CN112234160A - Lithium supplementing method for lithium ion battery negative electrode active material - Google Patents
Lithium supplementing method for lithium ion battery negative electrode active material Download PDFInfo
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Abstract
The invention discloses a lithium supplementing method for a negative electrode active material of a lithium ion battery, and belongs to the field of lithium ion batteries. The key point of the lithium supplementing method is that the negative active material is added into the organic lithium solution in two stages, so that the second stage lithium supplementing active material is obtained, and then the second stage lithium supplementing active material is added into the organic compound solution, calcined and cleaned, so that the lithium supplementing active material product is obtained. The invention adopts a two-stage method to supplement lithium, which is not only beneficial to forming a compact SEI film on the surface of the active material, but also enables the lithium supplementing degree of the active material to be higher, thereby achieving higher initial coulombic efficiency; by supplementing lithium to the cathode active material of the lithium ion battery, the initial coulombic efficiency and the electrochemical performance of the battery are obviously and effectively improved. The invention adopts the method of organic solution oxidation reduction to supplement lithium for the cathode active material, has mild process temperature, controllable lithium supplement amount and high precision, is suitable for the prior equipment and is beneficial to industrial application.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and relates to a lithium supplementing method for a negative electrode active material of a lithium ion battery.
Background
With the improvement of living standard of people, lithium ion batteries have been widely used in the field of energy storage systems and energy sources, and the development of lithium ion batteries with the characteristics of good environmental compatibility, low cost, high energy density, long cycle life and the like becomes the most competitive technology for meeting the current energy demand. The development of the technology is promoted by applying advanced electrode active substances, a silicon-based material is considered to be the electrode active substance with the highest potential to reach the high-energy-density lithium ion battery due to the higher specific capacity, however, the problems of irreversible loss of active lithium ions, larger volume expansion, low initial coulombic efficiency and the like caused by the SEI film formed on the surface after charging and discharging greatly limit the application of the silicon-based material in the field of the high-energy-density lithium ion battery.
In order to solve the problems of low initial coulombic efficiency of the negative electrode material and the like, a plurality of effective negative electrode lithium supplement methods are developed. For example, inert lithium powder is sprayed or smeared on a negative electrode plate and then rolled, lithium metal is used for dissolving and additionally supplementing lithium ions, and the method can accurately control lithium supplementation by quantitatively controlling the adding amount of the lithium powder, but the method has high safety risk and is difficult to process on a large scale; in addition, the lithium foil can be directly contacted with the cathode pole piece soaked with the electrolyte to supplement lithium, but the lithiation degree of the method is difficult to control and the requirement on the environment is high; the lithium salt or the lithium powder can be doped into the negative active material by a solid phase doping method, and then the lithium is supplemented into the negative active material by high-temperature calcination.
Although there are many methods to effectively improve the initial coulombic efficiency of the silicon-based negative active material, it is important to develop a feasible and effective lithium supplement method for the negative active material of the lithium ion battery in consideration of the factors of cost, safety, large-scale application and the like.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the invention aims to provide a lithium supplementing method for a negative electrode active material of a lithium ion battery. The invention can effectively solve the problem of low initial coulombic efficiency of the lithium ion battery cathode active material, and provides the lithium supplement method with mild and simple process and controllable lithium supplement amount.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a lithium supplementing method for a negative electrode active material of a lithium ion battery, which comprises the following steps:
1) uniformly dispersing a polycyclic aromatic organic compound in a solvent, dissolving to obtain a solution D, and uniformly dispersing a derivative of biphenyl or terphenyl in the solvent, dissolving to obtain a solution E;
2) uniformly dispersing lithium metal in the obtained solution D, dissolving to obtain an organic lithium solution F, uniformly dispersing the lithium metal in the obtained solution E, and dissolving to obtain an organic lithium solution G;
3) uniformly dispersing a negative electrode active substance in the obtained organic lithium solution F, and filtering after reaction to obtain a first-stage lithium supplement active substance H; uniformly dispersing the obtained first-stage lithium supplement active substance H in the obtained organic lithium solution G, and filtering after reaction to obtain a second-stage lithium supplement active substance J;
4) uniformly dispersing the obtained second-stage lithium supplement active substance J in a solution of a polycyclic aromatic organic compound to obtain a lithium supplement active substance K;
5) calcining the obtained lithium-supplementing active substance K in an inert atmosphere, cooling to obtain a product mixture, cleaning and soaking the obtained product mixture, filtering to obtain a solid product, washing and drying the obtained solid product to obtain a lithium-supplementing active substance, and completing lithium supplementation;
the steps 1) to 5) are carried out in an anhydrous and oxygen-free inert atmosphere.
Preferably, in step 1), the polycyclic aromatic organic compound includes one or more of biphenyl, p-terphenyl, m-terphenyl, 1, 2-terphenyl, naphthalene, anthracene, phenanthrene and pyrene.
Preferably, in step 1), the biphenyl or terphenyl derivative includes one or more of 2-methylbiphenyl, 2-ethylbiphenyl, 3 ' -dimethylbiphenyl, 4,4 ' -dimethyl-p-terphenyl, 4,4 ' -dimethylbiphenyl and 3,3 ', 4,4 ' -tetramethylbiphenyl.
Preferably, in step 1), the solvent is an ether, chain or cyclic carbonate organic solvent;
in the step 2), the lithium metal is a lithium sheet, a lithium ingot, a lithium strip, a lithium ribbon or lithium powder;
in the step 3), the negative electrode active material is a hard carbon negative electrode, a silicon-based negative electrode or an oxide negative electrode.
Preferably, in the step 2), the ratio of the amount of the lithium metal to the polycyclic aromatic organic compound is 0.1 to 50: 1, the ratio of the amount of lithium metal to the amount of biphenyl or terphenyl derivatives is 0.1 to 50: 1.
preferably, in the step 3), the reaction temperature is 10-80 ℃ and the reaction time is 0.1-100 h.
Preferably, in the step 1), the concentration ranges of the solution D and the solution E are 0.01-10 mol/L respectively;
in the step 3), the concentration range of the negative electrode active substance in the organic lithium solution F or the organic lithium solution G is 0.01-2G/mL;
in the step 4), the concentration range of the second-stage lithium supplement active substance J in the solution D is 0.01-2 g/mL.
Preferably, in the step 5), the calcining temperature is 450-800 ℃, and the calcining time is 0.5-24 h.
Preferably, in step 5), the calcining equipment is a tube furnace, a box furnace or a roller kiln.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a lithium supplementing method for a negative electrode active material of a lithium ion battery, wherein a two-stage method is adopted to supplement lithium in the lithium supplementing process of the negative electrode active material, the negative electrode active material in the first stage is favorable for forming a compact SEI film in an organic lithium solution F, and the negative electrode active material in the second stage is favorable for enabling the lithium supplementing degree of the active material in an organic lithium solution G to be higher, so that higher initial coulomb efficiency is achieved; therefore, the lithium supplementing method is beneficial to forming a compact and good SEI film on the surface of the active material, and enables the lithium supplementing degree of the active material to be higher, so that higher initial coulombic efficiency is achieved; by supplementing lithium to the cathode active material of the lithium ion battery, the initial coulombic efficiency and the electrochemical performance of the battery are obviously and effectively improved. According to the invention, the lithium is supplemented to the cathode active material by adopting an organic solution redox method, the reaction process is simple, the lithium supplementing amount can be controlled by adjusting the amount ratio of the lithium metal to the polycyclic aromatic organic compound in the lithium intercalation process and the concentration of the cathode active material in the organic lithium solution, and the solution reaction contact is relatively uniform, so that the lithium supplementing amount in the lithium supplementing process is easy to control, the accuracy is high, and the material uniformity is good.
Furthermore, the lithium supplementing method for the lithium ion battery cathode active material has mild reaction temperature, and can avoid direct lithium metal lithium supplementing or high-temperature reaction operation.
Furthermore, the invention is suitable for the existing production and manufacturing equipment, has simple and reliable process and easy amplification, and is beneficial to industrial application.
Drawings
FIG. 1 is a graph showing X-ray diffraction measurements of lithium-supplemented silica in an embodiment of a lithium supplementation method of the present invention;
FIG. 2 is an X-ray diffraction test chart of lithium-supplemented silicon carbon in an embodiment of a lithium supplementing method of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a lithium supplementing method for a negative electrode active material of a lithium ion battery, which comprises the following steps: step 1: dissolving an organic compound in an organic solvent to obtain an organic compound solution; step 2: adding lithium metal into an organic compound solution to obtain an organic lithium solution; and step 3: adding the negative active material into the organic lithium solution in two stages to obtain a lithium supplementing active material; and 4, step 4: adding a lithium-supplementing active substance into an organic compound solution; and 5: calcining and cleaning the lithium-supplementing active substance; and obtaining the lithium-supplementing active substance product.
The lithium supplementing method of the lithium ion battery negative electrode active material specifically comprises the following steps:
step 1, weighing organic compounds A and B with certain mass and respectively and completely dissolving the organic compounds A and B in an organic solvent C under the environment of low humidity and inert atmosphere to obtain a solution D and a solution E of the organic compounds with certain concentration;
the organic compound A is polycyclic aromatic organic compound, which comprises one or more than one of biphenyl, p-terphenyl, m-terphenyl, 1, 2-terphenyl, naphthalene, anthracene, phenanthrene, pyrene and the like;
the organic compound B is a derivative of biphenyl or terphenyl, and comprises one or more than one of 2-methyl biphenyl, 2-ethyl biphenyl, 3 ' -dimethyl biphenyl, 4,4 ' -dimethyl p-terphenyl, 4,4 ' -dimethyl biphenyl, 3 ', 4,4 ' -tetramethyl biphenyl and the like;
the organic solvent C is an ether, chain or cyclic carbonate organic solvent, preferably an ether organic solvent, and comprises tetrahydrofuran, glycol dimethyl ether or dioxane, and the like;
the organic solvent C is preferably a high-purity solvent subjected to water removal and oxygen removal;
the concentration ranges of the solution D and the solution E of the organic compound are 0.01-10 mol/L respectively;
step 2, respectively weighing a certain mass of lithium metal, adding the lithium metal into the solution D and the solution E of the organic compound, and dissolving the lithium metal to obtain an organic lithium solution F and an organic lithium solution G;
the lithium metal is lithium sheet, lithium ingot, lithium strip, lithium belt, lithium powder and the like;
the addition amount of the lithium metal is the molar ratio of lithium to the organic compound A or the organic compound B, and the molar ratio ranges from 0.1 to 50: 1;
step 3, adding a certain mass of negative active material into the organic lithium solution F at a certain reaction temperature in the first stage, mechanically stirring to react for a certain time, and filtering to obtain a first-stage lithium supplement active material H; in the second stage, adding the lithium supplement active substance H into the organic lithium solution G, continuously stirring and reacting for a certain time, and filtering to obtain a second stage lithium supplement active substance J;
the negative active material is a hard carbon negative electrode, a silicon-based negative electrode or an oxide negative electrode;
the reaction temperature for obtaining the first-stage lithium supplement active substance H and the second-stage lithium supplement active substance J is 10-80 ℃; the reaction time for obtaining the first-stage lithium supplement active substance H and the second-stage lithium supplement active substance J is 0.1-100H;
the concentration range of the negative electrode active substance in the organic lithium solution F or the organic lithium solution G is 0.01-2G/mL;
step 4, adding a certain mass of the second-stage lithium supplement active substance J into a certain volume of the solution D of the organic compound, mechanically stirring for a certain time, filtering, and drying to obtain a lithium supplement active substance K;
the concentration range of the lithium supplementing active substance J in the solution D at the second stage is 0.01-2 g/mL;
the mechanical stirring time is 0.5-72 h;
step 5, putting the lithium-supplementing active substance K into heating equipment under an inert atmosphere for calcining for a period of constant temperature, naturally cooling to room temperature, taking out, cleaning and soaking for a period of time, filtering, washing and drying to obtain a lithium-supplementing active substance product L, and completing lithium supplementation;
the inert atmosphere comprises nitrogen, helium and argon, preferably argon;
the heating equipment is a tubular furnace, a box furnace and a roller kiln;
the calcination time is 0.5 to 24 hours;
the calcination temperature is 450-800 ℃;
the cleaning medium is one or more of water, ethanol, methanol or acetic acid and the like which are mixed in any proportion;
the cleaning time is 0.2-48 h.
According to the lithium supplementing method for the negative electrode active material of the lithium ion battery, the key step 3 is divided into two stages, the negative electrode active material in the first stage is favorable for forming a compact SEI film in an organic lithium solution F, and the negative electrode active material in the second stage is favorable for enabling the lithium supplementing degree of the active material in the organic lithium solution G to be higher, so that the higher initial coulombic efficiency is achieved.
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
Firstly, weighing 185.1g of biphenyl and 273.3g of 3,3 '-dimethylbiphenyl to completely dissolve in 1000mL of tetrahydrofuran and 1000mL of ethylene glycol dimethyl ether respectively under the environment of low humidity and-20 ℃ and filling argon to obtain a biphenyl solution and a 3, 3' -dimethylbiphenyl solution; then respectively weighing 50G of lithium ingot, adding the lithium ingot into the biphenyl solution and the 3, 3' -dimethyl biphenyl solution, and dissolving the lithium ingot to obtain an organic lithium solution F1 and an organic lithium solution G1;
then at 30 ℃, adding 200G of silica into 1000mL of organic lithium solution F1, mechanically stirring for 14h, filtering, then adding the filtered product into 800mL of organic lithium solution G1, continuously stirring for 8h, and filtering to obtain lithium-supplemented silica J1; adding 150g of lithium-supplementing silicon oxide J1 into 500mL of 0.2mol/L biphenyl solution, mechanically stirring for 2.5h, filtering, and drying to obtain lithium-supplementing silicon oxide K1;
and putting the obtained lithium-supplementing silicon oxide K1 into a magnetic boat in a nitrogen atmosphere, calcining for 8h at the constant temperature of 700 ℃ in a box-type furnace, naturally cooling to room temperature, taking out, cleaning and soaking the product with deionized water for 12h, filtering, washing and drying to obtain a lithium-supplementing silicon oxide product L1, and completing lithium supplementation.
The button cell with the metal lithium as the counter electrode is prepared from the lithium-supplementing silicon oxide product L1, the initial coulombic efficiency is 91.2% by observing the first-cycle charge-discharge curve, the gram capacity exertion is 1580mAh/g, and the initial coulombic efficiency is obviously improved.
Example 2
Firstly, 1282.1g of naphthalene and 920.2g of 4,4 '-dimethylbiphenyl are weighed and completely dissolved in 1000mL of tetrahydrofuran respectively under the environment of low humidity of-20 ℃ and filled with argon to obtain a naphthalene solution and a 4, 4' -dimethylbiphenyl solution; then, respectively weighing 350G of lithium sheets and 525G of lithium sheets, adding the lithium sheets into the naphthalene solution and the 4, 4' -dimethylbiphenyl solution, and dissolving the lithium sheets to obtain an organic lithium solution F2 and an organic lithium solution G2;
adding 250G of silica into 1000mL of organic lithium solution F2 at 10 ℃, mechanically stirring for 50h, filtering, adding the filtered product into 800mL of organic lithium solution G2, continuously stirring for 4h, and filtering to obtain lithium-supplemented silica J2; adding 150g of lithium-supplementing silicon oxide J2 into 300mL of 1mol/L phenanthrene solution, mechanically stirring for 72 hours, filtering, and drying to obtain lithium-supplementing silicon oxide K2;
then putting the obtained lithium-supplementing silicon oxide K2 into a magnetic boat in an argon atmosphere, calcining for 24 hours in a roller kiln at constant temperature of 560 ℃, naturally cooling to room temperature, taking out, and then adding a catalyst with the volume ratio of 10: 1, washing and soaking the mixture for 48 hours by using a mixed solution of water and ethanol, filtering, washing and drying to obtain a product L2 of the lithium-supplementing silicon oxide, thereby completing lithium supplementation.
The button cell with the metal lithium as the counter electrode is prepared from the lithium-supplementing silicon oxide product L2, the initial coulombic efficiency is 89.3% by observing the first-cycle charge-discharge curve, the gram capacity exertion is 1602mAh/g, and the initial coulombic efficiency is obviously improved.
Example 3
Firstly, weighing 2.3g of p-terphenyl and 2.9g of 3,3 ', 4, 4' -tetramethylbiphenyl under the environment of low humidity and-20 ℃ and filled with argon, and completely dissolving the p-terphenyl and the 3,3 ', 4, 4' -tetramethylbiphenyl in 1000mL of tetrahydrofuran and 1000mL of ethylene glycol dimethyl ether respectively to obtain a p-terphenyl solution and a 3,3 ', 4, 4' -tetramethylbiphenyl solution; then, respectively weighing 35G of lithium tapes and 12G of lithium tapes, adding the lithium tapes into the p-terphenyl solution and the 3,3 ', 4, 4' -tetramethylbiphenyl solution, and dissolving the lithium tapes to obtain an organic lithium solution F3 and an organic lithium solution G3;
adding 100G of hard carbon into 1000mL of organic lithium solution F3 at 80 ℃, mechanically stirring for 20h, filtering, adding the filtered product into 50mL of organic lithium solution G3, continuously stirring for 0.1h, and filtering to obtain lithium-supplementing hard carbon J3; adding 12g of lithium-supplementing hard carbon J3 into 1200mL of 10mol/L anthracene solution, mechanically stirring for 0.5h, filtering, and drying to obtain lithium-supplementing hard carbon K3;
putting the obtained lithium-supplementing hard carbon K3 into a magnetic boat in a helium atmosphere, calcining for 0.5h at the constant temperature of 800 ℃ in a tube furnace, naturally cooling to room temperature, taking out, cleaning and soaking for 0.2h by using a mixed solution of ethanol and acetic acid with a volume ratio of 80:1, filtering, washing and drying to obtain a lithium-supplementing hard carbon product L3, and completing lithium supplementation;
the button battery with the metal lithium as the counter electrode is prepared from the lithium-supplement hard carbon product L3, the initial coulombic efficiency is 88.1 percent by observing the first-week charge-discharge curve, the gram capacity exertion is 457mAh/g, and the initial coulombic efficiency is obviously improved.
Example 4
Firstly, weighing 256.4g of biphenyl and 89.1g of anthracene into 1000mL of tetrahydrofuran to be completely dissolved to obtain a biphenyl/anthracene solution under the environment of low humidity and-20 ℃ and filling argon, and weighing 103.4g of 2-methylbiphenyl to be completely dissolved in 1000mL of dioxane to obtain a 2-dimethylbiphenyl solution; then, respectively weighing 92G and 0.4G of lithium strips, adding the lithium strips into the biphenyl/anthracene solution and the 2-methyl biphenyl solution, and dissolving the lithium strips to obtain an organic lithium solution F4 and an organic lithium solution G4;
adding 200G of silicon carbon into 1000mL of organic lithium solution F4 at 45 ℃, mechanically stirring for 100h, filtering, adding the filtered product into 900mL of organic lithium solution G4, continuously stirring for 12h, and filtering to obtain lithium-supplementing silicon carbon J4; adding 240g of lithium-supplementing silicon carbon J4 into 120mL of 1.8mol/L m-terphenyl solution, mechanically stirring for 3 hours, filtering, repeatedly replacing 120mL of 1.8mol/L m-terphenyl solution for more than three times, filtering again and drying to obtain lithium-supplementing silicon carbon K4;
putting the obtained lithium-supplementing silicon carbon K4 into a magnetic boat in an argon atmosphere, calcining the magnetic boat in a roller kiln at the constant temperature of 450 ℃ for 10h, naturally cooling the magnetic boat to room temperature, taking the magnetic boat out, cleaning and soaking the magnetic boat for 8h by using a mixed solution of methanol and water in a volume ratio of 1:1, filtering, washing and drying the mixed solution to obtain a lithium-supplementing silicon carbon product L4, and completing lithium supplementation;
the button battery with the metal lithium as the counter electrode is prepared from the lithium-supplementing silicon carbon product L4, the initial coulombic efficiency is 88.7 percent by observing the first-week charging and discharging curve, the gram capacity exertion is 937mAh/g, and the initial coulombic efficiency is obviously improved.
Comparative example 1
Firstly, weighing 185.1g of biphenyl and completely dissolving the biphenyl into 1000mL of tetrahydrofuran under the environment of low humidity of-20 ℃ and filling argon to obtain a biphenyl solution; then weighing 50g of lithium ingot, adding the lithium ingot into the biphenyl solution, and dissolving the lithium ingot to obtain an organic lithium solution F5;
then 200g of silica is added into 1000mL of organic lithium solution F5 at the temperature of 30 ℃, mechanical stirring is carried out for 14h, and then filtration is carried out, thus obtaining lithium-supplementing silica J5; adding 150g of lithium-supplementing silicon oxide J5 into 500mL of 0.2mol/L biphenyl solution, mechanically stirring for 2.5h, filtering, and drying to obtain lithium-supplementing silicon oxide K5;
then putting the obtained lithium-supplementing silicon oxide K5 into a magnetic boat in a nitrogen atmosphere, calcining for 8 hours at the constant temperature of 700 ℃ in a box-type furnace, naturally cooling to room temperature, taking out, cleaning and soaking the product with deionized water for 12 hours, filtering, washing and drying to obtain a lithium-supplementing silicon oxide product L5, and completing lithium supplementation;
the button cell with the electrode made of the lithium-supplemented silicon monoxide product L5 is prepared, and by observing the first-cycle charge-discharge curve, the initial coulombic efficiency is 86.6%, the gram capacity exertion is 1619mAh/g, and the initial coulombic efficiency is better improved.
Comparative example 2
And preparing the lithium-supplemented silicon monoxide into a button battery with a counter electrode made of lithium metal, and observing a first-cycle charge-discharge curve, wherein the initial coulombic efficiency is 80.9%, the gram capacity exertion is 1683mAh/g, and the initial coulombic efficiency is lower.
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1, it is known that a negative electrode active material of silicon oxide is compensated with lithium to generate Li2SiO3、Li2Si2O5Lithium silicate salts are used for indicating that lithium supplement is realized, and partial irreversible capacity loss caused by first charge and discharge is avoided;
referring to fig. 2, it can be seen that the silicon-carbon negative electrode active material is compensated with lithium to generate Li2SiO3Lithium silicate, which indicates that silicon oxide in the silicon-carbon material reacts with lithium, makes up for part of irreversible lithium consumption brought by first charge and discharge;
according to the invention, the lithium is supplemented by adopting a two-stage method in the lithium supplementing process of the cathode active material, the method is beneficial to forming a compact SEI film on the surface of the active material, and the lithium supplementing degree of the active material is higher, so that higher initial coulombic efficiency is achieved; by supplementing lithium to the cathode active material of the lithium ion battery, the initial coulombic efficiency and the electrochemical performance of the battery are obviously and effectively improved. According to the invention, the lithium is supplemented to the cathode active material by adopting an organic solution redox method, the reaction process is mild, the lithium supplementing amount in the lithium supplementing process is easy to control, the accuracy is high, and the material uniformity is good; the invention is suitable for the existing production and manufacturing equipment, has simple and reliable process and easy amplification, and is beneficial to industrial application.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (9)
1. A lithium supplementing method for a negative electrode active material of a lithium ion battery is characterized by comprising the following steps:
1) uniformly dispersing a polycyclic aromatic organic compound in a solvent, dissolving to obtain a solution D, and uniformly dispersing a derivative of biphenyl or terphenyl in the solvent, dissolving to obtain a solution E;
2) uniformly dispersing lithium metal in the obtained solution D, dissolving to obtain an organic lithium solution F, uniformly dispersing the lithium metal in the obtained solution E, and dissolving to obtain an organic lithium solution G;
3) uniformly dispersing a negative electrode active substance in the obtained organic lithium solution F, and filtering after reaction to obtain a first-stage lithium supplement active substance H; uniformly dispersing the obtained first-stage lithium supplement active substance H in the obtained organic lithium solution G, and filtering after reaction to obtain a second-stage lithium supplement active substance J;
4) uniformly dispersing the obtained second-stage lithium supplement active substance J in a solution of a polycyclic aromatic organic compound to obtain a lithium supplement active substance K;
5) calcining the obtained lithium-supplementing active substance K in an inert atmosphere, cooling to obtain a product mixture, cleaning and soaking the obtained product mixture, filtering to obtain a solid product, washing and drying the obtained solid product to obtain a lithium-supplementing active substance, and completing lithium supplementation;
the steps 1) to 5) are carried out in an anhydrous and oxygen-free inert atmosphere.
2. The method for supplementing lithium to the negative active material of the lithium ion battery according to claim 1, wherein in the step 1), the polycyclic aromatic organic compound comprises one or more of biphenyl, p-terphenyl, m-terphenyl, 1, 2-terphenyl, naphthalene, anthracene, phenanthrene and pyrene.
3. The method for supplementing lithium to the negative active material of the lithium ion battery according to claim 1, wherein in the step 1), the derivative of biphenyl or terphenyl comprises one or more of 2-methylbiphenyl, 2-ethylbiphenyl, 3 ' -dimethylbiphenyl, 4,4 ' -dimethyl-p-terphenyl, 4,4 ' -dimethylbiphenyl, and 3,3 ', 4,4 ' -tetramethylbiphenyl.
4. The method for supplementing lithium to the negative electrode active material of the lithium ion battery according to claim 1, wherein in the step 1), the solvent is an ether, chain or cyclic carbonate organic solvent;
in the step 2), the lithium metal is a lithium sheet, a lithium ingot, a lithium strip, a lithium ribbon or lithium powder;
in the step 3), the negative electrode active material is a hard carbon negative electrode, a silicon-based negative electrode or an oxide negative electrode.
5. The method for supplementing lithium to the negative electrode active material of a lithium ion battery according to claim 1, wherein the ratio of the amount of the lithium metal to the amount of the polycyclic aromatic organic compound in the step 2) is 0.1 to 50: 1, the ratio of the amount of lithium metal to the amount of biphenyl or terphenyl derivatives is 0.1 to 50: 1.
6. the method for supplementing lithium to the negative electrode active material of the lithium ion battery according to claim 1, wherein the reaction temperature in the step 3) is 10 to 80 ℃ and the reaction time is 0.1 to 100 hours.
7. The method for supplementing lithium to the negative electrode active material of the lithium ion battery according to claim 1, wherein in the step 3), the concentration range of the negative electrode active material in the organic lithium solution F or the organic lithium solution G is 0.01-2G/mL;
in the step 4), the concentration range of the second-stage lithium supplement active substance J in the solution D is 0.01-2 g/mL.
8. The method for supplementing lithium to the negative electrode active material of the lithium ion battery according to claim 1, wherein in the step 5), the calcination temperature is 450 to 800 ℃ and the calcination time is 0.5 to 24 hours.
9. The method for supplementing lithium to the negative electrode active material of the lithium ion battery according to claim 1, wherein in the step 5), the calcining equipment is a tube furnace, a box furnace or a roller kiln.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113066972A (en) * | 2021-03-19 | 2021-07-02 | 厦门高容新能源科技有限公司 | Lithium-supplementing silicon material, preparation method thereof, electrode containing lithium-supplementing silicon material and battery |
| CN114420915A (en) * | 2022-01-17 | 2022-04-29 | 厦门海辰新能源科技有限公司 | Lithium supplement for lithium battery and manufacturing method |
| CN114975898A (en) * | 2021-02-20 | 2022-08-30 | 贝特瑞新材料集团股份有限公司 | Negative electrode material for lithium ion battery, pre-lithiation treatment method of negative electrode material, and lithium ion battery |
| CN115642318A (en) * | 2021-07-19 | 2023-01-24 | 比亚迪股份有限公司 | Method for replenishing lithium to negative electrode, device for replenishing lithium to negative electrode, and battery |
| CN117059804A (en) * | 2023-10-13 | 2023-11-14 | 瑞浦兰钧能源股份有限公司 | Chemical pre-lithium agent, lithium ion battery and preparation method of lithium ion battery |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105932224A (en) * | 2016-05-23 | 2016-09-07 | 深圳大学 | Modified silicon-based negative electrode material, preparation method and application thereof |
| US20190051897A1 (en) * | 2016-02-23 | 2019-02-14 | Shin-Etsu Chemical Co., Ltd. | Negative electrode active material, material of mixed negative electrode active material, negative electrode for non-aqueous electrolyte secondary battery, lithium ion secondary battery, method for producing negative electrode active material and method for producing lithium ion secondary battery |
| CN109802109A (en) * | 2018-12-29 | 2019-05-24 | 上海力信能源科技有限责任公司 | A kind of prelithiation battery silicon-based anode and the method for being formed simultaneously SEI film |
| CN109923706A (en) * | 2016-09-02 | 2019-06-21 | 香港商Eo细胞有限公司 | With insertion silicon: the silicon-silicon oxide-lithium composite material of the silicon nanoparticle volume change compensation of silicic acid silicon lithium complex matrix, and periodical ex situ manufacturing method |
| CN110010863A (en) * | 2019-03-19 | 2019-07-12 | 合肥国轩高科动力能源有限公司 | Method for pre-lithiation of lithium ion battery negative electrode material |
| CN110071265A (en) * | 2019-04-02 | 2019-07-30 | 浙江工业大学 | A kind of silicon-carbon cathode prelithiation method |
| KR20190115706A (en) * | 2018-04-03 | 2019-10-14 | 주식회사 엘지화학 | Negative electrode for lithium secondary battery, preparing method thereof, and lithium secondary battery comprising the same |
| CN111180660A (en) * | 2019-12-31 | 2020-05-19 | 兰溪致德新能源材料有限公司 | Liquid-phase lithium supplementing method for positive and negative electrode materials of lithium battery |
| CN111313013A (en) * | 2020-03-02 | 2020-06-19 | 同济大学 | Preparation method and application of lithium-tin alloy powder for lithium ion battery cathode |
| CN111453713A (en) * | 2020-04-08 | 2020-07-28 | 合肥国轩高科动力能源有限公司 | Silicon oxide/carbon material and preparation method and application thereof |
| CN111615769A (en) * | 2018-03-07 | 2020-09-01 | 株式会社Lg化学 | Method for manufacturing negative electrode |
-
2020
- 2020-10-20 CN CN202011125970.6A patent/CN112234160B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190051897A1 (en) * | 2016-02-23 | 2019-02-14 | Shin-Etsu Chemical Co., Ltd. | Negative electrode active material, material of mixed negative electrode active material, negative electrode for non-aqueous electrolyte secondary battery, lithium ion secondary battery, method for producing negative electrode active material and method for producing lithium ion secondary battery |
| CN105932224A (en) * | 2016-05-23 | 2016-09-07 | 深圳大学 | Modified silicon-based negative electrode material, preparation method and application thereof |
| CN109923706A (en) * | 2016-09-02 | 2019-06-21 | 香港商Eo细胞有限公司 | With insertion silicon: the silicon-silicon oxide-lithium composite material of the silicon nanoparticle volume change compensation of silicic acid silicon lithium complex matrix, and periodical ex situ manufacturing method |
| CN111615769A (en) * | 2018-03-07 | 2020-09-01 | 株式会社Lg化学 | Method for manufacturing negative electrode |
| KR20190115706A (en) * | 2018-04-03 | 2019-10-14 | 주식회사 엘지화학 | Negative electrode for lithium secondary battery, preparing method thereof, and lithium secondary battery comprising the same |
| CN109802109A (en) * | 2018-12-29 | 2019-05-24 | 上海力信能源科技有限责任公司 | A kind of prelithiation battery silicon-based anode and the method for being formed simultaneously SEI film |
| CN110010863A (en) * | 2019-03-19 | 2019-07-12 | 合肥国轩高科动力能源有限公司 | Method for pre-lithiation of lithium ion battery negative electrode material |
| CN110071265A (en) * | 2019-04-02 | 2019-07-30 | 浙江工业大学 | A kind of silicon-carbon cathode prelithiation method |
| CN111180660A (en) * | 2019-12-31 | 2020-05-19 | 兰溪致德新能源材料有限公司 | Liquid-phase lithium supplementing method for positive and negative electrode materials of lithium battery |
| CN111313013A (en) * | 2020-03-02 | 2020-06-19 | 同济大学 | Preparation method and application of lithium-tin alloy powder for lithium ion battery cathode |
| CN111453713A (en) * | 2020-04-08 | 2020-07-28 | 合肥国轩高科动力能源有限公司 | Silicon oxide/carbon material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| JUYOUNG JANG等: "Molecularly Tailored Lithium-Arene Complex Enables Chemical Prelithiation of High-Capacity Lithium-Ion Battery Anodes", 《ANGEWANDTE CHEMIE》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114975898A (en) * | 2021-02-20 | 2022-08-30 | 贝特瑞新材料集团股份有限公司 | Negative electrode material for lithium ion battery, pre-lithiation treatment method of negative electrode material, and lithium ion battery |
| JP2023522669A (en) * | 2021-02-20 | 2023-05-31 | 貝特瑞新材料集団股▲ふん▼有限公司 | Negative electrode material, method of making and use thereof |
| CN113066972A (en) * | 2021-03-19 | 2021-07-02 | 厦门高容新能源科技有限公司 | Lithium-supplementing silicon material, preparation method thereof, electrode containing lithium-supplementing silicon material and battery |
| CN115642318A (en) * | 2021-07-19 | 2023-01-24 | 比亚迪股份有限公司 | Method for replenishing lithium to negative electrode, device for replenishing lithium to negative electrode, and battery |
| CN114420915A (en) * | 2022-01-17 | 2022-04-29 | 厦门海辰新能源科技有限公司 | Lithium supplement for lithium battery and manufacturing method |
| CN114420915B (en) * | 2022-01-17 | 2023-04-25 | 厦门海辰储能科技股份有限公司 | Lithium supplementing and manufacturing method of lithium battery |
| CN117059804A (en) * | 2023-10-13 | 2023-11-14 | 瑞浦兰钧能源股份有限公司 | Chemical pre-lithium agent, lithium ion battery and preparation method of lithium ion battery |
| CN117059804B (en) * | 2023-10-13 | 2024-03-19 | 瑞浦兰钧能源股份有限公司 | Chemical pre-lithium agent, lithium ion battery and preparation method of lithium ion battery |
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