CN111509214A - High-nickel layered composite material and lithium ion battery anode material prepared from same - Google Patents
High-nickel layered composite material and lithium ion battery anode material prepared from same Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-nickel layered composite material, and further discloses a preparation method of the high-nickel layered composite material, a lithium ion battery anode material prepared from the composite material, a lithium ion battery anode and a lithium ion battery. According to the preparation method of the high-nickel layered composite material, the prepared precursor containing Ni and Mn, the selected metal oxide and the lithium source material are subjected to high-temperature roasting, a certain amount of metal ions are uniformly doped in the material, and the control of the crystal structure of the anode material is realized by combining the design of the doping element types, the doping element content and the sintering process; and further through the coating treatment of the selected component materials, the oxygen release amount of the material in the circulation process is effectively reduced, and the coating layer and the body material are effectively fused in the coating process, so that the material is ensured not to fall off in the circulation process, and the structural stability of the material under the conditions of high temperature and high pressure is enhanced.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-nickel layered composite material, and further discloses a preparation method of the high-nickel layered composite material, a lithium ion battery anode material prepared from the composite material, a lithium ion battery anode and a lithium ion battery.
Background
In recent years, with the continuous development of new energy industry, nickel-cobalt-manganese (NCM) ternary positive electrode materials are more and more widely used in power batteries and consumer lithium batteries due to the advantages of high capacity, high cycle stability, moderate cost and the like. With the increasing demand of new energy passenger cars on endurance mileage, the demand on energy density of power batteries is also continuously promoted, and the application of high nickel materials in the power batteries is promoted.
Although the high-nickel ternary material has great advantages in energy density compared with other anode materials, L iNiO is inherited2The disadvantages of the method, such as easy deviation of the metering ratio in the synthesis process, easy conversion to the spinel structure in the circulation process and the like, lead to poor circulation performance, safety performance and storage performance of the high-nickel ternary material, and prevent the ternary material from being applied to the field of power batteries on a large scale. In addition, in the past years, the price of metallic cobalt has risen with the rapid increase of the yield of the nickel-cobalt-manganese ternary material, and from 21 ten thousand yuan/ton in 2015 to 68 ten thousand yuan/ton in 2017, the rising of the cobalt price also causes the rising of the price of the nickel-cobalt-manganese ternary material to be obvious. In order to reduce the cost, the nickel-cobalt-manganese ternary material is developed towards low cobalt content and even no cobalt content. At present, scientists in various countries have carried out many research and development works on nickel-manganese layered cathode materials, but most of nickel-manganese layered cathode materials with low cobalt content have the problems of poor rate capability, poor cycle performance and the like, and particularly, when the nickel content is high, the performance defect is more obvious. For example, the Chinese patent CN108199027A carries out niobium doping modification on the cobalt-free nickel-based positive electrode material, but the single element doping has very limited improvement on the multiplying power and the cycle performance of the cobalt-free nickel-based positive electrode material, and the requirement of a power battery is difficult to meet.
Moreover, most high-nickel ternary materials have poor stability, and oxygen is easily released in the circulation process, so that potential safety hazards are brought to the use of the battery. For example, chinese patent CN106654237A discloses a core-shell material doped with ceria, lanthana, zirconia, etc. to reduce oxygen release of the material, and simultaneously, the strong bonding ability of elements in the shell material, such as cerium, lanthanum, zirconium, aluminum, etc., to oxygen atoms is utilized to inhibit oxygen release, thereby enhancing the structural stability of the material under high temperature and high pressure conditions. However, the element such as cerium, lanthanum, zirconium, etc. doped in the core material is already in the crystal lattice of the nickel cobalt lithium manganate during the heat treatment, and does not exist in the form of oxide, so that the core material does not play a role in inhibiting the release of oxygen. Meanwhile, with the gradual increase of the cycle times, the core and shell materials are easy to separate, so that the anode material is peeled off, and the cycle performance of the anode material is seriously influenced.
In view of the above, there is a need for providing a modified low-cobalt/cobalt-free nickel-manganese layered cathode material, which can better improve the lithium ion conductivity of the material, and enable the cathode material to have high discharge capacity and coulombic efficiency, good cycle capacity retention rate and rate characteristics, meet the requirements of high energy density of power batteries, and is suitable for industrial mass production without affecting the discharge platform.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a high nickel layered composite material, which has a stable structure and good electrochemical performance;
the second technical problem to be solved by the invention is to provide a high nickel layered lithium ion battery anode material prepared from the high nickel layered composite material, so as to solve the problems of poor electrochemical performance and stability of the low cobalt/cobalt-free high nickel anode material in the prior art;
the third technical problem to be solved by the invention is to provide the lithium ion battery anode and the lithium ion battery prepared from the high-nickel layered lithium ion battery anode material.
In order to solve the technical problem, the high nickel layered composite material comprises a nickel cobalt lithium manganate body material containing doping elements and a coating layer formed by a composite material containing Ce and Zr elements; wherein the content of the first and second substances,
the bulk material has a structure as L i1+aNi1-b-c-dMnbMcM’dO2The general formula is shown in the specification, wherein M is selected from at least one of Co, B, Ca, Al, Mg, Sc or Zr, and M' is selected from at least one of Cr, W, Ti, Nb, Ta, Mo, V or Ce;
the a, the b, the c and the d satisfy the following quantity relationship: a is more than or equal to 0.05 and less than 0.1, b is more than or equal to 0 and less than 0.3, c is more than or equal to 0 and less than 0.1, d is more than or equal to 0 and less than 0.1, and c + d is more than or equal to 0 and less than or equal to 0.15;
preferably, a, b, c and d satisfy the following numerical relationship: a is more than or equal to 0 and less than 0.1, b is more than 0 and less than 0.3, c is more than or equal to 0 and less than 0.1, d is more than or equal to 0 and less than 0.1, and c + d is more than or equal to 0 and less than or equal to 0.15; or a is more than or equal to 0 and less than 0.1, b is more than or equal to 0 and less than 0.2, c is more than or equal to 0 and less than 0.1, d is more than or equal to 0 and less than 0.1, and c + d is more than or equal to 0 and less than or equal to 0.15; or-0.05, b 0-0.1, c 0-0.1, d 0-0.1, c + d 0-0.15;
the composite material forming the coating layer has, for example, CeeZrfN1-e-fThe general formula is shown in the specification, wherein N is at least one element selected from Sr, Mg, Ag, Sn, Ba, Ca, Pr, Tb or Y;
the e and the f satisfy the following quantity relation: 0< e <1, 0< f <1, 0< e + f ≦ 1.
Specifically, the molar ratio p of the coating layer to the bulk material is more than 0 and less than or equal to 0.05.
In the powder X-ray diffraction measurement of CuK α rays, the half-peak width of a diffraction peak with the diffraction angle 2 theta of 18.7 +/-1 degrees is not less than 0.08 and not more than 0.12 or not less than 0.14 and not more than 0.17, the diffraction peak with the diffraction angle 2 theta of 65 +/-1 degrees is split, the two diffraction peak positions are respectively 64.5 +/-0.5 degrees (α) and 64.9 +/-0.5 degrees (β), and the difference value of the 2 theta angle of the two diffraction peaks is not less than 0.38 (β - α) and not more than 0.47.
The invention also discloses a method for preparing the high-nickel laminated composite material, which comprises the following steps:
(1) according to the stoichiometric ratio of the selected materials, synthesizing a Ni source material and a Mn source material to obtain a required high-nickel precursor;
(2) compounding the high nickel precursor, the lithium source material and the oxide of the selected M element and/or the element in M' according to the stoichiometric ratio of the selected material, and roasting to obtain the required body material;
(3) and according to the stoichiometric ratio of the selected material, taking a compound of the selected element to coat the body material, and calcining to obtain the required high-nickel layered composite material.
Specifically, in the step (1), the synthesis method of the high nickel precursor includes a coprecipitation method and a ball milling method.
Specifically, the method for preparing the high-nickel precursor by a coprecipitation method comprises the following specific steps:
(a) preparing a metal ion solution, namely dissolving soluble salt containing a selected metal element in deionized water to prepare the metal ion solution with the total metal ion concentration of 1-3 mol/L;
(b) preparing a precipitant solution, namely dissolving alkali used as a precipitant in deionized water, and then adding ammonia water to prepare the precipitant solution with the alkali concentration of 1-3 mol/L and the ammonia water concentration of 0.1-0.5 mol/L;
(c) simultaneously adding the prepared metal ion solution and a precipitator sodium carbonate solution into a reactor, and controlling the volume ratio of the prepared metal ion solution to the precipitator sodium carbonate solution to be 1: 1.1-1.3, and controlling the pH value of the reaction to be 7-9; or simultaneously adding the metal ion solution and the precipitant sodium hydroxide solution into the reactor, wherein the volume ratio of the metal ion solution to the precipitant sodium hydroxide solution is 1: 2.1-2.3, and controlling the pH value of the reaction to be 7-11;
(d) and after the reaction is completed, carrying out suction filtration and washing precipitation to obtain a high-nickel precursor filter cake, wherein the high-nickel precursor is an insoluble mixture formed by insoluble Ni salt and Mn salt.
Specifically, the soluble nickel salt, cobalt salt, manganese salt, aluminum salt and the like of the coprecipitation are one or more selected from nickel chloride, cobalt chloride, manganese chloride, nickel sulfate, cobalt sulfate, manganese sulfate, aluminum sulfate, nickel nitrate, cobalt nitrate, manganese nitrate and aluminum nitrate; wherein the content ratio of metal ions such as nickel salt, cobalt salt, manganese salt, aluminum salt, etcExample corresponds to L i1+aNi1-b-c-dMnbMcM’dO2Stoichiometric ratio in the general formula; the a, the b, the c and the d satisfy the following quantity relationship: -0.05. ltoreq. a<0.1、0<b<0.3、0≤c<0.1、0≤d<0.1，0≤c+d≤0.15。
Specifically, the alkali used as the precipitant can be sodium hydroxide or sodium carbonate, i.e. the alkali solution containing ammonia water is a sodium hydroxide solution containing ammonia water or a sodium carbonate solution containing ammonia water, wherein the concentration of the sodium hydroxide or the sodium carbonate is controlled to be 1.0-3.0 mol/L, and the concentration of the ammonia water is controlled to be 0.1-0.5 mol/L.
Specifically, when the sodium hydroxide solution containing ammonia water is selected for the coprecipitation reaction, the volume ratio of at least one solution of soluble nickel salt, cobalt salt, manganese salt and aluminum salt to the sodium hydroxide solution containing ammonia water is controlled to be 1: 2.1 to 2.3, the reaction pH value is 7 to 11, the temperature is 40 to 60 ℃, and the reaction time is 12 to 24 hours.
When the coprecipitation reaction is carried out by selecting a sodium carbonate solution containing ammonia water, controlling the volume ratio of at least one solution of soluble nickel salt, cobalt salt, manganese salt and aluminum salt to the sodium carbonate solution containing ammonia water to be 1: 1.1 to 1.3, the reaction pH value is 7 to 9, the temperature is 40 to 60 ℃, and the reaction time is 12 to 24 hours.
Specifically, the method for preparing the high-nickel precursor by the ball milling method comprises the following specific steps:
(a) according to the chemical formula L i1+aNi1-b-c-dMnbMcM’dO2Weighing the raw materials according to the selected components and the stoichiometric ratio;
(b) adding liquid into the raw materials, and sufficiently grinding to form slurry with the median particle diameter D50 of less than 0.05 μm;
(c) and drying the ground slurry in a spray drying mode to obtain the required high-nickel precursor.
Specifically, the powder obtained in the spray drying step is controlled to be primary particles with the particle size of less than 0.05 mu m, and the primary particles are agglomerated to form spherical secondary particles with the particle size of 3-20 mu m.
Specifically, in the step (2), the roasting treatment step includes a step of heating to 600 ℃ at a heating rate of 2-5 ℃/min for carrying out first heat-preservation roasting for 5-8h, and a step of heating to 1000 ℃ at a heating rate of 2-5 ℃/min for carrying out second heat-preservation roasting for 10-36 h.
Specifically, in the step (3), the coating treatment step includes wet coating and/or mechano-fusion dry coating.
Specifically, in the step (3), the calcining step includes a step of heating to 700 ℃ at a heating rate of 2-5 ℃/min for heat preservation and calcining for 3-8 h.
Specifically, the preparation method of the high-nickel layered composite material comprises the following steps:
the nickel source material comprises at least one of metallic nickel, nickel protoxide, nickel sesquioxide, nickel hydroxide or nickel carbonate; and preferably nickel protoxide;
the manganese source material comprises at least one of manganese metal, manganese monoxide, manganese dioxide or manganese carbonate; and preferably manganese carbonate;
the lithium source material includes at least one of lithium carbonate, lithium hydroxide, or lithium nitrate.
The invention also discloses a high-nickel layered lithium ion battery cathode material prepared from the high-nickel layered composite material as claimed in claim 1 or 2.
The invention also discloses a lithium ion battery anode prepared from the high-nickel layered lithium ion battery anode material as claimed in claim 9 and a lithium ion battery.
Specifically, the lithium ion battery anode is formed by mixing the high-nickel layered lithium ion battery anode material, conductive carbon and a binder, and coating the obtained mixture on a supporting conductive substrate.
Specifically, the lithium ion battery is formed by placing a cathode, a diaphragm and an electrolyte, which are compatible with electricity, of the anode of the lithium ion battery in a container.
According to the preparation method of the high-nickel layered composite material, the prepared precursor containing Ni and Mn, the selected metal oxide and the lithium source material are subjected to high-temperature roasting, a certain amount of metal ions are uniformly doped in the material, and the control of the crystal structure of the anode material is realized by combining the design of the doping element types, the doping element content and the sintering process; and further through the coating treatment of the selected component materials, the oxygen release amount of the material in the circulation process is effectively reduced, and the coating layer and the body material are effectively fused in the coating process, so that the material is ensured not to fall off in the circulation process, and the structural stability of the material under the conditions of high temperature and high pressure is enhanced.
Compared with the traditional preparation method which adopts a single doping element, the preparation method of the high nickel laminated composite material can obviously improve the rate capability and the cycle performance of the anode material; compared with the method for improving oxygen release by singly adopting doping elements in the prior art, the method disclosed by the invention combines the doping elements with the crystallization control of the material, and can solve the problem of failure when the doping elements are singly used; compared with the problem that the core-shell structure of the material prepared by the traditional method is easy to separate, the coating treatment of the method can solve the problem of falling off of the shell material; compared with the commonly adopted preparation method of multi-step roasting and mixing, the method has the advantages of simple process, easy operation, low cost, environmental protection and suitability for large-scale production; compared with the method which can only improve part of the electrical properties of the anode material, the method can comprehensively improve various electrical properties of the composite anode material, including the first discharge specific capacity and the coulombic efficiency of the material, and simultaneously improve the cycle performance and the rate characteristic of the material.
In the powder X-ray diffraction measurement of CuK α ray, the half-peak width of the diffraction peak with the diffraction angle 2 theta of 18.7 +/-1 degrees is not less than 0.08 and not more than i is not more than 0.12 or not less than 0.14 and not more than 0.17, the diffraction peak with the diffraction angle 2 theta of 65 +/-1 degrees is split, the two diffraction peak positions are respectively 64.5 +/-0.5 degrees (α) and 64.9 +/-0.5 degrees (β), the difference of the 2 theta angles of the two diffraction peaks is not more than 0.38 (β - α) and not more than 0.47.
Drawings
In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific embodiments thereof and the accompanying drawings, in which,
FIG. 1 is an X-ray diffraction pattern of the composite materials prepared in examples 1 and 6;
FIG. 2 is a SEM image of the composite material prepared in example 1;
fig. 3 is a first cycle charge and discharge curve of the composite materials prepared in examples 1 and 6.
Detailed Description
Examples 1 to 15
The preparation of the high nickel layered composite of selected composition was carried out according to the formula as listed in table 1 below.
NiSO is prepared according to the proportion of Ni and Mn in the chemical formula listed in Table 14、MnSO4The solution was mixed and the total concentration of metal cations was controlled to 2.0 mol/L.
Preparation of NaOH and NH3·H2O mixed solution, and the concentration of NaOH is controlled to be 3.0 mol/L3·H2The O concentration was 0.30 mol/L.
And (3) dropwise adding the two solutions into a reaction container together by using a peristaltic pump, and controlling the volume ratio of the sulfate mixed solution to the alkali liquor to be 1: 2.1, controlling the pH value to be about 10, and heating in a water bath at 50 ℃ to react for 24 hours; after the reaction is finished, the mixture is filtered, washed and dried in a vacuum oven at 120 ℃ for 12 hours to obtain the required M (OH)2Precursor (M ═ Ni, Mn).
L iOH and ZrO were weighed in the proportions in the chemical formula shown in Table 12And MoO3And with the preparation of M (OH)2After being uniformly mixed, the mixture is subjected to heat preservation and calcination for 12 hours in an oxygen atmosphere according to the heat treatment temperature control mode in the following table 1, and is cooled to room temperature along with the furnace, so that the required bulk material of the high nickel layered composite material is obtained.
The oxides (e.g., CeO) of the bulk material and selected coating material were weighed according to the ratios in the formulas shown in Table 12、ZrO2) After being coated by a mechanical fusion machine, isAnd (3) carrying out heat preservation calcination for 6h in an oxygen atmosphere according to the heat treatment temperature control mode in the following table 1, and cooling to room temperature along with the furnace to obtain the high nickel layered composite material with the required chemical formula composition.
Comparative examples 1 to 4
The composite materials of selected composition were prepared according to the chemical formula shown in Table 1 below, and the specific preparation method was the same as in examples 1-15.
TABLE 1 composition of ingredients for preparing composites for each of the examples and comparative examples
FIG. 1 is an X-ray diffraction pattern of the composites obtained in examples 1 and 6, and it can be seen that the composite has a crystal structure of typical α -NaFeO2The layered structure, particularly the diffraction peak at the diffraction angle 2 theta of 65 +/-1 degrees is split, and the crystallinity of the cathode material is proved to be good, so that the composite material prepared by the scheme is a high-nickel layered material.
Fig. 2 is a scanning electron microscope image of field emission of the high nickel layered composite material prepared in example 1, and it can be seen from the scanning electron microscope image that the primary particles of the positive electrode material in example 1 are very uniform and polyhedral, and the stacking between the particles is very dense, such a structure is favorable for the insertion and extraction of lithium ions, and improves the specific discharge capacity and rate capability thereof, and the primary particles have good consistency and no obvious difference.
Application example
Preparation of the Anode of lithium ion Battery
The materials prepared in examples 1 to 15 and comparative examples 1 to 4 were used as active materials, respectively, with a conductive agent (SP), a binder (PVDF) in accordance with 8: 1: 1, dry-mixing the active substance and the conductive agent for 4 hours, dissolving PVDF in N-methylpyrrolidone, adding the mixed active substance and conductive agent into the mixed solution, uniformly stirring to form anode slurry, coating the anode slurry on an aluminum foil, and drying in a drying oven.
Half cell for preparing material test
Cutting each dried pole piece into a circular sheet with the diameter of 14mm by a punching machine, rolling, drying in a vacuum drying oven to be used as a positive electrode of the battery, wherein the negative electrode of the battery adopts metal lithium, the electrolyte mainly comprises DMC (dimethyl carbonate)/EC (ethylene carbonate)/DEC (diethyl carbonate) solution with the component of 1.0M L iPF6 (the ratio of the DMC to the EC to the diethyl carbonate is 1: 1: 1), and placing the positive electrode, the negative electrode and the electrolyte into a container to form the test battery.
Testing the electrochemical properties of materials
The charge-discharge voltage range of each test battery with the composition is 4.3-3.0V, and the first charge-discharge performance (0.1C, room temperature), the rate charge-discharge performance (1C, room temperature) and the cycle performance (1C, 45 ℃) of the test battery are tested.
Fig. 3 is a first cycle charge and discharge curve of a test battery composed of the composite materials prepared in example 1 and example 6, respectively.
The half-width of the diffraction peak at 18.7 ± 1 ° for 2 θ, the degree of splitting of the diffraction peak in the range of 65 ± 1 ° for 2 θ, and the electrical performance data of the assembled lithium ion battery in the voltage range of 4.3 to 3.0V for each of the above test batteries are shown in table 2 below.
TABLE 2 results of performance tests of materials prepared in each of examples and comparative examples
Therefore, the high nickel layered composite material has good electrical properties, including the improvement of the first discharge specific capacity and the coulombic efficiency of the material, and the cycle performance and the rate characteristic of the material are effectively improved, so that the high nickel layered composite material meets the performance requirements of the lithium ion battery anode material and is suitable for preparing the lithium ion battery.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The high-nickel layered composite material is characterized in that the cathode material comprises a nickel cobalt lithium manganate body material containing doping elements and a coating layer formed by a composite material containing Ce and Zr elements; wherein the content of the first and second substances,
the bulk material has a structure as L i1+aNi1-b-c-dMnbMcM’dO2The general formula is shown in the specification, wherein M is selected from at least one of Co, B, Ca, Al, Mg, Sc or Zr, and M' is selected from at least one of Cr, W, Ti, Nb, Ta, Mo, V or Ce;
the a, the b, the c and the d satisfy the following quantity relationship: a is more than or equal to 0.05 and less than 0.1, b is more than or equal to 0 and less than 0.3, c is more than or equal to 0 and less than 0.1, d is more than or equal to 0 and less than 0.1, and c + d is more than or equal to 0 and less than or equal to 0.15;
the composite material forming the coating layer has, for example, CeeZrfN1-e-fThe general formula is shown in the specification, wherein N is at least one element selected from Sr, Mg, Ag, Sn, Ba, Ca, Pr, Tb or Y;
the e and the f satisfy the following quantity relation: 0< e <1, 0< f <1, 0< e + f ≦ 1.
2. The nickel-rich layered composite material as claimed in claim 1, wherein the molar ratio p of the clad layer to the bulk material in the positive electrode material is 0< p ≦ 0.05.
3. A method for preparing a high nickel layered composite material according to claim 1 or 2, comprising the steps of:
(1) according to the stoichiometric ratio of the selected materials, synthesizing a Ni source material and a Mn source material to obtain a required high-nickel precursor;
(2) compounding the high nickel precursor, the lithium source material and the oxide of the selected M element and/or the element in M' according to the stoichiometric ratio of the selected material, and roasting to obtain the required body material;
(3) and according to the stoichiometric ratio of the selected material, taking a compound of the selected element to coat the body material, and calcining to obtain the required high-nickel layered composite material.
4. The method for preparing a high-nickel layered composite material according to claim 3, wherein in the step (1), the method for synthesizing the high-nickel precursor comprises a coprecipitation method and a ball milling method.
5. The method for preparing a high-nickel layered composite material as claimed in claim 3 or 4, wherein in the step (2), the baking treatment step comprises a step of heating to 300-.
6. The method for producing a high-nickel layered composite material according to any one of claims 3 to 5, wherein in the step (3), the coating treatment step comprises wet coating and/or mechano-fusion dry coating.
7. The method for preparing a high-nickel layered composite material as claimed in any one of claims 3 to 6, wherein in the step (3), the calcination step comprises a step of heating to 300-700 ℃ at a heating rate of 2-5 ℃/min for a holding calcination time of 3-8 h.
8. The method for producing a high-nickel layered composite material according to any one of claims 3 to 7, characterized in that:
the nickel source material comprises at least one of metallic nickel, nickel protoxide, nickel sesquioxide, nickel hydroxide or nickel carbonate;
the manganese source material comprises at least one of manganese metal, manganese monoxide, manganese dioxide or manganese carbonate;
the lithium source material includes at least one of lithium carbonate, lithium hydroxide, or lithium nitrate.
9. The high-nickel layered lithium ion battery cathode material prepared from the high-nickel layered composite material of claim 1 or 2.
10. A lithium ion battery positive electrode and a lithium ion battery prepared from the high-nickel layered lithium ion battery positive electrode material of claim 9.
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