CN113353992B - Pre-lithium material and preparation method thereof - Google Patents
Pre-lithium material and preparation method thereof Download PDFInfo
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- CN113353992B CN113353992B CN202110009043.6A CN202110009043A CN113353992B CN 113353992 B CN113353992 B CN 113353992B CN 202110009043 A CN202110009043 A CN 202110009043A CN 113353992 B CN113353992 B CN 113353992B
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- 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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Abstract
The invention discloses a pre-lithium material and a preparation method thereof, and the chemical formula is LiNi (1‑x) Me x O, wherein x is 10 ‑6 ～10 ‑1 Me is a third metal except Li and Ni, and the pre-lithium material has the characteristics of high purity, high density, high lithium removal capacity and the like; the invention also discloses a preparation method of the pre-lithium material, which selects nickel salt and additive, adopts chemical coprecipitation method, calcination, induction environment, induction chemical substance and combination thereof to induce crack structure, and obtains precursor which is mixed with Li 2 O is mixed, sintered and crushed to obtain the pre-lithium material, and in the method, the crystal structure is changed and the unit cell volume is further enlarged through the induction action of induced environment or induced chemical substances, so that lithium ions can be more fully reacted with NiO, segregation is reduced, the purity and the density of the pre-lithium material are improved, the lithium removal capacity is further improved, and the overall capacitance of the lithium ion battery is promoted.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a pre-lithium material, in particular to a high-purity pre-lithium material and a preparation method thereof.
Background
In order to improve the energy density of lithium ion batteries, silicon anode materials with high specific capacity are becoming the choice of battery enterprises and material suppliers, and become one of the most potential anode materials of next generation lithium ion batteries. However, the large volume expansion of silicon cathodes and the low first coulombic efficiency limit their practical application. The coulomb efficiency of the positive electrode material is far higher than that of the negative electrode, so that the capacity of the positive electrode material cannot be fully exerted, and the waste of the positive electrode material and the reduction of the battery capacity are caused. This is mainly because the surface of the negative electrode material forms a solid electrolyte film, i.e., an SEI film, during the first charge, which consumes lithium ions, which are almost entirely provided by the positive electrode material in the battery. Accordingly, a concept of "lithium replenishment" is proposed to replenish lithium ions consumed for forming an SEI film during the first charge of a battery by "lithium replenishment" on a negative electrode, a positive electrode, or a separator.
The process of lithium supplementing of the positive electrode is to add high-lithium capacity materials into the positive electrode in the process of homogenizing the positive electrode, and to supplement irreversible lithium capacity of the first charge and discharge in the process of charging, the surplus lithium elements are separated from the high-lithium capacity positive electrode materials and are inserted into the negative electrode.
Therefore, a lithium source is found out of the positive electrode material, so that lithium ions of the external lithium source are consumed in the formation of the SEI film, the waste of lithium ions extracted from the positive electrode material can be ensured, and the capacity of the full battery can be improved finally. This process of providing an external lithium source, known as a pre-lithiation material, is known as pre-lithiation.
The research of the pre-lithium material is a research hotspot in the field of lithium batteries in recent years, patent CN 107221650B mentions a lithium supplementing additive and a preparation method thereof, and the lithium supplementing additive is prepared by mixing a plurality of substances in a certain proportion and sintering the substances in multiple steps, but the purity of the active ingredients is lower, and the particles of partial products have small activity so as to be difficult to store, and the passivation treatment is needed to be carried out again, so that the process is complex. Patent CN 107819113A discloses a lithium supplementing additive, and a preparation method and application thereof, wherein the lithium supplementing additive is used as a core-shell structure, a core material is a conductive carbon material, and a shell material is lithium oxide; the lithium oxide is deposited on the surface of the conductive carbon material, nano-layer shells are formed by nano-sized lithium oxide particles, and the preparation process is complex and difficult.
In the prior patent and research, li is synthesized 2 NiO 2 The raw materials and the method mainly select Li 2 O/LiOH and the corresponding nickel salts, and additives are added for solid phase synthesis, but during the actual synthesis it was found that, although Li is synthesized 2 NiO 2 But the impurity components are larger and the content is lower, mainly because NiO is easy to agglomerate and deviate in the synthesis processAnalysis and poor reproducibility.
Therefore, research on a pre-lithium material with high purity and good lithium supplementing performance is an important point of current research.
Disclosure of Invention
The invention mainly aims to overcome the defects of the prior art and provides a pre-lithium material and a preparation method thereof, wherein the pre-lithium material has the characteristics of high purity, high density, high lithium removal capacity and the like.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
according to one aspect of the present invention, there is provided a pre-lithium material having the chemical formula LiNi (1-x) Me x O, wherein x is 10 -6 ～10 -1 Me is a third metal other than Li and Ni.
According to an embodiment of the present invention, the third metal is one or two or more elements selected from Sr, Y, nb, ce, ta, mo and W.
According to one embodiment of the invention, the pre-lithium material contains cracks with a crack width of 0.5nm to 1nm or 1nm to 100nm and a crack length of 0.5nm to 1nm or 1nm to 500nm.
According to one embodiment of the invention, the pre-lithium material has a median particle diameter D50 of 1-20 μm and a specific surface area of 0.1m 2 /g～100m 2 /g; preferably, the pre-lithium material has a median particle diameter D50 of 3-15 μm and a specific surface area of 5m 2 /g～50m 2 /g。
According to another aspect of the present invention, there is provided a method for preparing a pre-lithium material, comprising the main steps of:
s1, selecting nickel salt and an additive, and preparing a precursor 1 by adopting a chemical coprecipitation method;
s2, calcining the precursor 1 in an inert atmosphere to prepare a precursor 2;
s3, carrying out induction operation on the precursor 2 to induce a crack structure, and preparing a precursor 3;
s4 mixing the precursor 3 with Li in equimolar ratio 2 Mixing O, sintering under inert atmosphere, and pulverizing to obtain the pre-lithium material.
According to an embodiment of the invention, the nickel salt comprises one or more of nickel sulfate, nickel nitrate, nickel chloride, nickel bromide.
According to an embodiment of the invention, the additive comprises one or a mixture of two or more compounds containing Sr, Y, nb, ce, ta, mo or W.
According to an embodiment of the present invention, the chemical formula of the precursor 2 is Ni (1-x) Me x The total content of free water and crystal water in the precursor 2 is controlled within 0.001% by mol percent.
According to an embodiment of the present invention, the inert gas is selected from the group consisting of nitrogen, helium, neon, argon and mixtures thereof.
According to one embodiment of the invention, the induction operation is performed by placing in an induction environment, adding an induction chemical, or placing in an induction environment with an induction chemical.
According to an embodiment of the present invention, the induction environment includes a low temperature environment, a high pressure environment, a high temperature quenching environment, and a combination thereof.
According to an embodiment of the present invention, the temperature of the low temperature environment is-100 ℃ to-250 ℃.
According to an embodiment of the invention, the pressure of the high pressure environment is between 10bar and 500bar.
According to one embodiment of the invention, the high temperature quenching environment is heated to 300-800 ℃ and then cooled to room temperature in liquid nitrogen at high speed.
According to an embodiment of the invention, the inducing chemical comprises one or a mixture of two or more compounds of Sr, Y, nb, ce, ta, mo or W.
Compared with the prior art, the invention has the beneficial effects that:
1. the pre-lithium material has the characteristics of high purity, high density, high lithium removal capacity and the like;
2. according to the method for preparing the pre-lithium material, through the induction of the induction environment or the induction of chemical substances, the crystal structure is changed, the unit cell volume is further enlarged, lithium ions are promoted to react with NiO more fully, so that segregation is reduced, the purity and the compactness of the pre-lithium material are improved, the lithium removal capacity is further improved, and the overall capacitance of the lithium ion battery is promoted.
Drawings
FIG. 1 is an SEM image of example 2;
fig. 2 is a first charge capacity map of example 2.
Detailed Description
Exemplary embodiments that embody features and advantages of the present invention are described in detail in the following description. It will be understood that the invention is capable of various modifications in various embodiments, all without departing from the scope of the invention, and that the description is intended to be illustrative in nature and not to be limiting.
In one embodiment of the present invention, a pre-lithium material is provided, the chemical formula of which is LiNi (1-x) Me x O, wherein x is 10 -6 ～10 -1 For example, x is 10 -6 、10 -5 、10 -4 、10 -3 、10 -2 、10 -1 The method comprises the steps of carrying out a first treatment on the surface of the Me is a third metal other than Li and Ni,
in one embodiment of the present invention, the third metal includes one or more of Sr, Y, nb, ce, ta, mo or W.
In one embodiment of the invention, the pre-lithium material contains cracks with a crack width of 0.5nm to 1nm or 1nm to 100nm, for example, a crack width of 0.5nm, 0.8nm, 1nm, 10nm, 100nm; the crack length is 0.5nm to 1nm or 1nm to 500nm, for example, the crack length is 0.5nm, 0.8nm, 1nm, 10nm, 20nm, 200nm, 300nm, 400nm, 500nm.
In one embodiment of the invention, the pre-lithium material has a median particle size D50 of 1 μm to 20 μm, for example, the pre-lithium material has a median particle size D50 of 1 μm, 5 μm, 10 μm, 16 μm, 20 μm; preferably, the pre-lithium material has a median particle size D50 of 3 μm to 15 μm, for example the pre-lithium material has a median particle size D50 of 3 μm, 6 μm, 9 μm, 12 μm, 15 μm
In one embodiment of the invention, the specific surface area of the pre-lithium material is 0.1m 2 /g～100m 2 Per gram, e.g. the specific surface area of the prelithium material is 0.1m 2 /g、10m 2 /g、60m 2 /g、100m 2 /g; preferably, the ratio of the pre-lithium materials is calculatedArea of 5m 2 /g～50m 2 Per g, e.g. a pre-lithium material having a specific surface area of 5m 2 /g、20m 2 /g、30m 2 /g、40m 2 /g、50m 2 /g。
In one embodiment of the present invention, a method for preparing a pre-lithium material is provided, which mainly includes the steps of:
s1, selecting nickel salt and an additive, and preparing a precursor 1 by adopting a chemical coprecipitation method;
s2, calcining the precursor 1 in an inert atmosphere to prepare a precursor 2;
s3, carrying out induction operation on the precursor 2 to induce a crack structure, and preparing a precursor 3;
s4 mixing the precursor 3 with Li in equimolar ratio 2 Mixing O, sintering under inert atmosphere, and pulverizing to obtain the pre-lithium material.
In one embodiment of the present invention, the nickel salt comprises one or more of nickel sulfate, nickel nitrate, nickel chloride, and nickel bromide.
In one embodiment of the invention, the additive comprises a mixture of one or more compounds comprising Sr, Y, nb, ce, ta, mo, W. Wherein the compound of Sr comprises SrCO 3 SrO or SrSO 4 The compound of Y includes Y (NO 3 ) 3 、Y 2 (SO 4 )3、Y 2 O 3 、YBr 3 Or Y 2 (CO 3 ) 3 The Nb compound comprises LiNbO 3 、NbCl 5 Or NbN, ce compounds including CeCl 3 、CeBr 3 Or Ce (Ce) 2 O 3 The compound of Ta comprises TaCl 5 Or TaBr 5 The compound of Mo comprises MoO 3 、Mo(SO 4 ) 3 Or Mo (NO) 3 ) 3 The compound of W is Na 2 WF 8 。
In one embodiment of the present invention, the chemical formula of the precursor 2 is Ni (1-x) Me x The total content of free water and crystal water in the precursor 2 is controlled to be within 0.001%, for example, 0.001%, 0.0008%, 0.0006%, 0.0004%, 0.0002% by mole percentage of O.
In one embodiment of the present invention, the inert gas includes nitrogen, helium, neon, argon and mixtures thereof.
In one embodiment of the invention, the induction is performed in an induction environment, by adding an induction chemical or by adding an induction chemical to the induction environment.
In one embodiment of the present invention, the induction environment includes a low temperature environment, a high pressure environment, a high temperature quenching environment, and combinations thereof.
In one embodiment of the invention, the low temperature environment is at a temperature of-100 ℃ to-250 ℃, such as-100 ℃, -150 ℃, -200 ℃, -250 ℃.
In one embodiment of the invention, the pressure in the high-pressure environment is between 10bar and 500bar, for example 100bar, 200bar, 400bar, 500bar.
In one embodiment of the present invention, the high temperature quenching environment is heated to 300-800 ℃ and then the heated temperature is, for example, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, and then the temperature is reduced to room temperature in liquid nitrogen at high speed.
In one embodiment of the invention, the inducing chemical comprises one or a mixture of more than two compounds of Sr, Y, nb, ce, ta, mo or W. Wherein the compound of Sr comprises SrCO 3 SrO or SrSO 4 The compound of Y includes Y (NO 3 ) 3 、Y 2 (SO 4 ) 3 、Y 2 O 3 、YBr 3 Or Y 2 (CO 3 ) 3 The Nb compound comprises LiNbO 3 、NbCl 5 Or NbN, ce compounds including CeCl 3 、CeBr 3 Or Ce (Ce) 2 O 3 The compound of Ta comprises TaCl 5 Or TaBr 5 The compound of Mo comprises MoO 3 、Mo(SO 4 ) 3 Or Mo (NO) 3 ) 3 The compound of W is Na 2 WF 8 。
The pre-lithium material and the preparation method thereof according to the present invention are further described below with reference to specific examples.
Example 1
10kg of analytically pure nickel sulfate and 0.01g of a fraction were takenAdding the separated and purified cerium sulfate serving as a raw material into a reaction vessel according to the proportion of 5L of sulfate solution, 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water to react, filtering, washing and drying the precipitate to prepare a precursor 1, namely Ni (1-x) Me x (OH) 2 Wherein Me is Ce and x is 10 -5 The method comprises the steps of carrying out a first treatment on the surface of the Sintering under nitrogen atmosphere at pressure of 30bar under 750 deg.C for 60min to obtain precursor 2, denoted Ni (1-x) Me x O, wherein Me is Ce and x is 10 -5 The method comprises the steps of carrying out a first treatment on the surface of the Adding 0.005g of cerium sulfate serving as an induction chemical substance into the precursor 2, uniformly mixing, placing in a liquid nitrogen-196 ℃ environment for 60min, and under the cooperation of the low-temperature environment and the induction chemical substance, inducing the mutation of a crystal structure, and changing the grain size of the crystal structure to prepare the precursor 3; li in equimolar ratio to precursor 3 2 O is mixed, sintered under nitrogen atmosphere, the pressurized pressure of sintering is 40bar, the sintering temperature is 800 ℃, the sintering time is 80min, then the mixture is cooled to room temperature, and then crushed to the particle diameter median D50 of 10 mu m, the pre-lithium material is prepared, the pre-lithium material contains cracks, the width and the length of small cracks are 0.5 nm-1 nm, the width and the length of large cracks are 1 nm-50 nm and 10 nm-400 nm respectively, the purity of the pre-lithium material is 94.5%, the pre-lithium material is used as a lithium battery anode material, graphite is used as a lithium battery anode material, and an ethyl carbonate solution of lithium hexafluorophosphate is used as electrolyte to prepare the lithium battery, and the 4.5V primary charging capacity of the battery is 410.5mAh/g.
Example 2
Taking 10kg of analytically pure nickel chloride and 0.1g of analytically pure niobium pentachloride as raw materials, preparing 1mol/L sulfate solution, adding the sulfate solution of 5L and 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water into a reaction vessel for reaction, filtering, washing and drying the precipitate to prepare a precursor 1, namely Ni (1-x) Me x (OH) 2 Wherein Me is Nb and x is 10 -3 The method comprises the steps of carrying out a first treatment on the surface of the Sintering under nitrogen atmosphere at pressure of 30bar, sintering temperature of 750deg.C, sintering timeFor 60min, precursor 2, designated Ni, was prepared (1-x) Me x O, wherein Me is Nb and x is 10 -3 The method comprises the steps of carrying out a first treatment on the surface of the Adding 0.02g of induction chemical substance niobium pentachloride into the precursor 2, uniformly mixing, then placing in an isostatic pressure environment, pressing to 150bar, wherein the pressing time is 30min, heating to 500 ℃ after decompression, the heating time is 60min, rapidly cooling to room temperature through liquid nitrogen, and under the cooperation of the pressurization environment and the induction chemical substance, causing the crystal structure to be mutagenized, changing the grain size of the precursor, so as to prepare the precursor 3; li in equimolar ratio to precursor 3 2 O is mixed, sintered under nitrogen atmosphere, the pressurized pressure of sintering is 40bar, the sintering temperature is 800 ℃, the sintering time is 80min, then the mixture is cooled to room temperature, the mixture is crushed to the particle diameter median D50 of 10 mu m, the pre-lithium material is prepared, the pre-lithium material contains cracks, the width and the length of small cracks are 0.5 nm-0.8 nm, the width and the length of large cracks are 1 nm-90 nm and 5 nm-300 nm respectively, the purity of the pre-lithium material is 97.6%, the pre-lithium material is used as a lithium battery anode material, graphite is used as a lithium battery anode material, and an ethyl carbonate solution of lithium hexafluorophosphate is used as electrolyte, and the 4.5V primary charge capacity of the battery is 431.1mAh/g.
Example 3
Taking 10kg of analytically pure nickel bromide and 0.005g of analytically pure tantalum bromide as raw materials, preparing 1mol/L sulfate solution, adding the sulfate solution into a reaction vessel according to the proportion of 5L of sulfate solution, 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water for reaction, filtering, washing and drying the precipitate to prepare a precursor 1, namely Ni (1-x) Me x (OH) 2 Wherein Me is Ta and x is 10 -6 The method comprises the steps of carrying out a first treatment on the surface of the Sintering under nitrogen atmosphere at pressure of 30bar under 750 deg.C for 60min to obtain precursor 2, denoted Ni (1-x) Me x O, wherein Me is Ta and x is 10 -6 The method comprises the steps of carrying out a first treatment on the surface of the Adding 0.02g of induction chemical substance tantalum bromide into the precursor 2, heating to 800 ℃ for 60min, rapidly cooling to room temperature by liquid nitrogen, inducing martensitic transformation, inducing crystal structure mutagenesis under the cooperation of high-temperature quenching environment and induction chemical substance,changing the grain size of the precursor to prepare a precursor 3; li in equimolar ratio to precursor 3 2 O is mixed, sintered under nitrogen atmosphere, the pressurized pressure of sintering is 40bar, the sintering temperature is 800 ℃, the sintering time is 80min, then the mixture is cooled to room temperature, the mixture is crushed to the particle diameter median D50 of 10 mu m, the pre-lithium material is prepared, the pre-lithium material contains cracks, the width and the length of small cracks are 0.5 nm-0.7 nm, the width and the length of large cracks are 3 nm-70 nm and 5 nm-500 nm respectively, the purity of the pre-lithium material is 96.1%, the pre-lithium material is used as a lithium battery anode material, graphite is used as a lithium battery anode material, and an ethyl carbonate solution of lithium hexafluorophosphate is used as electrolyte, and the 4.5V primary charge capacity of the battery is 423.2mAh/g.
Example 4
Mixing 10kg of analytically pure nickel sulfate and 0.01g of analytically pure yttrium sulfate and 0.01g of analytically pure strontium sulfate in equal proportion as raw materials to prepare 1mol/L sulfate solution, adding 5L of sulfate solution and 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water into a reaction vessel for reaction, filtering, washing and drying the precipitate to prepare a precursor 1, namely Ni (1-x) Me x (OH) 2 Wherein Me is Y and Sr, and x is 10 -5 The method comprises the steps of carrying out a first treatment on the surface of the Sintering under nitrogen atmosphere at pressure of 30bar under 750 deg.C for 60min to obtain precursor 2, denoted Ni (1-x) Me x O, wherein Me is Ce and x is 10 -5 The method comprises the steps of carrying out a first treatment on the surface of the Adding 0.005g of cerium sulfate serving as an induction chemical substance into the precursor 2, uniformly mixing, placing in a liquid nitrogen-196 ℃ environment for 60min, and under the cooperation of the low-temperature environment and the induction chemical substance, inducing the mutation of a crystal structure, and changing the grain size of the crystal structure to prepare the precursor 3; li in equimolar ratio to precursor 3 2 O is mixed, sintered under nitrogen atmosphere, the pressurized pressure of sintering is 40bar, the sintering temperature is 800 ℃, the sintering time is 80min, then cooled to room temperature, and crushed until the median diameter D50 is 10 mu m, thus preparing the pre-lithium material which contains cracks, the width and the length of small cracks are 0.5 nm-1 nm, and the width and the length of large cracks are 8 nm-90 nm and 4 nm-45 nm respectivelyThe purity of the pre-lithium material is 95.1 percent at 0nm, the pre-lithium material is used as a lithium battery anode material, graphite is used as a lithium battery cathode material, and an ethyl carbonate solution of lithium hexafluorophosphate is used as an electrolyte to prepare the lithium ion battery, and the 4.5V primary charging capacity of the battery is 413.6mAh/g.
Example 5
Mixing 10kg of analytically pure nickel sulfate and 0.002g of analytically pure yttrium sulfate, analytically pure strontium sulfate, niobium pentachloride, cerium sulfate, tantalum bromide and the like in a ratio of 1mol/L of sulfate solution, adding the mixture of 5L of sulfate solution, 8L of 1mol/L of sodium hydroxide solution and 0.2L of 10mol/L of ammonia water into a reaction vessel for reaction, filtering, washing and drying a precipitate to prepare a precursor 1, namely Ni (1-x) Me x (OH) 2 Wherein Me is Sr, Y, nb, ce and Ta, x is 10 -5 The method comprises the steps of carrying out a first treatment on the surface of the Sintering under nitrogen atmosphere at pressure of 30bar under 750 deg.C for 60min to obtain precursor 2, denoted Ni (1-x) Me x O, wherein Me is Sr, Y, nb, ce and Ta, x is 10 -5 The method comprises the steps of carrying out a first treatment on the surface of the Adding 0.01g of induction chemical substance tantalum bromide into the precursor 2, uniformly mixing, placing in a liquid nitrogen-196 ℃ environment for 60min, and under the cooperation of low-temperature environment and the induction chemical substance, inducing the mutation of a crystal structure, and changing the grain size of the crystal structure to prepare the precursor 3; li in equimolar ratio to precursor 3 2 O is mixed, sintered under nitrogen atmosphere, the pressurized pressure of sintering is 40bar, the sintering temperature is 800 ℃, the sintering time is 80min, then the mixture is cooled to room temperature, the mixture is crushed to the particle diameter median D50 of 10 mu m, the pre-lithium material is prepared, the pre-lithium material contains cracks, the width and the length of small cracks are 0.5 nm-0.9 nm, the width and the length of large cracks are 2 nm-50 nm and 15 nm-350 nm respectively, the purity of the pre-lithium material is 95.6%, the pre-lithium material is used as a lithium battery anode material, graphite is used as a lithium battery anode material, and a lithium hexafluorophosphate ethyl carbonate solution is used as electrolyte, and the 4.5V primary charge capacity of the battery is 416.1mAh/g.
Example 6
10kg of analytically pure nickel sulfate was takenMixing with 0.001g of analytically pure yttrium sulfate, analytically pure strontium sulfate, niobium pentachloride, cerium sulfate and tantalum bromide in equal proportion as raw materials to prepare 1mol/L sulfate solution, adding 5L sulfate solution, 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water into a reaction vessel for reaction, filtering, washing and drying the precipitate to prepare a precursor 1, namely Ni (1-x) Me x (OH) 2 Wherein Me is Sr, Y, nb, ce and Ta, x is 10 -6 The method comprises the steps of carrying out a first treatment on the surface of the Sintering under nitrogen atmosphere at pressure of 30bar under 750 deg.C for 60min to obtain precursor 2, denoted Ni (1-x) Me x O, wherein Me is Sr, Y, nb, ce and Ta, x is 10 -6 The method comprises the steps of carrying out a first treatment on the surface of the Adding 0.015g of induction chemical substance tantalum bromide into the precursor 2, uniformly mixing, placing in a liquid nitrogen-150 ℃ environment for 60min, and under the cooperation of low-temperature environment and the induction chemical substance, inducing the mutation of a crystal structure, and changing the grain size of the crystal structure to prepare a precursor 3; li in equimolar ratio to precursor 3 2 O is mixed, sintered under nitrogen atmosphere, the pressurized pressure of sintering is 40bar, the sintering temperature is 800 ℃, the sintering time is 80min, then the mixture is cooled to room temperature, and then crushed to the particle diameter median D50 of 10 mu m, the pre-lithium material is prepared, the pre-lithium material contains cracks, the width and the length of small cracks are 0.6 nm-1 nm, the width and the length of large cracks are 20 nm-80 nm and 30 nm-450 nm respectively, the purity of the pre-lithium material is 94.7%, the pre-lithium material is used as a lithium battery anode material, graphite is used as a lithium battery anode material, and an ethyl carbonate solution of lithium hexafluorophosphate is used as electrolyte to prepare the lithium battery, and the 4.5V primary charging capacity of the battery is 413.2mAh/g.
Comparative example 1
Taking 10kg of analytically pure nickel sulfate as a raw material, preparing 1mol/L sulfate solution, adding the sulfate solution into a reaction container according to the proportion of 5L of sulfate solution, 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water for reaction, filtering, washing and drying precipitate to prepare a precursor 1, namely Ni (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Sintering under nitrogen atmosphere at a pressure of 30bar and a sintering temperature of 75Sintering at 0 ℃ for 60min to prepare a precursor 2, which is marked as NiO; adding 0.005g of cerium sulfate serving as an induction chemical substance into the precursor 2, uniformly mixing, heating the mixture to 700 ℃ for 60min, then rapidly cooling to room temperature through liquid nitrogen to induce martensitic transformation, placing the mixture in a liquid nitrogen-196 ℃ environment for 60min, and under the cooperation of a high-temperature quenching environment, a low-temperature environment and the induction chemical substance, inducing the crystal structure to be mutagenized, and changing the grain size of the mixture to prepare the precursor 3; li in equimolar ratio to precursor 3 2 O is mixed, sintered under nitrogen atmosphere, the pressurized pressure of sintering is 40bar, the sintering temperature is 800 ℃, the sintering time is 80min, then the mixture is cooled to room temperature, and crushed to the particle diameter median D50 of 10 mu m, a sample of comparative example 1 is prepared, the sample contains cracks, the width and length of the cracks are 120 nm-1000 nm and 300 nm-2500 nm, the purity of the sample is 65.1%, the sample is used as a lithium battery anode material, graphite is used as a lithium battery cathode material, and an ethyl carbonate solution of lithium hexafluorophosphate is used as electrolyte to jointly prepare a lithium ion battery, and the 4.5V primary charging capacity of the battery is 313.6mAh/g.
Comparative example 2
Taking 10kg of analytically pure nickel sulfate and 0.01g of analytically pure niobium pentachloride as raw materials, preparing 1mol/L sulfate solution, adding the sulfate solution with the ratio of 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water into a reaction container for reaction according to the ratio of 5L of sulfate solution to 8L of 1mol/L sodium hydroxide solution, filtering, washing and drying the precipitate to prepare a precursor 1, namely Ni (1-x) Me x (OH) 2 Wherein Me is Nb and x is 10 -5 The method comprises the steps of carrying out a first treatment on the surface of the Sintering under nitrogen atmosphere at pressure of 30bar under 750 deg.C for 60min to obtain precursor 2, denoted Ni (1-x) Me x O, wherein Me is Nb and x is 10 -5 The method comprises the steps of carrying out a first treatment on the surface of the Li in equimolar ratio to precursor 2 2 O-mixing, sintering under nitrogen atmosphere at pressure of 40bar and sintering temperature of 800 deg.C for 80min, cooling to room temperature, pulverizing to obtain sample of comparative example 2 containing cracks with width and length of 10 μmThe purity of the sample is 60.3% in 250-1200 nm and 500-3000 nm, the sample is used as a lithium battery anode material, graphite is used as a lithium battery cathode material, and an ethyl carbonate solution of lithium hexafluorophosphate is used as an electrolyte to prepare the lithium ion battery, and the 4.5V primary charging capacity of the battery is 256.3mAh/g.
Comparative example 3
Taking 10kg of analytically pure nickel sulfate as a raw material, preparing 1mol/L sulfate solution, adding the sulfate solution into a reaction container according to the proportion of 5L of sulfate solution, 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water for reaction, filtering, washing and drying precipitate to prepare a precursor 1, namely Ni (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Sintering under nitrogen atmosphere, wherein the pressurized pressure of sintering is 30bar, the sintering temperature is 750 ℃, the sintering time is 60min, and a precursor 2 which is recorded as NiO is prepared; adding 0.02g of induction chemical substance tantalum bromide into the precursor 2, uniformly mixing, placing in a liquid nitrogen-196 ℃ environment for 60min, and under the cooperation of low-temperature environment and the induction chemical substance, inducing the mutation of a crystal structure, and changing the grain size of the crystal structure to prepare a precursor 3; li in equimolar ratio to precursor 3 2 O is mixed, sintered under nitrogen atmosphere, the pressurized pressure of sintering is 40bar, the sintering temperature is 800 ℃, the sintering time is 80min, then the mixture is cooled to room temperature, and crushed to the particle diameter median D50 of 10 mu m, a sample of comparative example 3 is prepared, the sample contains cracks, the width and length of the cracks are 500 nm-2500 nm and 800 nm-3500 nm, the purity of the sample is 55.6%, the sample is used as a lithium battery anode material, graphite is used as a lithium battery cathode material, and an ethyl carbonate solution of lithium hexafluorophosphate is used as electrolyte to jointly prepare a lithium ion battery, and the first charge capacity of 4.5V of the battery is 231.1mAh/g.
Comparative example 4
Taking 10kg of analytically pure nickel sulfate as a raw material, preparing 1mol/L sulfate solution, adding the sulfate solution into a reaction container according to the proportion of 5L of sulfate solution, 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water for reaction, filtering, washing and drying precipitate to prepare a precursor 1, namely Ni (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Sintering under nitrogen atmosphere, the pressed sinteringThe pressure of (2) is 30bar, the sintering temperature is 750 ℃, the sintering time is 60min, and a precursor 3 which is NiO is prepared; li in equimolar ratio to precursor 3 2 O is mixed, sintered under nitrogen atmosphere, the pressurized pressure of sintering is 40bar, the sintering temperature is 800 ℃, the sintering time is 80min, then the mixture is cooled to room temperature, and crushed to the particle diameter median D50 of 10 mu m, a sample of comparative example 4 is prepared, the sample contains cracks, the width and length of the cracks are 200 nm-1800 nm and 600 nm-2200 nm, the purity of the sample is 67.4%, the sample is used as a lithium battery anode material, graphite is used as a lithium battery cathode material, and an ethyl carbonate solution of lithium hexafluorophosphate is used as electrolyte to jointly prepare a lithium ion battery, and the 4.5V primary charging capacity of the battery is 333.2mAh/g.
Cracks of the examples or comparative examples were determined by scanning electron microscope SEM 3000.
Median particle diameter median D50 of the samples of the examples or comparative examples was determined by LS-909E laser particle size analyzer.
The BET specific surface area of the sample in the example or comparative example was measured in accordance with GB/T19587-2017 "BET method for measuring solid substance specific surface area by gas adsorption".
The purity of the samples in the examples or comparative examples was calculated by fitting the shape of the peaks of xrd by means of an X-ray diffractometer (D8 Advance).
The samples in the examples or the comparative examples are used as lithium battery anode materials, graphite is used as lithium battery cathode materials, and ethyl carbonate solution of lithium hexafluorophosphate is used as electrolyte to prepare a lithium ion battery, and the 4.5V primary charging capacity of the battery is measured according to YS/T798-2012 lithium nickel cobalt manganese oxide.
Comparative examples 1 to 6 and comparative examples 1 to 4, the specific surface area of the precursor 3 was measured, and the purity of the pre-lithium material in examples 1 to 6 and the samples in comparative examples 1 to 4, and the first charge capacity at a charge voltage of 4.5V were measured, respectively, and the results of the related test experiments are shown in Table 1
Table 1 results of comparative tests of examples and comparative examples
As can be seen from table 1, the specific surface area of the precursor 3 in examples 1 to 6 is much higher than that of the precursor 3 in comparative examples 1 to 4, and the larger the specific surface area of the precursor 3, the more the crack structure is, the more the pre-lithium material with high purity is prepared; from the purity experimental data of examples 1 to 6 and comparative examples 1 to 4, experimental results are mutually verified, and the greater the specific surface area, the higher the purity of the pre-lithium material; in the method for preparing the pre-lithium material, the induction effect of the induction environment or the induction chemical substances is utilized to change the crystal structure and further enlarge the unit cell volume, so that lithium ions can react with NiO more fully to reduce segregation, the purity and the compactness of the pre-lithium material are improved, the lithium removal capacity is further improved, and the pre-lithium material prepared by the various induction factors in examples 1-6 has obvious advantages in the aspect of the first charge capacity under the condition of 4.5V of charging voltage compared with the sample prepared by the single or no induction factors in comparative examples 1-4, which further indicates that the pre-lithium material prepared by the various induction factors has high lithium removal capacity in the data of the first charge capacity.
It will be appreciated by persons skilled in the art that the embodiments described herein are merely exemplary and that various other alternatives, modifications and improvements may be made within the scope of the invention. Thus, the present invention is not limited to the above-described embodiments, but only by the claims.
Claims (8)
1. A pre-lithium material is characterized in that the chemical formula of the pre-lithium material is Li 2 Ni (1-x) Me x O 2 Wherein x is 10 -6 ～10 -1 Me is a third metal other than Li and Ni; the third metal is selected from one or two of Sr, Y, nb, ce, ta, mo and W;
the preparation method of the pre-lithium material comprises the following steps:
s1, selecting nickel salt and an additive, and preparing a precursor 1 by adopting a chemical coprecipitation method;
s2, calcining the precursor 1 in an inert atmosphere to prepare a precursor 2;
s3, carrying out induction operation on the precursor 2 to induce a crack structure, and preparing a precursor 3;
s4 mixing the precursor 3 with Li in equal molar ratio 2 Mixing O, sintering under inert atmosphere, and crushing to prepare the pre-lithium material;
wherein the additive comprises one or more than two of compounds containing Sr, Y, nb, ce, ta, mo or W;
in step S3, the induction operation is performed by placing the induction device in an induction environment and adding an induction chemical for treatment, wherein the induction environment comprises one or more of a low-temperature environment, a high-pressure environment and a high-temperature quenching environment; the temperature of the low-temperature environment is minus 100 ℃ to minus 250 ℃; the pressure of the high-pressure environment is 10 bar-500 bar; the high-temperature quenching environment is that the high-temperature quenching environment is heated to 300-800 ℃ firstly, and then placed in liquid nitrogen to be cooled to room temperature; the inducing chemical substance is one or more than two of Sr, Y, nb, ce, ta, mo or W compounds.
2. The pre-lithium material according to claim 1, wherein the pre-lithium material comprises cracks, the width of the cracks is 0.5nm to 1nm or 1nm to 100nm, and the length of the cracks is 0.5nm to 1nm or 1nm to 500nm.
3. The pre-lithium material according to claim 1, wherein the pre-lithium material has a median particle diameter D50 of 1 μm to 20 μm and a specific surface area of 0.1m 2 /g～100m 2 /g。
4. The material according to claim 3, wherein the particle diameter median D50 of the material is 3-15 μm and the specific surface area is 5m 2 /g～50m 2 /g。
5. A method of preparing a pre-lithium material according to any one of claims 1 to 4, said method comprising:
s1, selecting nickel salt and an additive, and preparing a precursor 1 by adopting a chemical coprecipitation method;
s2, calcining the precursor 1 in an inert atmosphere to prepare a precursor 2;
s3, carrying out induction operation on the precursor 2 to induce a crack structure, and preparing a precursor 3;
s4 mixing the precursor 3 with Li in equal molar ratio 2 Mixing O, sintering under inert atmosphere, and crushing to prepare the pre-lithium material;
wherein the additive comprises one or more than two of compounds containing Sr, Y, nb, ce, ta, mo or W;
in step S3, the induction operation is performed by placing the induction device in an induction environment and adding an induction chemical for treatment, wherein the induction environment comprises one or more of a low-temperature environment, a high-pressure environment and a high-temperature quenching environment; the temperature of the low-temperature environment is minus 100 ℃ to minus 250 ℃; the pressure of the high-pressure environment is 10 bar-500 bar; the high-temperature quenching environment is that the high-temperature quenching environment is heated to 300-800 ℃ firstly, and then placed in liquid nitrogen to be cooled to room temperature; the inducing chemical substance is one or more than two of Sr, Y, nb, ce, ta, mo or W compounds.
6. The method of claim 5, wherein the nickel salt comprises one or more of nickel sulfate, nickel nitrate, nickel chloride, and nickel bromide.
7. The method of claim 5, wherein the precursor 2 has a chemical formula of Ni (1-x) Me x O, the total amount of free water and crystal water in the precursor 2 is controlled within 0.001% by mole percent.
8. The method of claim 5, wherein the inert atmosphere is one or more selected from the group consisting of nitrogen, helium, neon, and argon.
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