CN117334997B - Inorganic nitride and organosilane composite solid electrolyte and preparation method and application thereof - Google Patents

Inorganic nitride and organosilane composite solid electrolyte and preparation method and application thereof Download PDF

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CN117334997B
CN117334997B CN202311389322.5A CN202311389322A CN117334997B CN 117334997 B CN117334997 B CN 117334997B CN 202311389322 A CN202311389322 A CN 202311389322A CN 117334997 B CN117334997 B CN 117334997B
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inorganic nitride
lithium
organosiloxane
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solid electrolyte
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范修林
马宝琛
张海阔
陈立新
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Zhejiang University ZJU
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Abstract

The application provides an inorganic nitride and organosilane composite solid electrolyte, and a preparation method and application thereof, and belongs to the technical field of inorganic and organic solid mixed electrolytes. Is compounded by inorganic nitride and organosilane, wherein the inorganic nitride is expressed as: (Li 3N)x(MOn)y(LiR)1‑x‑y, the percentage of inorganic nitride relative to organosilane is 5-25 wt%), the composite solid electrolyte has the characteristics of high ionic conductivity, wide electrochemical window and high mechanical strength, the electrochemical window can reach more than 4.5V, the ionic conductivity reaches more than 10 ‑4 S/cm, and the application prospect in all-solid lithium metal batteries is wide.

Description

Inorganic nitride and organosilane composite solid electrolyte and preparation method and application thereof
Technical Field
The application relates to an inorganic nitride and organosilane composite solid electrolyte, and a preparation method and application thereof, belonging to the technical field of inorganic and organic solid mixed electrolytes.
Background
In recent years, lithium metal solid-state batteries have received much greater attention and research than conventional graphite lithium ion batteries due to their higher battery energy density (> 300 Wh/kg). And the key point of the stable and efficient operation of the all-solid-state battery is whether to match the solid-state electrolyte compatible with the anode and the cathode.
The solid electrolytes reported so far mainly include both inorganic solid electrolytes and polymer solid electrolytes, but the solid electrolytes disclosed herein have advantages and disadvantages:
The inorganic solid electrolyte mainly comprises solid electrolytes in the forms of oxides, sulfides, halides and the like, the ionic conductivity level of the inorganic solid electrolyte is greatly improved and broken through, and the basic requirement (10 < -4 > S/cm) of battery circulation is met; however, due to poor contact of the inorganic solid electrolyte with lithium metal, uneven deposition current on the negative side can lead to lithium dendrite growth, ultimately leading to cell failure shorting.
The polymer solid electrolyte has more excellent interface wettability, can greatly reduce interface impedance and stabilize uniform deposition of lithium ions on the negative electrode side. However, the current polymer electrolytes suffer from their lower room temperature ionic conductivity and narrower electrochemical window. Such as: a widely studied polymer system of Polyoxyethylene (PEO) has good stability to lithium metal, but its room temperature ion conductivity is only 10 -6 S/cm and decomposition occurs at around 3.9V (vs Li +/Li), so it is difficult to apply it to positive electrode materials such as high-voltage lithium nickel manganese cobalt oxide ternary, lithium nickel manganese oxide, and lithium cobalt oxide.
Disclosure of Invention
In view of the above, the application firstly provides an inorganic nitride and organosilane composite solid electrolyte, which not only improves the ionic conductivity of polymer organic electrolyte through the composite of organic and inorganic electrolyte, but also effectively solves the problems of serious side reactions of lithium metal cathode side and electrolyte and the like by taking organosilane, in particular siloxane polymer system as polymer organic electrolyte.
Specifically, the application is realized by the following scheme:
an inorganic nitride and organic silicon composite solid electrolyte is formed by compositing inorganic nitride and organic silane,
The inorganic nitride is expressed as: (Li 3N)x(MOn)y(LiR)1-x-y, wherein:
X is more than or equal to 0.1 and less than or equal to 0.3,0.2 and y is more than or equal to 0.5, n is the amount of oxygen element required to satisfy the stoichiometric ratio,
M is at least one of lithium, boron, sodium, aluminum, silicon, phosphorus, calcium, scandium, titanium, vanadium, chromium, manganese, gallium, germanium, arsenic, zirconium, tin, antimony, lanthanum, barium and bismuth,
R is at least one of halogen elements;
the monomers of the organosilane are expressed as: Wherein:
R 1、R2、R3 is independently selected from at least one of alkoxy, fluoroalkyl, halogen, alkyl substituted phenyl or halogenated benzene ring;
The percentage of inorganic nitride relative to organosilane is 5-25 wt%.
The composite solid electrolyte has the characteristics of high ionic conductivity, wide electrochemical window and high mechanical strength, the electrochemical window can reach more than 4.5V, the ionic conductivity can reach more than 10 -4 S/cm, and the application prospect in all-solid lithium metal batteries is wide.
Further, as preferable:
In the inorganic nitride, R is any one of fluorine, chlorine, bromine and iodine.
In the inorganic nitride, x=0.2, y=0.3, M is any one of lithium, aluminum, silicon and calcium, and R is any one of chlorine, bromine and iodine.
The inorganic nitride is any one of (Li3N)0.2(Li2O)0.3(LiCl)0.5、(Li3N)0.2(Li2O)0.3(LiI)0.5、(Li3N)0.3(Li2O)0.4(LiI)0.3(Li3N)0.3、(Li3N)0.3(Li2O)0.4(LiCl)0.3.
The percentage of the inorganic nitride relative to the organosilane is 10-15 wt%.
The monomer of the organosilane is a vinyl siloxane compound, more preferably, the monomer of the organosilane is at least one of vinyl trimethoxy silane, vinyl triethoxy silane, methyl vinyl dimethoxy silane, propenyl trimethoxy silane, vinyl tri (2-methoxyethoxy) silane and vinyl tri [ (1-methylvinyl) oxy ] silane.
The second aspect of the applicant aims to provide a preparation method of the composite solid electrolyte, which comprises the following steps:
Step one, preparing inorganic nitride: the method comprises the steps of taking lithium nitride Li 3 N, oxide MO n and lithium halide LiR as raw materials, uniformly mixing the three raw materials through a ball milling mechanical method, performing preliminary reaction, tabletting, and performing heat treatment under the protection of N 2 atmosphere to obtain inorganic nitride powder.
Preferably:
The adding mole ratio of the lithium nitride Li 3 N, the oxide MO n and the lithium halide LiR is 1-3:2-5:2-8.
The ball-material ratio is controlled to be 20-25:1, and the ball milling time is 6-10 h.
The heat treatment temperature is 300-500 ℃ and the treatment time is 6-8 h.
Step two: preparing a precursor liquid: adding the inorganic nitride powder obtained in the first step into an organic electrolyte monomer, adding lithium salt and an initiator, wherein the addition amount of the inorganic solid electrolyte relative to the organic electrolyte monomer is 5-25 wt%, and the molar concentration of the lithium salt relative to the electrolyte monomer is 3-6 mol/L, and uniformly mixing to obtain the precursor liquid. The lithium salt is added in the preparation process, so that on one hand, the crystallinity of the polymer can be effectively reduced, a cooperative ion transmission mode among polymer chain segments is formed, and the ion conductivity of the whole composite polymer electrolyte is improved; on the other hand, the coordination of the Li ions and the polymer chain segments can inhibit the oxidative decomposition of a polymer network at the positive electrode side, preferentially form a LiF-rich SEI component which is mainly decomposed by FSI - at the negative electrode side, effectively passivate the surface of lithium metal and inhibit the continuous side reaction of electrolyte and the lithium metal negative electrode.
Preferably:
The lithium salt is at least one selected from lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium oxalato-borate, lithium difluoro-oxalato-borate, lithium hexafluorophosphate and lithium tetrafluoroborate.
Step three: organic-inorganic compounding: and taking the glass fiber diaphragm as a carrier, fully infiltrating precursor liquid, and thermally polymerizing under the protection of inert atmosphere to obtain the composite solid electrolyte of inorganic nitride and organosilane.
The thermal polymerization temperature is 70-100 ℃, and the treatment time is 6-8 h.
Compared with the high-temperature sintered oxide solid electrolyte, the organic-inorganic composite solid electrolyte can be prepared in a combined mode of a ball milling method and a low-temperature atmosphere sintering method, so that the low-cost mass preparation of the composite solid electrolyte is finished, and the preparation process is simple; compared with sulfide solid electrolyte which is easy to decompose and release toxic gas of hydrogen sulfide, the organic-inorganic composite solid electrolyte has the advantages that raw materials adopted in the preparation process are not easy to volatilize, the electrolyte is environment-friendly, and the safety and the high efficiency of a synthesis process can be greatly improved.
It is an object of the third aspect of the applicant to provide the use of the above composite solid state electrolyte as an electrolyte for an all solid state lithium metal battery, such as a Li/Al, li/Li or Li/LiNi 0.8Co0.1Mn0.1O2 battery.
The inorganic component in the composite solid electrolyte is in a lithium intercalation saturated state, the nitride of the inorganic component has the characteristic of thermodynamic stability on a lithium metal anode, and the polysilane of the organic component has good reduction resistance stability, has good interface wettability, reduces interface impedance, and can inhibit side reaction of a solid electrolyte interface; the electrolyte has good mechanical strength, can inhibit the growth and puncture of lithium dendrite, can realize long cycle life and high coulombic efficiency of a lithium battery when used in an all-solid-state lithium ion battery, has good compatibility with a lithium metal negative electrode, has good ion conductivity, greatly improves the cycle life of the all-solid-state lithium metal battery, and has good practicability.
Drawings
FIG. 1 is a graph showing the cycle performance test of the composite solid electrolyte prepared in example 1 when it is used for assembling a Li/Li symmetrical battery;
FIG. 2 is a graph showing the cycle performance test of the composite solid electrolyte prepared in example 2 when it is used to assemble a Li/Li symmetrical battery;
FIG. 3 is a graph showing the cycle performance test of the composite solid electrolyte prepared in example 3 when it is used to assemble a Li/Li symmetrical battery;
FIG. 4 is a graph showing the cycle performance test of the composite solid electrolyte prepared in example 4 when it was used to assemble a Li/Li symmetrical battery;
FIG. 5 is a graph showing the cycle performance test of the electrolyte prepared in comparative example 1 when it was used to assemble a Li/Li symmetric battery;
FIG. 6 is a graph showing the cycle performance test of the electrolyte prepared in comparative example 2 when it is used to assemble a Li/Li symmetric battery;
FIG. 7 is a graph showing the cycle performance test of the composite solid electrolyte prepared in example 1 when it was used to assemble Li/LiNi 0.8Co0.1Mn0.1 lithium metal batteries;
FIG. 8 is a graph showing the cycle performance test of the composite solid electrolyte prepared in example 2 when it was used to assemble a Li/LiNi 0.8Co0.1Mn0.1 lithium metal battery;
FIG. 9 is a graph showing the cycle performance test of the composite solid electrolyte prepared in example 3 when it was used to assemble a Li/LiNi 0.8Co0.1Mn0.1 lithium metal battery;
FIG. 10 is a graph showing the cycle performance test of the composite solid electrolyte prepared in example 4 when it was used to assemble a Li/LiNi 0.8Co0.1Mn0.1 lithium metal battery;
FIG. 11 is a graph showing the cycle performance test of the electrolyte prepared in comparative example 3 when used in the assembly of a Li/LiNi 0.8Co0.1Mn0.1 lithium metal battery;
fig. 12 is a graph showing the cycle performance test of the electrolyte prepared in comparative example 4 when it was used to assemble Li/LiNi 0.8Co0.1Mn0.1 lithium metal batteries.
Detailed Description
Example 1
The method for preparing the inorganic nitride and organosilane composite solid electrolyte comprises the following steps of:
(1) In a glove box in an argon atmosphere, placing raw materials of lithium nitride, lithium oxide and lithium chloride in a mortar according to a molar ratio of 2:3:5, pre-grinding and mixing for 0.5h, and placing the mixed powder in an agate ball milling tank, wherein the ball-material ratio is 25:1, and the vibration ball milling time is 8h. And cold pressing the ball-milled precursor powder into a wafer by a tablet press under 300Mpa pressure, placing the wafer in a metal nickel crucible, performing heat treatment for 6 hours at 300 ℃ in a tube furnace in a nitrogen atmosphere, taking out the block, putting the block in a glove box, and grinding the block in a mortar for 0.5 hour again to obtain the nitride solid electrolyte powder.
(2) 1Ml of organosilane monomer vinyl tri (2-methoxyethoxy) silane (VTMS) is taken and placed in a strain bottle, and 3mol/L of lithium difluorosulfimide salt, 0.3wt% of initiator azodiisobutyronitrile and 10wt% of halide solid electrolyte powder are added, and after magnetic stirring for 1h at room temperature, halide composite electrolyte precursor liquid for thermal polymerization is obtained.
Wherein, the structural formula of the vinyl tri (2-methoxyethoxy) silane is as follows:
(3) And (3) dripping 100 mu L of halide composite electrolyte precursor liquid onto the surface of the glass fiber membrane to fully infiltrate the glass fiber membrane, and then placing the glass fiber membrane in an environment of 80 ℃ for thermal polymerization to prepare the halide organic composite solid electrolyte.
Example 2
This embodiment is identical to the arrangement of embodiment 1, except that: in step (1), lithium chloride is replaced with lithium iodide.
Example 3
This embodiment is identical to the arrangement of embodiment 1, except that: in the step (1), the lithium oxide is replaced by calcium oxide, and the heat treatment temperature is 400 ℃.
Example 4
This embodiment is identical to the arrangement of embodiment 1, except that: the lithium oxide in step (1) is replaced by germanium oxide, and the heat treatment temperature is 500 ℃.
Example 5
This embodiment is identical to the arrangement of embodiment 1, except that: in the step (1), the molar ratio of the lithium nitride to the lithium oxide to the lithium chloride is 3:4:3.
Example 6
This embodiment is identical to the arrangement of embodiment 1, except that: in step (2), the organosilane monomer is vinyltris (1-methoxy-2-propoxy) silane (VMPS).
The structural formula of the vinyl tri (1-methoxy-2-propoxy) silane is as follows:
Example 7
This embodiment is identical to the arrangement of embodiment 1, except that: in step (2), the organosilane monomer is tri-t-butoxyvinylsilane (VTBS).
The tri-tert-butoxyvinylsilane has the structural formula:
example 8
This embodiment is identical to the arrangement of embodiment 1, except that: in the step (2), the organosilane monomer is vinyltriethoxysilane (TVS).
The vinyl triethoxysilane has the structural formula:
example 9
This case is identical to the setup of example 1, except that: the mass percentage of the nitride solid electrolyte powder added to the monomer precursor liquid was 5wt%.
Example 10
This case is identical to the setup of example 1, except that: the mass percentage of the nitride solid electrolyte powder added into the monomer precursor liquid is 20wt%.
Comparative example 1
The preparation method of the electrolyte in the case is as follows:
In a glove box in an argon atmosphere, mixing lithium nitride and lithium oxide raw materials according to a molar ratio of 1:1, placing the mixture in a mortar, pre-grinding and mixing for 0.5h, and then placing the mixed powder in an agate ball milling tank, wherein the ball-material ratio is 25:1, and the vibration ball milling time is 8h. And cold pressing the ball-milled precursor powder into a wafer by a tablet press under the pressure of 300Mpa, placing the wafer into a metal nickel crucible, and carrying out heat treatment for 8 hours at 300 ℃ in a tube furnace in which nitrogen is introduced, and then grinding again to obtain the solid electrolyte powder. 1ml of silane monomer vinyl tri (2-methoxyethoxy) silane is taken and placed in a strain bottle, 3mol/L of lithium difluorosulfonimide salt, 0.3wt% of initiator azodiisobutyronitrile and 10wt% of halide solid electrolyte powder are added, and after magnetic stirring is carried out at room temperature for 1h, halide composite electrolyte precursor liquid for thermal polymerization is obtained. 100 mu L of prepolymer is dripped on the surface of a glass fiber diaphragm to be fully soaked, and then the glass fiber diaphragm is placed in an environment of 80 ℃ for thermal polymerization, so that the solid electrolyte is prepared.
Comparative example 2
The scheme is the same as that of comparative example 1, and the difference is that: the molar ratio of the lithium nitride to the lithium chloride is 1:1.
Comparative example 3
This case was identical to the setting of comparative example 1, except that: vinyl tris (2-methoxyethoxy) silane was replaced with polyoxyethylene (PEO, molecular weight 50 w).
Comparative example 4
This case was identical to the setting of comparative example 1, except that: no nitride solid electrolyte powder is added to the monomer precursor liquid.
Performance tests were performed on the electrolytes prepared in the above examples and comparative examples, and Li/Al, li/Li, and Li/LiNi 0.8Co0.1Mn0.1O2 batteries were fabricated and tested:
(1) Positive electrode side: uniformly mixing LiNi 0.8Co0.1Mn0.1O2, carbon black and PVDF binder according to the mass ratio of 96:2:2, then scraping the mixture on an aluminum foil, and drying the mixture for 12 hours at 80 ℃;
(2) Li negative electrode: adopting a metal lithium sheet with the diameter of 10mm and the thickness of 400 mu m;
(3) Solid electrolyte: the electrolytes prepared in examples 1 to 10 or comparative examples 1 to 4 were used;
(4) And (3) battery assembly: in a glove box (O 2<0.1ppm,H2 O <0.1 ppm), assembling according to the sequence of 2032 positive electrode shell-positive electrode plate-solid electrolyte membrane-lithium metal negative electrode plate-gasket-elastic plate-2032 negative electrode shell to obtain a button cell;
(5) The performance of the solid electrolyte contained in the button cell was tested.
1. Ion conductivity
The solid electrolytes prepared in examples 1 to 10 and comparative examples 1 to 4 were subjected to ac impedance method to test their ionic conductivity, test method: the solid state electrolytes prepared in examples 1 to 10 and comparative examples 1 to 4, whose ion conductivity data at room temperature are shown in Table 1, were prepared using stainless steel as symmetric electrodes at both ends at a test frequency of 100kHz to 0.1 Hz.
Table 1: electrolyte ionic conductivity comparison table prepared by different schemes
Solid electrolyte Ion conductivity Voltage window
Example 1 (Li3N)2(Li2O)3(LiCl)5-VTMS 5.9×10-4S/cm >4.6V
Example 2 (Li3N)2(Li2O)3(LiI)5-VTMS 4×10-4S/cm >4.5V
Example 3 (Li3N)2(CaO)3(LiCl)5-VTMS 3.6×10-4S/cm >4.7V
Example 4 (Li3N)2(GeO2)3(LiCl)5-VTMS 3.8×10-4S/cm >4.5V
Example 5 (Li3N)3(Li2O)4(LiCl)3-VTMS 4.5×10-4S/cm >4.8V
Example 6 (Li3N)2(Li2O)3(LiCl)5-VMPS 4.9×10-4S/cm >4.5V
Example 7 (Li3N)2(Li2O)3(LiCl)5-VTBS 2×10-4S/cm >4.5V
Example 8 (Li3N)2(Li2O)3(LiCl)5-TVS 1.5×10-4S/cm >4.6V
Example 9 5wt％(Li3N)2(Li2O)3(LiCl)5-VTMS 2×10-4S/cm >4.6V
Example 10 20wt％(Li3N)2(Li2O)3(LiCl)5-VTMS 3.2×10-4S/cm >4.5V
Comparative example 1 (Li3N)1(LiO)1-VTMS 6.3×10-5S/cm >4.2V
Comparative example 2 (Li3N)1(LiCl)1-VTMS 7.8×10-5S/cm >4.5V
Comparative example 3 (Li3N)1(LiO)1-PEO 5×10-5S/cm >4V
Comparative example 4 VTMS 6×10-5S/cm >4.7V
。
As can be seen from the data in Table 1, the inorganic nitride and organosilane composite solid electrolytes prepared in examples 1 to 10 have ion conductivities of 10 -4 S/cm, which indicates that the nitride and polysiloxane composite solid electrolytes prepared in the scheme have higher ion conductivities, and the electrochemical windows are all larger than 4.5V, which indicates that the composite solid electrolytes prepared in the examples can be matched with high-voltage positive electrode materials.
The test structures of comparative examples 1 to 4 show that the ionic conductivity is lower than the order of magnitude of 10 -4 S/cm, which indicates that the ionic conductivity level of the electrolyte can be effectively improved after the nitride solid electrolyte is compounded with the silane polymer electrolyte relative to a single component.
Meanwhile, in the experimental process, we can also see that the influence of each component of the composite solid electrolyte on the performance is also different:
(1) Under the same conditions, the improvement effect on the ionic conductivity and the voltage window of the halide is better when R is chlorine than when R is iodine, and the method is particularly shown in the examples 1 and 2. When the halogen doping amount is high (the raw material accounts for 50mol percent), compared with iodine ions, the chlorine ions have weaker blocking effect on an ion passage due to smaller ion radius, the ion migration barrier is low, and the ion conductivity is higher; and because the chlorine ion has larger electronegativity, the integral interatomic bonding energy is higher after participating in forming an anion framework, and the oxidation resistance is stronger than that of an iodide ion framework, so that the voltage window can be further widened.
(2) Under the same conditions, when M in the oxide is lithium, the heat treatment condition is mild, especially the treatment temperature is far lower than that when M is other elements such as calcium and germanium, and the ion conductivity improvement effect is better; however, when M is calcium, the improvement of the voltage window is preferable, and examples 1,2 and 3 are specifically described. Lithium oxide can provide more lithium element ratio and lithium migration sites, and is more beneficial to migration and diffusion of lithium ions in a crystal lattice than other metal cation systems.
(3) Under the same conditions, the organosilane has different substituents and different effects of improving ion conductivity and voltage window, and when the organosilane is a siloxane polymer system (such as vinyl siloxane compound), the ionic conductivity and the voltage window parameters are ideal, wherein the vinyl tri (2-methoxyethoxy) silane has the best effect as shown in the combination of the embodiment 1 and the embodiments 6, 7 and 8. This is because vinyltris (2-methoxyethoxy) silane itself has a longer ether segment and more lithium ion coordination sites, readily forms a coupling solvation effect, more fully dissociates the lithium salt and increases the ionic conductivity of the polymer network.
(4) The effect of the addition amount of the inorganic nitride to the organosilane monomer was very remarkable, and the ionic conductivity was far lower than that of example 1, although the voltage window level was the same as that of example 1, when the addition amount of the inorganic nitride was 5wt% in example 9 and the addition amount of the inorganic nitride was 5wt% in example 10, respectively, with the same composition. The main reason is that inorganic nitride is used as an active inorganic filler (inorganic substance with intrinsic ion conduction property), on one hand, the crystallinity of a polymer network can be reduced, and on the other hand, a lithium ion rapid migration mode at the interface of a polymer chain and inorganic substance particles is formed through Lewis acid-base effect, so that the ion conductivity of the composite solid electrolyte is effectively improved.
2. Cycling curve in Li/Li symmetric cells
Fig. 1 to 6 are cycle curves of lithium (Li/Li) symmetrical batteries corresponding to the composite solid state electrolytes of examples 1 to 4 and comparative examples 1 to 2, respectively, circulating at room temperature (25 ℃) at a current density of 0.1mA/cm 2, and it can be seen that: the composite solid electrolytes of examples 1 to 3 can be stably circulated for a period of time exceeding 200 hours (see fig. 1 to 3); whereas example 4 was stable for more than 150 hours (see fig. 4), it was demonstrated that the nitride organic composite solid state electrolytes of examples 1 to 4 had good ability to inhibit lithium dendrite growth.
The single nitride solid electrolyte and the silane polymer dielectric composite (comparative example 1 and comparative example 2) can not effectively inhibit the growth of lithium dendrites, the cycle performance of the lithium dendrite is poor in a Li/Li symmetrical battery, and the stable cycle duration can only be kept within 50 hours (see fig. 5 and 6).
Meanwhile, the applicant also counted the cycle curves of examples 5 to 10 in Li/Li symmetric cells, which correspond to composite solid electrolytes exhibiting the same inhibition effect on lithium dendrite growth.
3. Cycle life curve in Li/LiNi 0.8Co0.1Mn0.1O2 cell
Fig. 7 to 12 are test results of the lithium metal batteries Li/LiNi 0.8Co0.1Mn0.1O2 (3-4.3V) corresponding to the nitride solid-state electrolytes in examples 1 to 4 and comparative examples 3 to 4, respectively, simulating the cycling of the solid-state batteries at room temperature (25 ℃) at a rate of 0.2C.
Table 2: comparison table of cyclic test results of batteries prepared by different schemes
Capacity retention rate Coulombic efficiency
Example 1 93％ 99.9% Or more
Example 2 95％ 99.9% Or more
Example 3 92％ 99.9% Or more
Example 4 90％ 99.6% Or more
Comparative example 3 65％ 99% Or more
Comparative example 4 85％ 99.5% Or more
。
As can be seen by comparing fig. 7 to 10 with table 2: the composite solid electrolyte of the nitride solid electrolyte and the polysiloxane electrolyte in examples 1 to 4 is adopted, and after the composite solid electrolyte circulates for 100 cycles in a Li/LiNi 0.8Co0.1Mn0.1O2 battery, the capacity retention rate is above 90 percent and can reach 95 percent at most (see figure 8); the coulomb efficiency is as high as more than 99.9 percent. Compared with the traditional single oxide or sulfide solid electrolyte, the cycle capacity retention rate and the coulombic efficiency are greatly improved.
With PEO-based composite solid state batteries, after 100 cycles (see fig. 11), the capacity retention was only 65% or more, the coulombic efficiency was only 99%, far below that of the examples, indicating a rapid capacity decay due to poor oxidation resistance (< 4V) and incompatibility with high voltage positive electrode materials.
When only a VTMS-based polymer electrolyte was used (see fig. 12), the cell polarization was large due to its low conductivity, the initial specific discharge capacity (166 mAh/g) was lower than that of examples 1 to 4 as a solid electrolyte, and the 100-turn capacity retention was 85%.
From the above, it can be seen that: the inorganic nitride and organosilane composite solid electrolyte provided by the application has better lithium metal negative electrode side matching property and high-voltage positive electrode side compatibility, and can realize the stable circulation of a lithium metal all-solid battery.

Claims (10)

1. An inorganic nitride and organosiloxane composite solid electrolyte, characterized in that:
The inorganic nitride is (Li 3N）x（MOn）y（LiR）1-x-y,
0.1 X is more than or equal to 0.3,0.2 and y is more than or equal to 0.5, n is the amount of oxygen element required to satisfy the stoichiometric ratio,
M is at least one of lithium, calcium and germanium,
R is at least one of halogen elements;
The monomer general formula of the organosiloxane is expressed as follows:
，
wherein R 1、R2、R3 is alkoxy;
the percentage of the inorganic nitride relative to the organosiloxane is 5-25 wt%.
2. An inorganic nitride and organosiloxane composite solid state electrolyte according to claim 1, characterised in that: in the inorganic nitride, R is any one of chlorine, bromine and iodine.
3. An inorganic nitride and organosiloxane composite solid state electrolyte according to claim 1 or 2 characterised in that: the inorganic nitride is any one of （Li3N）0.2（Li2O）0.3（LiCl）0.5、（Li3N）0.2（Li2O）0.3（LiI）0.5、（Li3N）0.3（Li2O）0.4（LiCl）0.3.
4. An inorganic nitride and organosiloxane composite solid state electrolyte according to claim 1, characterised in that: the percentage of the inorganic nitride relative to the organosiloxane is 10-15 wt%.
5. An inorganic nitride and organosiloxane composite solid state electrolyte according to claim 1, characterised in that: the organic siloxane is at least one of vinyl tri (1-methoxy-2-propoxy) silane, tri-tert-butoxy vinyl silane, vinyl trimethoxy silane, vinyl triethoxy silane, methyl vinyl dimethoxy silane and vinyl tri (2-methoxyethoxy) silane.
6. A method for preparing the inorganic nitride and organosiloxane composite solid electrolyte according to claim 1, comprising the steps of:
Firstly, carrying out preliminary and uniform mixing on three raw materials of lithium nitride Li 3 N, oxide MO n and lithium halide LiR by a ball milling mechanical method, and carrying out heat treatment at 300-500 ℃ under the protection of N 2 atmosphere to obtain inorganic nitride;
Step two, adding organic siloxane, lithium salt and an initiator into the inorganic nitride, and uniformly mixing to obtain precursor liquid;
And thirdly, taking the glass fiber diaphragm as a carrier, fully infiltrating precursor liquid, and thermally polymerizing at 70-100 ℃ under the protection of inert atmosphere to obtain the inorganic nitride and organosiloxane composite solid electrolyte.
7. The method for preparing the inorganic nitride and organosiloxane composite solid electrolyte according to claim 6, wherein the method comprises the following steps: in the first step, the ball-material ratio is controlled to be 20-25:1, and the ball milling time is 6-10 hours.
8. The method for preparing the inorganic nitride and organosiloxane composite solid electrolyte according to claim 6, wherein the method comprises the following steps: in the second step, the lithium salt is at least one selected from lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium oxalato borate, lithium difluorooxalato borate, lithium hexafluorophosphate and lithium tetrafluoroborate.
9. The method for preparing the inorganic nitride and organosiloxane composite solid electrolyte according to claim 6 or 8, characterized in that: in the second step, the molar concentration of the lithium salt relative to the monomers of the organosiloxane is 3-6 mol/L.
10. Use of the composite solid state electrolyte of claim 1, wherein: an inorganic nitride and organosiloxane composite solid electrolyte is used for lithium metal batteries.
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