reaction kettle to be 12, introducing nitrogen for protection, controlling the temperature of the reaction kettle to be 50 ℃, stopping the injection of the premixed solution until the injection of the nickel-cobalt-manganese mixed salt solution is finished, aging for 12 hours, performing solid-liquid separation on the obtained slurry, washing the obtained solid material, drying the obtained solid material in an oven for 12 hours at 120 ℃, and obtaining the spherical nickel-cobalt-manganese hydroxide with obvious porous surface limit of loose holes formed by stacking nano flakes with the median particle size of 3.0 mu mA precursor, wherein the molecular formula of the precursor is Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 ；
(3) Placing the prepared spherical nickel cobalt manganese hydroxide precursor and a flux-resistant CaO into a high-efficiency mixer, and mixing at a high speed of 1000r/min for 30min to obtain a mixture A, wherein the doping mole ratio of Ca element is 500ppm, and the oxygen flow is 3Nm 3 In the atmosphere of/h, the mixture A is put into a sagger and placed into a resistance furnace, the temperature is raised from room temperature to 600 ℃ at the heating rate of 2 ℃/min for presintering for 5h, and the presintering nickel cobalt manganese oxide precursor is obtained after annealing;
(4) Weighing lithium hydroxide and presintered nickel cobalt manganese oxide precursor according to a molar ratio of 1.05:1, placing the lithium hydroxide and presintered nickel cobalt manganese oxide precursor into a high-efficiency mixer, and mixing at a high speed of 1000r/min for 30min to obtain a mixture B; placing the mixture B in a sagger, placing in a resistance furnace, sintering for 15h at a temperature rising rate of 2 ℃/min from room temperature to 850 ℃, and introducing flow rate of 5Nm into the resistance furnace during sintering 3 And (3) naturally cooling the oxygen per hour to room temperature, taking out, crushing, dissociating and grading to obtain the nano-sized single-crystal nickel cobalt lithium manganate positive electrode material with the median particle diameter of 650nm, wherein the molecular formula of the positive electrode material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 ；
(5) Weighing sulfur powder and polyacrylonitrile powder with the mass ratio of 0.5, dissolving the polyacrylonitrile powder in dimethyl sulfoxide, heating to 60 ℃, and stirring for 60min to form a solution with the mass fraction of 5 wt%; adding sulfur powder into the solution, stirring for 30min to disperse uniformly; placing the solution after uniform dispersion into an oil bath at 150 ℃ for heating reaction for 8 hours, and performing crosslinking and bonding reaction to form a homogeneous colloid solution; filtering out unreacted sulfur powder from the homogeneous colloid solution cooled to room temperature to obtain a colloid solution precursor;
(6) The mass ratio is 100: and 95, uniformly mixing the glue solution precursor and the prepared nano-sized single-crystalline nickel cobalt lithium manganate positive electrode material, spin-coating the mixture on a flat plate to form a colloid film with the thickness of 170 mu m, vacuum drying at 120 ℃ for 12 hours to obtain a precursor film, annealing the precursor film in an argon environment at 350 ℃ for 5 hours, cooling to 200 ℃, annealing in an air environment for 5 hours, and cooling to obtain the three-dimensional self-supporting lithium battery positive electrode composite material.
Example 2
The positive electrode material of this example was prepared as follows:
(1) Respectively dissolving nickel sulfate, cobalt sulfate and aluminum chloride with deionized water, uniformly mixing the three solutions to obtain a nickel-cobalt-aluminum mixed salt solution, wherein the molar ratio of nickel ions to cobalt ions to manganese ions in the nickel-cobalt-aluminum mixed salt solution is 0.88:0.09:0.03, preparing an ammonia water solution with the concentration of 6.0mol/L and a sodium hydroxide solution with the concentration of 11.0mol/L, and mixing the solution to obtain a premix;
(2) Adding the two filtered solutions into a reaction kettle with the rotating speed of 800r/min in parallel, regulating the flow rate of the solution of the premixed solution to control the pH value in the reaction kettle to be 13, introducing nitrogen for protection, controlling the temperature of the reaction kettle to be 60 ℃, stopping the injection of the premixed solution until the injection of the nickel-cobalt-aluminum mixed salt solution is finished, aging for 10 hours, performing solid-liquid separation on the obtained slurry, washing the obtained solid material, and drying the obtained solid material in an oven at 120 ℃ for 18 hours to obtain a spherical nickel-cobalt-aluminum hydroxide precursor with obvious porous surface limit, wherein the molecular formula of the precursor is Ni, and the nano-platelets with the median particle size of 2.5 mu m are stacked to form a porous particle size 0.88 Co 0.09 Al 0.03 (OH) 2 ；
(3) The prepared spherical nickel cobalt aluminum hydroxide precursor and the flux-resistant CaF 2 Mixing with high-efficiency mixer at 1000r/min for 30min to obtain mixture A with F element doping mole ratio of 1000ppm at oxygen flow rate of 3Nm 3 In the atmosphere of/h, the mixture A is arranged in a sagger and placed in a resistance furnace, the temperature is raised from room temperature to 500 ℃ at the heating rate of 2 ℃/min for presintering for 5h, and the presintering nickel cobalt aluminum oxide precursor is obtained after annealing;
(4) Weighing lithium hydroxide and presintered nickel cobalt aluminum oxide precursor according to a molar ratio of 1.08:1, placing the lithium hydroxide and presintered nickel cobalt aluminum oxide precursor into a high-efficiency mixer, and mixing at a high speed of 1000r/min for 30min to obtain a mixture B; placing the mixture B in a sagger, placing in a resistance furnace, heating from room temperature to 800 ℃ at a heating rate of 2 ℃/min, sintering for 18h, and sinteringIn the process, the flow rate of the gas introduced into the resistance furnace is 5Nm 3 And (3) naturally cooling the oxygen per hour to room temperature, taking out, crushing, dissociating and grading to obtain the nano-sized single-crystalline nickel cobalt lithium aluminate positive electrode material with the median particle diameter of 550nm, wherein the molecular formula of the positive electrode material is LiNi 0.88 Co 0.09 Mn 0.03 O 2 。
(5) Weighing sodium sulfide and polyacrylonitrile powder with the mass ratio of 0.5, dissolving the polyacrylonitrile powder in dimethyl sulfoxide, heating to 60 ℃, and stirring for 60min to form a solution with the mass fraction of 4 wt%; adding sodium sulfide into the solution, stirring for 30min to disperse uniformly; placing the solution after uniform dispersion into an oil bath at 150 ℃ for heating reaction for 8 hours, and performing crosslinking and bonding reaction to form a homogeneous colloid solution; filtering out unreacted sulfur powder from the homogeneous colloid solution cooled to room temperature to obtain a colloid solution precursor;
(6) The mass ratio is 125: and 95, uniformly mixing the glue solution precursor and the prepared nano-sized single-crystalline nickel cobalt lithium manganate positive electrode material, spin-coating the mixture on a flat plate to form a colloid film with the thickness of 170 mu m, vacuum drying at 120 ℃ for 12 hours to obtain a precursor film, annealing the precursor film at 360 ℃ in an argon environment for 8 hours, cooling to 250 ℃, annealing in an air environment for 3 hours, and cooling to obtain the three-dimensional self-supporting lithium battery positive electrode composite material.
Example 3
The positive electrode material of this example was prepared as follows:
(1) Respectively dissolving nickel sulfate, cobalt sulfate and manganese sulfate with deionized water, uniformly mixing the three solutions to obtain a nickel-cobalt-manganese mixed salt solution, wherein the molar ratio of nickel ions to cobalt ions to manganese ions in the nickel-cobalt-manganese mixed salt solution is 0.75:0.10:0.15, preparing an ammonia water solution with the concentration of 6.0mol/L and a sodium hydroxide solution with the concentration of 10.0mol/L, and mixing the solution to obtain a premix;
(2) Adding the two filtered solutions into a reaction kettle with the rotating speed of 1000r/min in parallel, regulating the flow rate of the premixed solution to control the pH value in the reaction kettle to be 13, introducing nitrogen for protection, controlling the temperature of the reaction kettle to be 50 ℃, stopping the injection of the premixed solution after the injection of the nickel-cobalt-manganese mixed salt solution is finished, and ageingAfter 10h of chemical treatment, carrying out solid-liquid separation on the obtained slurry, washing the obtained solid material, and drying the solid material in an oven at 120 ℃ for 12h to obtain a spherical nickel-cobalt-manganese hydroxide precursor with obvious porous surface limit, wherein the spherical nickel-cobalt-manganese hydroxide precursor is formed by stacking nano sheets with the median particle size of 3.5 mu m, and the molecular formula of the precursor is Ni 0.75 Co 0.1 Mn 0.15 (OH) 2 ；
(3) The prepared spherical nickel cobalt manganese hydroxide precursor and the fusing inhibitor B 2 O 3 Mixing with a high-efficiency mixer at 1000r/min for 30min to obtain a mixture A with B element doping mole ratio of 1500ppm at oxygen flow rate of 3Nm 3 In the atmosphere of/h, the mixture A is put into a sagger and placed into a resistance furnace, the temperature is raised from room temperature to 600 ℃ at the heating rate of 2 ℃/min for presintering for 6h, and the presintering nickel cobalt manganese oxide precursor is obtained after annealing;
(4) Weighing lithium hydroxide and presintered nickel cobalt manganese oxide precursor according to a molar ratio of 1.03:1, placing the lithium hydroxide and presintered nickel cobalt manganese oxide precursor into a high-efficiency mixer, and mixing at a high speed of 1000r/min for 30min to obtain a mixture B; placing the mixture B in a sagger, placing in a resistance furnace, sintering for 18h at a temperature rising rate of 2 ℃/min from room temperature to 900 ℃, and introducing flow rate of 2Nm into the resistance furnace during sintering 3 And (3) naturally cooling the oxygen per hour to room temperature, taking out, crushing, dissociating and grading to obtain the nano-sized single-crystalline nickel cobalt lithium manganate positive electrode material with the median particle diameter of 750nm, wherein the molecular formula of the positive electrode material is LiNi 0.75 Co 0.1 Mn 0.15 O 2 ；
(5) Weighing sodium thiosulfate and polyacrylonitrile powder with the mass ratio of 0.5, dissolving the polyacrylonitrile powder in dimethyl sulfoxide, heating to 60 ℃, and stirring for 60min to form a solution with the mass fraction of 8 wt%; adding sodium thiosulfate into the solution, and stirring for 30min to uniformly disperse the sodium thiosulfate; placing the solution after uniform dispersion into an oil bath at 250 ℃ for heating reaction for 6 hours, and performing crosslinking and bonding reaction to form a homogeneous colloid solution; filtering out unreacted sulfur powder from the homogeneous colloid solution cooled to room temperature to obtain a colloid solution precursor;
(6) The mass ratio is 62.5: and 95, uniformly mixing the glue solution precursor and the prepared nano-sized single-crystalline nickel cobalt lithium manganate positive electrode material, spin-coating the mixture on a flat plate to form a colloid film with the thickness of 170 mu m, vacuum drying at 120 ℃ for 12 hours to obtain a precursor film, annealing the precursor film in an argon environment at 450 ℃ for 5 hours, cooling to 200 ℃, annealing in an air environment for 5 hours, and cooling to obtain the three-dimensional self-supporting lithium battery positive electrode composite material.
Comparative example 1
As a control, a commercially available conventional NCM811 positive electrode material was used.
And (3) testing:
1) The precursor and the positive electrode material prepared in example 1 were subjected to scanning electron microscopy, and the results are shown in fig. 1 to 4. As can be seen from fig. 1, the hydroxide precursor prepared in example 1 is spherical with a well-defined loose porous surface formed by nano-platelet stacking; as can be seen from fig. 2, the overall morphology of the pre-fired oxide precursor prepared in example 1 is still in the form of nano-platelet stacked spheres, and the nano-platelet gaps become larger and more pronounced than those of the hydroxide precursor; as can be seen from fig. 3, the positive electrode material prepared in example 1 exhibits nano-sized single crystalline shape; as can be seen from fig. 4, the composite material prepared in example 1 is three-dimensional porous dendrite crosslinked, and as can be seen from the physical diagram of example 1 in fig. 5, the composite material is entirely in a flexible film shape.
3) The three-dimensional self-supporting positive electrode composite material prepared in example 1 and a commercially available conventional NCM811 positive electrode material were subjected to electrochemical performance tests, and the results are shown in FIGS. 6 to 11 and Table 1. The conventional NCM811 positive electrode material had the same element molar ratio as the positive electrode material prepared in example 1. FIG. 6 is a graph of the initial charge and discharge at room temperature current density of 0.2C and 3.0V to 4.3V for a 2032 button cell made of the three-dimensional self-supporting positive electrode composite material obtained in example 1 and a conventional NCM811 positive electrode material, respectively; FIG. 7 is a graph of the initial charge and discharge at ambient temperature current density of 0.1C and 3.0V to 4.3V for a 2032 button cell made of the three-dimensional self-supporting positive electrode composite material obtained in example 2; fig. 8 is a graph of the initial charge and discharge at normal temperature current density of 0.1C and voltage of 3.0V to 4.3V for a 2032 button cell made of the three-dimensional self-supporting positive electrode composite material obtained in example 3. Fig. 9 is a graph showing that 2032 button cells each prepared from the three-dimensional self-supporting positive electrode composite material obtained in example 1 and the conventional NCM811 positive electrode material were cycled at a current density of 1C (1C from week 3, with 0.2C charge/discharge for one week and 0.5C charge/discharge for one week for the first 2 weeks) for 97 weeks at a voltage of 3.0V to 4.3V. FIG. 10 is a graph showing that 2032 button cell fabricated from the three-dimensional self-supporting positive electrode composite material obtained in example 2 circulates for 97 weeks at a current density of 1C and a voltage of 3.0V to 4.3V; fig. 11 is a graph showing that 2032 button cell fabricated with the three-dimensional self-supporting positive electrode composite material obtained in example 3 circulates for 97 weeks at a current density of 1C and a voltage of 3.0V to 4.3V.
The electrochemical performance test method comprises the following steps: taking a conventional NCM811 positive electrode material of comparative example 1, uniformly mixing the positive electrode material with acetylene black and polyvinylidene fluoride (PVDF) in a proper amount of N-methylpyrrolidone (NMP) solution according to a mass ratio of 95:2.5:2.5, and then coating the mixture on an aluminum foil to prepare a positive electrode plate; cutting the three-dimensional self-supporting positive electrode composite material prepared in each embodiment into the same size as a conventional NCM811 positive electrode plate; the negative electrode sheet adopts a lithium sheet, and is added with a diaphragm and electrolyte, wherein the electrolyte is LiPF of 1mol/L 6 The solution is a mixed solution of EC, DEC and DMC, the volume ratio of EC, DEC and DMC is 1:1:1, and the button cell with model 2032 is assembled in a glove box filled with argon. The test is carried out on a LAND battery tester, the test voltage range is 3.0V-4.3V, and the test temperature is 25 ℃ at room temperature.
TABLE 1 electrochemical Performance test results
As can be seen from fig. 6 to 11 and table 1, the three-dimensional self-supporting positive electrode composite material prepared in example 1 has high capacity of first charge and discharge, high efficiency, and capacity retention rate of more than 80% after 1C cycle for 90 weeks. The three-dimensional self-supporting positive electrode composite material prepared in the embodiment 1 is superior to the conventional NCM811 positive electrode material in initial charge and discharge efficiency, rate discharge performance and cycle performance.
Compared with the secondary spheroid polycrystalline particle material in the prior art recorded in the background art, the three-dimensional self-supporting lithium battery anode composite material prepared by the application effectively combines the characteristics of single crystal, nanometer and the like, and has the following advantages in the comprehensive view: (1) The monocrystalline material has the characteristic of smooth particle surface, and is favorable for full contact and cladding treatment with the conductive material; (2) The surface tension of the monocrystal material is high, and solvent molecules are difficult to enter the crystal lattice of the material in the lithium intercalation process, so that the co-intercalation of the solvent molecules can be prevented, and the cycle life of the battery can be prolonged; (3) The monocrystal structure is more beneficial to the transmission of lithium ions in the material; (4) The single crystal material has high mechanical strength, can prevent the material from being broken and crushed in the rolling process of manufacturing the pole piece to cause rapid performance attenuation, and can realize high compaction density, and the high compaction density is beneficial to reducing the internal resistance of the electrode, reducing ohmic polarization and increasing the volume energy density of the battery; (5) The nano-scale particle size shortens the path of ion diffusion, which is beneficial to solid-phase diffusion of lithium ions, thereby reducing the solid-phase diffusion resistance and improving the power performance, the high-rate rapid charge-discharge performance and the low-temperature electrochemical performance; (6) The single crystal material has large specific surface area, high surface energy and large proportion of surface atoms, is favorable for increasing interface reaction active points, promoting the reduction of interface resistance, being favorable for fully carrying out lithium ion deintercalation of reaction and reducing the occurrence of irreversible reaction, and meanwhile, the high porosity of the surface of the nano material also increases lithium intercalation vacancies, so the nano material has higher capacity than the common positive electrode material; (7) The nano-crystallization and the single crystallization are beneficial to further reduction of the grain size, and the reaction resistance of the material in a low-temperature environment is further reduced along with the reduction of primary grains, so that the material has higher cycle stability and higher compaction density; (8) The effective combination of nanocrystallization and monocrystal enables the material to have higher chemical stability and excellent electrical performance, has obvious dynamic advantages compared with ternary materials prepared by the traditional process, obtains the electrode material with high specific capacitance, high power, high multiplying power, high energy density and long cycle life, and meets the actual use requirements.
Furthermore, agglomeration of nanoparticles during synthesis and use is a major problem in nanocrystallization of materials. Compared with the prior patent, the application not only adopts an innovative sintering method to single-crystallize ternary material nanometer, but also prepares the ternary material nanometer into the self-supporting electrode with a three-dimensional structure by a simple and effective means. The three-dimensional self-supporting electrode has the following advantages: (1) The three-dimensional structure shortens the lithium ion diffusion path by combining the internal particle nano structure while increasing the active material load of unit foot area, and simultaneously improves the capacity and the charge and discharge rate of the battery; (2) Compared with the traditional powder material, the three-dimensional self-supporting positive electrode can eliminate the conductive agent and the adhesive, greatly reduce the manufacturing cost, and simultaneously remove the non-conductive adhesive to improve the utilization rate of the active material and the dynamic rate of electrode reaction and improve the electrochemical performance; (3) The three-dimensional structure can increase the contact area of the electrode/electrolyte membrane to effectively improve the utilization rate of the anode material, and can effectively improve the charge and discharge rate of the battery while improving the specific capacity of the unit area, thereby simultaneously obtaining high energy density and high power density; (4) The three-dimensional self-supporting electrode thin film has immeasurable application prospect in the field of all-solid-state lithium batteries, and can possibly become the development direction of new generation new energy batteries.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (9)
1. A preparation method of a lithium battery anode material is characterized by comprising the following steps: the method comprises the following steps:
step one: weighing soluble nickel salt, cobalt salt and M salt in proportion and preparing a mixed salt solution A with a certain concentration with deionized water; mixing a complexing agent and a precipitator to obtain a premix B; m is Mn or Al; the solution obtained by filtering the mixed salt solution A and the premixed solution B respectively is sequentially added into a reaction kettle which is communicated with protective atmosphere for reaction, and the reaction conditions are controlled to generate precursor crystal nucleus and grow up gradually; aging for a certain time, filtering, washing and drying the reaction slurry after the granularity reaches a preset value to obtain a spherical nickel cobalt manganese or nickel cobalt aluminum hydroxide precursor with obvious porous surface limit formed by nano sheet stacking;
step two: uniformly mixing the prepared hydroxide precursor with a flux, obtaining a mixture A, presintering for 2-10 h at 200-700 ℃ in an oxygen-containing atmosphere, and annealing to obtain a presintered nickel-cobalt-manganese or nickel-cobalt-aluminum oxide precursor;
step three: uniformly mixing the prepared presintered nickel cobalt manganese or nickel cobalt aluminum oxide precursor with lithium salt to obtain a mixture B, sintering the mixture B at 500-1000 ℃ for 1-20 h in an oxygen-containing atmosphere, and annealing to obtain nano-sized single-crystalline nickel cobalt lithium manganate or nickel cobalt lithium aluminate anode material;
the said solvent is selected from CaO, caF 2 、CaCO 3 、H 2 BO 3 、B 2 O 3 At least one of (a) and (b); the doping mass proportion of the fusing inhibitor is 500 ppm-4000 ppm.
2. The method for preparing the lithium battery anode material according to claim 1, wherein the method comprises the following steps: the shape of the hydroxide precursor is a sphere with obvious porous surface limit formed by nano sheet stacking, the median particle diameter is 1.0-5.0 mu m, and the specific surface area is 5.0-20.0m 2 Per gram, the tap density is 1.0-2.5 g/cm 3 。
3. The method for preparing a positive electrode material for lithium battery according to claim 1, wherein the molecular formula of the positive electrode material is Li 1+n Ni x Co y M z O 2 Wherein M is Mn or Al, x+y+z= 1,0.6 is less than or equal to x and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.4, and n is more than or equal to 0.1 and less than or equal to 0.5.
4. The method for preparing a lithium battery positive electrode material according to claim 1, wherein the median particle size of the nano-sized single-crystal nickel cobalt lithium manganate or nickel cobalt lithium aluminate positive electrode material is less than 1 μm, and the nano-sized single-crystal nickel cobalt lithium manganate or nickel cobalt lithium aluminate positive electrode material is 100 nm-990 nm.
5. The method for preparing a lithium battery positive electrode material according to claim 1, wherein the lithium salt is at least one selected from the group consisting of lithium hydroxide, lithium oxide, lithium fluoride, lithium carbonate, lithium nitrate and lithium acetate, and the molar ratio of the lithium source to the presintered nickel cobalt manganese or nickel cobalt aluminum oxide precursor is 0.95:1 to 1.5:1.
6. The method for preparing the lithium battery anode material according to claim 1, wherein the method comprises the following steps: the preparation method further comprises the following steps: dissolving a sulfur source and polyacrylonitrile in an organic solvent for crosslinking and combining reaction to obtain a glue solution precursor with a certain concentration, uniformly mixing the glue solution precursor with the prepared nano-sized single-crystal nickel cobalt lithium manganate or nickel cobalt lithium aluminate positive electrode material, spin-coating on a flat plate, vacuum drying at 60-120 ℃ for 2-24 h to obtain a precursor film on the flat plate, annealing the precursor film in an atmosphere environment at 300-500 ℃ for 5-24 h, cooling to 150-250 ℃, annealing in an air environment for 2-8 h, and cooling to obtain the three-dimensional self-supporting lithium battery positive electrode composite material.
7. The method for preparing a lithium battery anode material according to claim 6, wherein in the crosslinking and combining reaction, polyacrylonitrile is dissolved in an organic solution, and the heating and stirring time is 10-100 min, so that a solution with a mass fraction of 1-12 wt% is formed; adding a sulfur source into the solution, and stirring for 10-100 min, wherein the mass ratio of the sulfur source to the polyacrylonitrile is 0.5-5; placing the dispersed solution into an oil bath at 150-300 ℃ for heating reaction for 5-24 h to form a homogeneous solution; filtering the above homogeneous solution cooled to room temperature to obtain unreacted sulfur source, and obtaining the glue solution precursor.
8. The method for preparing a lithium battery positive electrode material according to claim 6, wherein the sulfur source is at least one of sulfur, sodium thiosulfate or sodium sulfide; the organic solvent is at least one of dimethyl sulfoxide, DMF, acetone or DMAC.
9. A lithium battery cathode material, characterized in that the lithium battery cathode material is prepared by the method according to any one of claims 1-8.
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