CN114976197B - Method for improving interface between high nickel material and LATP solid electrolyte and battery - Google Patents

Method for improving interface between high nickel material and LATP solid electrolyte and battery Download PDF

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CN114976197B
CN114976197B CN202210514769.XA CN202210514769A CN114976197B CN 114976197 B CN114976197 B CN 114976197B CN 202210514769 A CN202210514769 A CN 202210514769A CN 114976197 B CN114976197 B CN 114976197B
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nickel material
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latp
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CN114976197A (en
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王立帆
詹纯
王磊营
王睿
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University of Science and Technology Beijing USTB
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    • H01—ELECTRIC ELEMENTS
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Abstract

The invention relates to a high nickel material and LATThe improvement method of the P solid electrolyte interface and the battery belong to the technical field of solid lithium batteries, and can solve the problem that the LATP and NCM interface is unstable in the deep lithium removal state of the high-nickel positive electrode material, so that the capacity is attenuated; the method reduces Ni in the circulation process by coating lithium and oxygen double-ion conductors on the surface of the high-nickel material 2+ Improving the interface problem between the high nickel material and the LATP solid electrolyte; s1, dissolving lanthanum nitrate in deionized water to obtain a first solution; s2, adding a high nickel material precursor to obtain a second solution; s3, drying and grinding to obtain a coating sample precursor; s4, mixing and grinding the mixture with lithium hydroxide monohydrate to obtain a grinding sample; s5, calcining the grinding sample to obtain a high-nickel material coated by the lithium-oxygen double-ion conductor; s6, the obtained high-nickel material and LATP solid electrolyte are used in the solid battery to achieve battery performance after interface improvement.

Description

Method for improving interface between high nickel material and LATP solid electrolyte and battery
Technical Field
The invention relates to the technical field of solid-state lithium batteries, in particular to an improvement method of a high-nickel material and LATP solid electrolyte interface and a battery.
Background
With the rapid increase of carbon dioxide emissions and greenhouse gases in various countries, climate change has become a global issue facing humans. Lithium Ion Batteries (LIBs) have received attention in recent years as a key technology to support the development of renewable energy sources to reduce environmental pollution. Among them, solid-state lithium ion batteries are a big hot spot in the industry due to their higher energy density and higher safety. In this context, ternary high-nickel materials are expected to become the positive electrode materials of the next-generation solid-state batteries by virtue of their higher energy density and operating voltage. However, until now, solid-state lithium ion batteries still face problems such as poor positive-solid electrolyte interface, too high interface impedance, and the like.
A great deal of research finds that the main mechanism affecting the stability of the high nickel cathode material is: 1) The interfacial chemical reaction generates a new phase to destroy the stability of the positive electrode-solid electrolyte interface; 2) The loose interface contact caused by the positive electrode volume change in the charge and discharge process causes the loss of high interface impedance or first-circle capacity; 3) Ni in high nickel layered cathode material in highly delithiated state 3+ And O 2- Oxidation reaction occurs to generate Ni 4+ And high active oxygen; 4) The high active oxygen at the electrode/electrolyte interface escapes from the surface lattice, resulting in poor interface stability; 5) The space charge layer creates an impediment to interfacial lithium ion conduction. Although these explanations appear to be dispersed in different aspects, they are all closely related to the high nickel positive electrode material and solid state electrolyte interface. In summary, interface problems have been considered as a key factor affecting solid state lithium ion batteries.
Accordingly, there is a need to develop an improved method of interfacing high nickel materials with LATP solid state electrolytes to address the deficiencies of the prior art to solve or mitigate one or more of the problems described above.
Disclosure of Invention
In view of the above, the invention provides a method for improving the interface between a high nickel material and a LATP solid electrolyte and a battery, which can solve the problem that the high nickel positive electrode material of a titanium aluminum lithium phosphate solid battery is unstable at the interface between LATP and NCM in a deep lithium removal state, so that the capacity attenuation is serious.
In one aspect, the invention provides a method for improving the interface between a high nickel material and a LATP solid electrolyte, which is characterized in that the improvement method reduces Ni in the circulation process by coating a lithium-oxygen double ion conductor on the surface of the high nickel material 2+ To improve the interface problem between the high nickel material and the LATP solid electrolyte.
In aspects and any one of the possible implementations as set forth above, there is further provided an implementation, the steps of the improvement method including:
s1, dissolving lanthanum nitrate in deionized water, and stirring to prepare a first solution;
s2, adding the high-nickel material precursor into the first solution, and stirring to prepare a second solution;
s3, drying and grinding the second solution to obtain a coating sample precursor;
s4, uniformly grinding the coating sample precursor and lithium hydroxide monohydrate to obtain a grinding sample;
s5, calcining the grinding sample to obtain a high-nickel material coated by a lithium-oxygen double-ion conductor;
and S6, the high-nickel material obtained in the step S5 and the LATP solid electrolyte are used in the solid battery to realize battery performance after interface improvement.
In aspects and any one of the possible implementations described above, there is further provided an implementation, the lithium-oxygen double ion conductor is specifically La 4 NiLiO 8 。
In the aspects and any possible implementation manner as described above, there is further provided an implementation manner, where the concentration of the first solution in the step S1 is 0.01-0.03mol/L.
In the aspects and any possible implementation manner as described above, further provided is an implementation manner, where the high nickel material in step S2 has a chemical formula of LiNi 0.9 Co 0.05 Mn 0.05 O 2 。
In the aspect and any possible implementation manner as described above, there is further provided an implementation manner, and a specific manner of drying in step S3 is oil bath evaporation.
In aspects and any one of the possible implementations described above, there is further provided an implementation in which the oil bath is evaporated to dryness at a temperature of 80 ℃ to 100 ℃.
In the aspect and any possible implementation manner as described above, there is further provided an implementation manner, wherein the amount of the lithium-oxygen double ion conductor coated in the step S5 is 1wt% to 5wt% of the high nickel material.
In the aspect and any possible implementation manner as described above, there is further provided an implementation manner, where the parameters of the calcination processing in step S5 include: the atmosphere is oxygen, the calcination temperature is 800 ℃, and the calcination time is 12 hours.
In another aspect, the present invention provides a lithium aluminum titanium phosphate solid state battery that employs the improvement method described in any of the above to improve the interface problem between its high nickel positive electrode material and the LATP solid state electrolyte.
Compared with the prior art, one of the technical schemes has the following advantages or beneficial effects: the invention adopts a simple wet chemical deposition method to deposit lanthanum nitrate in situForming a uniform coating layer on the surface of the high-nickel positive electrode material, and annealing and calcining under a certain atmosphere to prepare the lithium-oxygen double-ion conductor La 4 NiLiO 8 Coated high nickel positive electrode material (NCM@La 4 NiLiO 8 )；
The other technical scheme has the following advantages or beneficial effects: the introduction of the lithium and oxygen double-ion conductor can simultaneously achieve the purposes of stabilizing the interface between the LATP and the NCM and stabilizing lattice oxygen, and effectively inhibit the cycle performance deterioration of the high-nickel positive electrode material for the lithium aluminum titanium phosphate solid-state battery.
Of course, it is not necessary for any of the products embodying the invention to achieve all of the technical effects described above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction (XRD) pattern of a high nickel positive electrode material for lithium aluminum titanium phosphate solid electrolyte batteries prepared in comparative example 1, example 2, example 3 and example 4 according to the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the initial high nickel positive electrode material for a lithium aluminum titanium phosphate solid state battery prepared according to comparative example 1 of the present invention;
FIG. 3 is a lithium-oxygen double ion conductor La prepared in example 3 of the present invention 4 NiLiO 8 Scanning Electron Microscope (SEM) images of coated high nickel positive electrode material for lithium titanium aluminum phosphate solid state batteries;
fig. 4 is a cycle performance test chart of the high nickel cathode materials for lithium aluminum titanium phosphate solid state batteries prepared in comparative example 1, example 2, example 3 and example 4 of the present invention;
FIG. 5 is a graph showing the fitting of the Ti 2p peaks on the surface of LATP for lithium aluminum titanium phosphate solid-state battery prepared in comparative example 1 of the present invention;
fig. 6 is a graph of a LATP surface Ti 2p peak fit for lithium aluminum titanium phosphate solid state battery prepared in example 3 of the present invention.
Detailed Description
For a better understanding of the technical solution of the present invention, the following detailed description of the embodiments of the present invention refers to the accompanying drawings.
It should be understood that the described embodiments are merely some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Aiming at the defects of the prior art, a great deal of research is carried out at present, and the stability of the material is mainly improved through pretreatment, doping modification, surface coating and the like. Wherein, the surface coating is a widely used method for improving the stability of the interface of the high nickel anode and the solid electrolyte, which can stabilize the surface structure of the material and inhibit side reactions. Therefore, from the point of view of the interface between the positive electrode and the solid electrolyte, it is proposed to introduce stable oxygen vacancies on the surface of the positive electrode material by using a lithium-oxygen double-ion conductor coating method, and capture and stabilize the high-activity oxygen formed at the interface during the cycle. Meanwhile, la coated on the surface of NCM material 4 NiLiO 8 (LNLO) reduces Ni during its cycling 2+ Is free of Ni 2+ With Ti 4+ Thereby improving the NCM-LATP interface problem and stabilizing the NCM and LATP structures.
The invention provides a surface-coated lithium-oxygen double-ion conductor La 4 NiLiO 8 The modification mode of (2) reduces Ni in the circulation process 2+ Is free of Ni 2+ With Ti 4+ Thereby improving the NCM-LATP interface problem; and by lithium and oxygen double ion conductor La 4 NiLiO 8 The oxygen vacancies and the oxygen gaps of the cathode material achieve the purpose of stabilizing high active oxygen in the cathode material. The method comprises the steps of depositing lanthanum nitrate on the surface of a high nickel positive electrode material (NCM) in situ, and then calcining a precursor material and lithium source under a certain atmosphere to obtain NCM@La 4 NiLiO 8 A composite material. The invention develops a modification method of a high-nickel anode material coated by a lithium-oxygen double-ion conductor and used for a lithium aluminum titanium phosphate solid-state battery by utilizing the advantages of simplicity and high efficiency of a wet chemical deposition method.
The modification method comprises the following steps:
(1) Dissolving lanthanum nitrate in deionized water, and stirring for 30min to obtain a solution A;
the concentration of the solution A is 0.01-0.03mol/L;
(2) Pouring the prepared high-nickel ternary positive electrode material precursor into the solution A, and stirring for 30min to obtain a solution B;
the chemical formula of the high nickel positive electrode material is LiNi 0.9 Co 0.05 Mn 0.05 O 2 ；
(3) Evaporating the solution B in an oil bath, evaporating to dryness, and grinding to obtain a coating sample precursor C;
the evaporating temperature of the oil bath is 80-100 ℃;
(4) Uniformly grinding the coating sample precursor C and lithium hydroxide monohydrate to obtain a grinding sample D;
(5) Calcining the ground sample D in a certain atmosphere, naturally cooling to room temperature to finally obtain the lithium-oxygen double-ion conductor La 4 NiLiO 8 Coated high nickel ternary positive electrode material;
lithium and oxygen double ion conductor La 4 NiLiO 8 The coating amount of the catalyst is 1 to 5 weight percent relative to the high nickel anode material;
the atmosphere is oxygen; the calcination temperature is 800 ℃; the calcination time was 12h.
The lithium-oxygen double-ion conductor La prepared by the method 4 NiLiO 8 The coated high-nickel positive electrode material can be used as an electrode material to be applied to a titanium aluminum lithium phosphate solid electrolyte battery.
The mechanism of the invention is as follows:
lithium and oxygen double ion conductor La 4 NiLiO 8 Exhibits a higher structural flexibility in terms of oxygen stoichiometry. When the high nickel anode material is in a high lithium removal state, the lithium and oxygen double ion conductor La 4 NiLiO 8 The abundant oxygen vacancies in the catalyst can be trapped by the surfaceReactive oxygen species generated by the reverse reaction. In addition, the high-activity oxygen-containing substances escaping from the surface can also be absorbed and stored in the lithium-oxygen double-ion conductor La 4 NiLiO 8 In the oxygen gaps of the layers, by incorporating the oxygen gaps into the crystal lattice, excess oxygen can be contained, preventing the release of oxygen, thereby improving the safety performance of the battery. And lithium and oxygen double ion conductor La 4 NiLiO 8 The Li vacancies in the coating provide a rapid path for lithium ions to pass through the coating, thereby effectively alleviating capacity loss. And La (La) 4 NiLiO 8 The layer effectively isolates Ni in NCM 2+ And Ti in LATP 4+ Avoiding the reaction of Ti 4+ Is reduced to Ti 3+ The high nickel anode material and the solid electrolyte structure of the lithium aluminum titanium phosphate are stabilized, and the NCM-LATP interface problem is further improved. Therefore, the surface coating modification of the lithium and oxygen double-ion conductor is beneficial to improving the lithium ion transmission efficiency of the material, reducing the removal of lattice oxygen, stabilizing the high-nickel anode material and the solid electrolyte structure of the lithium aluminum titanium phosphate, and improving the electrochemical performance of the lithium aluminum titanium phosphate solid battery.
Comparative example 1: the preparation method of the original high-nickel positive electrode material comprises the following steps:
(1) Uniformly grinding 2g of the prepared high-nickel positive electrode material precursor and lithium hydroxide monohydrate to obtain a grinding sample;
(2) And (3) calcining the grinding sample in an oxygen atmosphere at 800 ℃ for 12 hours, and naturally cooling to room temperature to finally obtain the original high-nickel anode material.
Example 2: lithium and oxygen double-ion conductor La 4 NiLiO 8 The modification method of the coated high-nickel positive electrode material comprises the following steps:
1) Dissolving 0.0116g of lanthanum nitrate in deionized water, and stirring for 30min to obtain solution A;
2) Pouring the prepared high-nickel ternary positive electrode material precursor into the solution A, and stirring for 30min to obtain a solution B;
3) Placing the solution B in an oil bath at 90 ℃ under stirring, evaporating to dryness, and grinding after evaporating to dryness to obtain a coating sample precursor C;
4) Uniformly grinding the coating sample precursor C and lithium hydroxide monohydrate to obtain a grinding sample D;
5) Calcining the ground sample D at 800 ℃ for 12 hours in an oxygen atmosphere, naturally cooling to room temperature, and finally obtaining the lithium-oxygen double-ion conductor La 4 NiLiO 8 Coated high nickel ternary positive electrode material, wherein lithium and oxygen double ion conductor La 4 NiLiO 8 The coating amount was 1wt%.
Example 3: lithium and oxygen double-ion conductor La 4 NiLiO 8 The modification method of the coated high-nickel positive electrode material comprises the following steps:
1) 0.0347g of lanthanum nitrate is dissolved in deionized water and stirred for 30min to prepare solution A;
2) Pouring the prepared high-nickel ternary positive electrode material precursor into the solution A, and stirring for 30min to obtain a solution B;
3) Placing the solution B in an oil bath at 90 ℃ under stirring, evaporating to dryness, and grinding after evaporating to dryness to obtain a coating sample precursor C;
4) Uniformly grinding the coating sample precursor C and lithium hydroxide monohydrate to obtain a grinding sample D;
5) Calcining the ground sample D at 800 ℃ for 12 hours in an oxygen atmosphere, naturally cooling to room temperature, and finally obtaining the lithium-oxygen double-ion conductor La 4 NiLiO 8 Coated high nickel ternary positive electrode material, wherein lithium and oxygen double ion conductor La 4 NiLiO 8 The coating amount was 3wt%.
Example 4: lithium and oxygen double-ion conductor La 4 NiLiO 8 The modification method of the coated high-nickel positive electrode material comprises the following steps:
1) 0.0578g of lanthanum nitrate is dissolved in deionized water and stirred for 30min to prepare solution A;
2) Pouring the prepared high-nickel ternary positive electrode material precursor into the solution A, and stirring for 30min to obtain a solution B;
3) Placing the solution B in an oil bath at 90 ℃ under stirring, evaporating to dryness, and grinding after evaporating to dryness to obtain a coating sample precursor C;
4) Uniformly grinding the coating sample precursor C and lithium hydroxide monohydrate to obtain a grinding sample D;
5) Calcining the ground sample D at 800 ℃ for 12 hours in an oxygen atmosphere, and naturally cooling toAt room temperature, finally obtaining the lithium-oxygen double-ion conductor La 4 NiLiO 8 Coated high nickel ternary positive electrode material, wherein lithium and oxygen double ion conductor La 4 NiLiO 8 The coating amount was 5wt%.
Test case
And (3) half-cell assembly: the high nickel cathode materials prepared in comparative example 1, example 2, example 3 and example 4 were mixed with Super P and PVDF in mass ratio 75:15:10, pulping and coating, cutting into pole pieces with the diameter of 12mm, taking metal lithium as a negative electrode, adopting a LATP solid electrolyte synthesized by a solid-phase sintering method, and assembling into a half cell in an argon glove box.
And (3) charge and discharge testing: the voltage range of the button cell for charging and discharging is 2.8-4.3V, the smaller current density of 6mA/g is adopted for twice activation before the cycle test, and then the charge and discharge cycle test is carried out at the current density of 18mA/g (0.1C) in the same voltage range. All electrochemical performance tests were performed at room temperature.
FIG. 1 is an X-ray diffraction (XRD) pattern of a high nickel positive electrode material for lithium titanium aluminum phosphate solid-state batteries prepared in comparative example 1, example 2, example 3 and example 4, and it can be seen that four materials all belong to a layered alpha-NaFeO of R-3m space group 2 Structure is as follows. The high nickel positive electrode materials prepared in example 2, example 3 and example 4 all exhibited four low intensity diffraction peaks between 20-35 deg., all of which were attributed to the lithium and oxygen double ion conductor La 4 NiLiO 8 (PDF # 52-1671) shows that the surface of the high nickel positive electrode material is successfully coated with the lithium and oxygen double ion conductor La 4 NiLiO 8 . (003) And (104) the diffraction peaks were narrow and sharp, indicating that the material was well crystalline, and the (006)/(102) and (018)/(110) diffraction peaks were clearly split, indicating that the material had a good layered structure.
By comparing fig. 2 and 3, which represent SEM images of the high-nickel cathode materials for lithium aluminum titanium phosphate solid-state batteries prepared in comparative examples 1 and 3, respectively, it can be seen that the high-nickel cathode material prepared in comparative example 1 has a spherical structure with a particle size distribution of about 10 μm. And lithium and oxygen double ion conductor La 4 NiLiO 8 Cladding examples3, a small amount of nano particles are attached to the surface of the particles (as shown in figure 3), indicating that the lithium and oxygen double ion conductor La 4 NiLiO 8 The surface of the high nickel positive electrode material is successfully coated.
FIG. 4 is a graph showing the cycle performance of the high nickel positive electrode materials for lithium titanium aluminum phosphate solid state batteries prepared in comparative example 1, example 2, example 3 and example 4 after being assembled into half batteries, and it can be seen that the lithium and oxygen double ion conductor La 4 NiLiO 8 The capacity retention rate of the coated high-nickel positive electrode material is obviously improved. The discharge specific capacity of the comparative example 1 after 100 cycles is only 97mAh/g, and the capacity of the high nickel cathode material prepared in example 3 after 100 cycles is 150.89mAh/g. Thus, the lithium-oxygen double ion conductor La 4 NiLiO 8 The coating can effectively stabilize the material structure, relieve NCM-LATP interface reaction and improve the circulation stability.
Fig. 5 and 6 are fitted graphs of the Ti 2p peaks on the surface of LATP after the high-nickel cathode materials prepared in comparative example 1 and example 3 are assembled into a half cell cycle of 100 cycles. Ti was detected at the interface of NCM-LATP in comparative example 1 3+ Signals (fig. 5). However, in example 3 no Ti was detected at the LNLO-3@NCM-LATP interface 3+ Is shown (fig. 6). This indicates that the lithium and oxygen double ion conductor La 4 NiLiO 8 Coating can effectively relieve Ti 4+ And Ni 2+ Is reacted to form Ti 3+ Thereby achieving the purpose of stabilizing the NCM-LATP interface.
The modification method of the high-nickel positive electrode material for the lithium aluminum titanium phosphate solid-state battery, which is coated by the lithium and oxygen double-ion conductor and provided by the embodiment of the application, is described in detail. The above description of embodiments is only for aiding in understanding the method of the present application and its core ideas; meanwhile, as those skilled in the art will have modifications in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such product or system. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a commodity or system comprising such elements. By "substantially" is meant that within an acceptable error range, a person skilled in the art is able to solve the technical problem within a certain error range, substantially achieving the technical effect.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. The specific meaning of these terms in this application will be understood by those of ordinary skill in the art as appropriate. The term "and/or" as used herein is merely one association relationship describing the associated object, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.

Claims (7)

1. A method for improving interface between high-nickel material and LATP solid electrolyte is characterized in that the improvement method is characterized in that lithium and oxygen double-ion conductors are coated on the surface of the high-nickel material, so that Ni in the circulation process is reduced 2+ Improving the interface problem between the high nickel material and the LATP solid electrolyte;
the improvement method comprises the following steps:
s1, dissolving lanthanum nitrate in deionized water, and stirring to prepare a first solution;
s2, adding the high-nickel material precursor into the first solution, and stirring to prepare a second solution;
s3, drying and grinding the second solution to obtain a coating sample precursor;
s4, uniformly grinding the coating sample precursor and lithium hydroxide monohydrate to obtain a grinding sample;
s5, calcining the grinding sample to obtain a high-nickel material coated by a lithium-oxygen double-ion conductor;
s6, the high nickel material obtained in the S5 and the LATP solid electrolyte are used in the solid battery to realize battery performance after interface improvement;
the lithium and oxygen double ion conductor is La 4 NiLiO 8 ，
The chemical formula of the high nickel material is LiNi 0.9 Co 0.05 Mn 0.05 O 2 ，
The amount of the lithium and oxygen double-ion conductor coated in the step S5 is 1-5 wt% of the high-nickel material.
2. The method for improving the interface between a high nickel material and a LATP solid electrolyte according to claim 1, wherein the concentration of the first solution in the step S1 is 0.01 to 0.03mol/L.
3. The method for improving the interface between a high nickel material and a LATP solid electrolyte according to claim 1, wherein the specific manner of drying in step S3 is oil bath evaporation.
4. The method for improving the interface between a high nickel material and a LATP solid electrolyte according to claim 3, wherein the temperature of the oil bath evaporating to dryness is 80 ℃ to 100 ℃.
5. The method for improving the interface between a high nickel material and a LATP solid electrolyte according to claim 1, wherein the amount of the lithium, oxygen double ion conductor coated in step S5 is 3wt% of the high nickel material.
6. The method for improving the interface between a high nickel material and a LATP solid electrolyte according to claim 1, wherein the parameters of the calcination process in step S5 include: the atmosphere is oxygen, the calcination temperature is 800 ℃, and the calcination time is 12 hours.
7. A lithium titanium aluminum phosphate solid state battery, characterized in that the lithium titanium aluminum phosphate solid state battery adopts the improvement method according to any one of claims 1 to 6 to improve the interface problem between the high nickel positive electrode material and the LATP solid state electrolyte.
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