CN105140560A - Lithium ion solid conductor stable on metal lithium, preparation method of lithium ion solid conductor, and full-solid lithium secondary battery - Google Patents
Lithium ion solid conductor stable on metal lithium, preparation method of lithium ion solid conductor, and full-solid lithium secondary battery Download PDFInfo
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Abstract
The invention provides a lithium ion solid conductor material shown as a formula (I): (100-x)(yLi2S.zP2S5).xM. In the formula (I), the x is greater than 0 but smaller than or equal to 40, a ratio of the y to the z is 3:1; the M is lithium halide. According to a lithium ion solid conductor, lithium halide compounds are introduced into sulphide electrolyte, so that halogen atoms and metal lithium mutually act to form a buffer layer, like an SEI film in a liquid lithium battery; the further reaction between the electrolyte material ingredient and the metal lithium is effectively relieved; the stability of the electrolyte and the metal lithium electrode is improved. In addition, the lithium halide compounds are introduced into the sulphide electrolyte; a multi-dimensional passage for lithium ion transmission is provided; the activity space is increased; the lithium ion conductivity improvement is caused. Therefore the ion conductivity of the sulphide electrolyte can also be improved through the introduction of lithium halide.
Description
Technical field
The invention belongs to technical field of lithium batteries, be specifically related to a kind of lithium ion solid conductor material stable to lithium metal and preparation method thereof and a kind of all solid lithium secondary battery.
Background technology
All solid lithium secondary battery refers to that each unit of battery comprises positive pole, negative pole and electrolyte, all adopts the lithium secondary battery of solid-state material.Lithium secondary battery is large with power output, energy density is high, cyclicity is superior, the many advantages extensive use in daily life such as memory-less effect and non-environmental-pollution, become the first choice of the rechargable power supplies of portable type electronic product, be also considered to the Vehicular dynamic battery of most competitiveness.Because all solid lithium secondary battery has the incomparable fail safe of liquid lithium secondary cell, and be expected to the potential safety hazard thoroughly eliminated in use procedure, more meet the demand of electric automobile and scale energy storage field future development.
At present, each electronic product has been widely used in using graphite as the lithium ion battery of negative pole, but the theoretical specific capacity of graphite only has 372mAh/g, and there is larger irreversible capacity loss in first charge-discharge process, so be difficult to the negative material becoming high-energy-density secondary cell.
Along with the development of science and technology and the active demand to high-energy-density negative material, lithium metal is paid close attention to again as the research of the negative material of secondary cell.Lithium metal relative standard hydrogen electrode electromotive force is-3.045V, and specific capacity is 3861mAh/g, is ideal high-energy lithium cell cathode material.Its charge density is very large and have stable helium type electric double layer, makes it be easy to polarize other molecules or ion, therefore has very large unsteadiness.Basically, lithium metal uses as secondary battery negative pole, and subject matter is: the continuous increase of the lower charge and discharge cycles efficiency that (1) complicated interfacial reaction causes and interface impedance; (2) generation of " dendrite " and " dead lithium ", the safety issue brought and electrode active material loss.This two problems seriously constrains current lithium base secondary cell, comprises the development of lithium ion battery, solid lithium battery, lithium-sulfur cell and lithium-air battery, becomes its major technology bottleneck.
The exploitation lithium battery with high energy storage of future generation, needs lithium metal as negative pole and high-tension electrolyte.And current electrolysis material adopts sulfide solid electrolyte mostly, sulfide solid electrolyte, owing to having relatively high conductivity and wide electrochemical window, is a kind of inoganic solids Lithium Ionic Conducting Materials that can be advantageously applied to all solid lithium secondary battery.But the unsteadiness of sulfide solid electrolyte to lithium metal significantly limit its Application and Development in all solid lithium secondary battery.
Therefore, develop lithium metal chemically stable and there is the new material of good lithium ion conducting characteristic, significant to all kinds of high-energy-density of development, macrocyclic solid state secondary battery technology based on lithium anode.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of lithium ion solid conductor material stable to lithium metal and preparation method thereof and a kind of all solid lithium secondary battery, lithium ion solid conductor material provided by the invention is stablized lithium metal, and has good chemical property.
The invention provides a kind of such as formula the lithium ion solid conductor material shown in (I),
(100-x) (yLi
2szP
2s
5) xM formula (I)
In formula (I): 0<x≤40, y:z=3:1;
M is lithium halide.
Preferably, 0<x≤20.
Preferably, 0.5<x≤16.
Preferably, M is LiF, LiCl, LiBr or LiI.
Present invention also offers a kind of preparation method such as formula the lithium ion solid conductor material shown in (I), comprise the following steps:
A) by Li
2s, P
2s
5with M mixed grinding, obtain just expecting;
B) under the condition of inert gas, described just material is heat-treated, obtains such as formula the lithium ion solid conductor material shown in (I);
(100-x) (yLi
2szP
2s
5) xM formula (I)
In formula (I): 0<x≤40, y:z=3:1;
M is lithium halide.
Preferably, mechanical lapping is ground to described in.
Preferably, described mechanical lapping is high-energy ball milling, and the rotating speed of described high-energy ball milling is 200 ~ 500rpm, and the time is 5h ~ 60h, and ratio of grinding media to material is (1 ~ 60): 1.
Preferably, described inert gas is selected from nitrogen or argon gas.
Preferably, described heat treated temperature is 100 ~ 500 DEG C, and the time is 0.5 ~ 20h.
Present invention also offers a kind of all solid lithium secondary battery, comprise positive pole, negative pole and electrolyte, described electrolyte is the lithium ion solid conductor material that above-mentioned lithium ion solid conductor material or above-mentioned preparation method prepare.
Compared with prior art, the invention provides a kind of such as formula the lithium ion solid conductor material shown in (I), (100-x) (yLi
2szP
2s
5) xM, in formula (I): 0<x≤40, y:z=3:1; M is lithium halide.Lithium ion solid conductor of the present invention owing to introducing lithium halide compound in sulfide electrolyte, make between halogen atom and lithium metal, to act on formation resilient coating, as the SEI film in liquid lithium battery, the further reaction of effective alleviation electrolyte composition and lithium metal, improves the stability of electrolyte and metal lithium electrode.In addition, in sulfide electrolyte, introduce the more-dimensional channels that halide provides lithium ion transport, add its activity space, result in the raising of lithium ion conductivity.Therefore, the introducing of lithium halide also can improve the electrolytical ionic conductivity of sulfide.
Result shows, in 6000 minutes, electric lithium ion solid conductor material prepared by the present invention, with between lithium metal, obvious electrochemical reaction does not occur, and has good stability.Its optimum conductivity is 1.13 × 10
-3~ 1.93 × 10
-3scm
-1, along with the rising of temperature, conductivity also improves accordingly.Described electric lithium ion solid conductor material assembling is prepared into all-solid-state battery, circulates and obviously decay did not occur in 100 weeks, the optimum capability retention of battery reaches 90.3% ~ 93.4%.
Accompanying drawing explanation
Fig. 1 is the AC impedance spectrogram of lithium ion solid conductor material prepared by the embodiment of the present invention 1;
Fig. 2 is the conductivity map under the lithium ion solid conductor material different temperatures of the embodiment of the present invention 1 preparation;
Fig. 3 is that the lithium ion solid conductor material of the embodiment of the present invention 1 preparation is to lithium stability test result;
Fig. 4 is the cycle performance resolution chart of the battery that the lithium ion solid conductor material of the embodiment of the present invention 1 preparation prepares;
Fig. 5 is that the lithium ion solid conductor material of the embodiment of the present invention 5 preparation is to lithium stability test result;
Fig. 6 is the cycle performance resolution chart of the battery that the lithium ion solid conductor material of the embodiment of the present invention 5 preparation prepares;
Fig. 7 is that the lithium ion solid conductor material of the embodiment of the present invention 8 preparation is to lithium stability test result;
Fig. 8 is the cycle performance resolution chart of the battery that the lithium ion solid conductor material of the embodiment of the present invention 8 preparation prepares;
Fig. 9 is that the lithium ion solid conductor material of the embodiment of the present invention 11 preparation is to lithium stability test result;
Figure 10 is the cycle performance resolution chart of the battery that the lithium ion solid conductor material of the embodiment of the present invention 11 preparation prepares;
Figure 11 is the conductivity of lithium ion solid conductor material prepared by the embodiment of the present invention 1 ~ 12.
Embodiment
The invention provides a kind of such as formula the lithium ion solid conductor material shown in (I),
(100-x) (yLi
2szP
2s
5) xM formula (I)
In formula (I): 0<x≤40, y:z=3:1;
M is lithium halide.
Lithium ion solid conductor material provided by the invention for introduce lithium halide compound in sulfide, and in the present invention, described sulfide has the atomic ratio of formula (II),
YLi
2szP
2s
5formula (II)
Wherein, in formula (II), the mol ratio of described y and z is 3:1.
Described lithium halide compound is M, and preferably, described M is selected from LiF, LiCl, LiBr or LiI.
In lithium ion solid conductor material provided by the invention, the mol ratio of the sulfide shown in described formula (II) and M is preferably (100-x): x.Wherein, 0<x≤40, preferably, and 0<x≤20, preferred, 0.5<x≤16.
Present invention also offers a kind of preparation method such as formula the lithium ion solid conductor material shown in (I), comprise the following steps:
A) by Li
2s, P
2s
5with M mixed grinding, obtain just expecting;
B) under the condition of inert gas, described just material is heat-treated, obtains such as formula the lithium ion solid conductor material shown in (I);
(100-x) (yLi
2szP
2s
5) xM formula (I)
In formula (I): 0<x≤40, y:z=3:1;
M is lithium halide.
The present invention is first by Li
2s, P
2s
5with M mixed grinding, obtain just expecting.In the present invention, preferably under the condition of inert gas, Li is carried out
2s, P
2s
5with weighing and the mixed grinding of M, described inert gas is preferably nitrogen or argon gas.Wherein, described Li
2s and P
2s
5mol ratio be preferably 3:1, Li
2s and P
2s
5the sulfide be mixed to get and the mol ratio of M are preferably (100-x): x.Wherein, 0<x≤40, preferably, and 0<x≤20, preferred, 0.5<x≤16.
The present invention is to described Li
2s, P
2s
5do not have particular restriction with the mode of M mixed grinding, well known to a person skilled in the art the method for mixed grinding.In the present invention, preferably adopt mechanical lapping, be more preferably high-energy ball milling.The rotating speed of described high-energy ball milling is 200 ~ 500rpm, is preferably 300 ~ 400rpm; The time of described high-energy ball milling is 5h ~ 60h, is preferably 10 ~ 30h; The ratio of grinding media to material of described high-energy ball milling is preferably (1 ~ 60): 1, is more preferably (40 ~ 55): 1.
After grinding terminates, obtain just expecting.Described just material is heat-treated, lithium ion solid conductor material can be obtained.Before heat-treating, the present invention also comprises described just material is carried out compressing tablet, obtains sheet and just expects.The method of the present invention to described compressing tablet does not have particular restriction, well known to a person skilled in the art tabletting method.In the present invention, preferably compressing tablet is carried out as follows:
First material after described grinding is carried out compressing tablet under the pressure condition of 10MPa, obtains sheet and just expect.
The sheet obtained just expects to be placed in sintering mold by the present invention, under the condition of inert gas, heat-treats, and obtains such as formula the lithium ion solid conductor material shown in (I).In the present invention, described inert gas is preferably nitrogen or argon gas.Described heat treated temperature is 100 ~ 500 DEG C, is preferably 200 ~ 500 DEG C; The described heat treated time is 0.5 ~ 20h, is preferably 1 ~ 10h.
Heat treated concrete grammar of the present invention is preferably as follows:
Described sheet is just expected, with the heating of the heating rate of 1 ~ 3 DEG C/min, be warming up to 100 ~ 500 DEG C, cool to room temperature with the furnace after insulation 0.5 ~ 20h, obtain flaky lithium ion solid conductor material.
Present invention also offers a kind of all solid lithium secondary battery, comprise positive pole, negative pole and electrolyte, described electrolyte is the lithium ion solid conductor material that above-mentioned lithium ion solid conductor material or above-mentioned preparation method prepare.In the present invention, described positive pole is preferably cobalt acid lithium, LiMn2O4, LiFePO4, is more preferably cobalt acid lithium; Described negative pole is preferably Carbon anode, lithium anode, is more preferably lithium anode material.
Lithium ion solid conductor of the present invention owing to introducing lithium halide compound in sulfide electrolyte, make between halogen atom and lithium metal, to act on formation resilient coating, as the SEI film in liquid lithium battery, the further reaction of effective alleviation electrolyte composition and lithium metal, improves the stability of electrolyte and metal lithium electrode.In addition, in sulfide electrolyte, introduce the more-dimensional channels that halide provides lithium ion transport, add its activity space, result in the raising of lithium ion conductivity.Therefore, the introducing of lithium halide also can improve the electrolytical ionic conductivity of sulfide.
Result shows, in 6000 minutes, electric lithium ion solid conductor material prepared by the present invention, with between lithium metal, obvious electrochemical reaction does not occur, and has good stability.Its optimum conductivity is 1.13 × 10
-3~ 1.93 × 10
-3scm
-1, along with the rising of temperature, conductivity also improves accordingly.Described electric lithium ion solid conductor material assembling is prepared into all-solid-state battery, circulates and obviously decay did not occur in 100 weeks, the optimum capability retention of battery reaches 90.3% ~ 93.4%.
In order to understand the present invention further, be described lithium ion solid conductor material provided by the invention and preparation method thereof and a kind of all solid lithium secondary battery below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Under argon gas atmosphere protection, purity is respectively the Li of more than 99%
2s, P
2s
5after weighing according to mol ratio 75:25, then by (75Li
2s25P
2s
5): the molar ratio of LiI=90:10 adds LiI, to be less than in water content under the condition of 10ppm with 500rpm rotating speed ground and mixed evenly, obtain powder after high-energy ball milling 12h under 45:1 ratio of grinding media to material condition and just expect, take out powder and just expect that porphyrize evenly adopts 10MPa pressure compressing tablet to obtain sheet afterwards and just expects, sheet is just expected load sintering mold.250 DEG C are heated to the heating rate of 2 DEG C/min by being equipped with the sintering mold that above-mentioned sheet just expects, insulation 2h, the grinding of sheet sintered product is taken out evenly be less than the condition of 100ppm after cooling to room temperature with the furnace in water content under, obtaining powder is all solid lithium secondary battery lithium ion solid conductor material, i.e. 90% (75Li
2s25P
2s
5) 10%LiI (mol%) glass ceramics.
To 90% (75Li
2s25P
2s
5) 10%LiI (mol%) lithium ion solid conductor material carries out electrochemical property test and to lithium stability test.By above-mentioned lithium ion solid conductor powder body material under water content is less than 10ppm, 10MPa pressure condition, be pressed into the sheet 90% (75Li that diameter is 10mm, thickness is 1mm
2s25P
2s
5) 10%LiI (mol%) glass ceramics lithium ion solid conductor.Then take carbon as blocking electrode, carry out EIS test at different temperatures, test its electric conductivity, as shown in Figure 1, Fig. 1 is the AC impedance spectrogram of lithium ion solid conductor material prepared by the embodiment of the present invention 1 to result, and Fig. 2 is the conductivity under its different temperatures.As can be seen from Figure 1, body series has ionic conduction characteristic, and under 25 DEG C of conditions, lithium ion conductivity is 1.61 × 10
-3scm
-1, show that all solid lithium secondary battery lithium ion solid conductor material of gained at room temperature has good conductivity, Fig. 2 shows along with the rising of working temperature is conducive to the conduction of material to lithium ion.
By the 90% (75Li obtained
2s25P
2s
5) 10%LiI (mol%) lithium ion solid conductor, be clipped in two lithium metals in electrode, carry out lithium stability test to it, test result is as shown in Figure 3.Its result shows, in 6000 minutes, prepares electrolyte, with between lithium metal, obvious electrochemical reaction does not occur, totally have good stability.
Adopt cobalt acid lithium to be positive pole, employing lithium metal is negative pole, is assembled into all solid lithium secondary battery together with above-mentioned lithium ion solid conductor material, and its first charge-discharge curve chart sees Fig. 4.As can be seen from Figure 4, the not generation significantly decay that all-solid-state battery circulates 100 weeks, battery still has extraordinary capacity, and capability retention reaches 93.4%.
Embodiment 2
Under argon gas atmosphere protection, purity is respectively the Li of more than 99%
2s, P
2s
5after weighing according to mol ratio 75:25, pressing (75Li
2s25P
2s
5): the molar ratio of LiI=95:5 adds LiI, to be less than in water content under the condition of 10ppm with 200rpm rotating speed ground and mixed evenly, obtain powder after high-energy ball milling 18h under 40:1 ratio of grinding media to material condition and just expect, take out powder and just expect that porphyrize evenly adopts 10MPa pressure compressing tablet to obtain sheet afterwards and just expects, sheet is just expected load sintering mold.300 DEG C are heated to the heating rate of 1 DEG C/min by being equipped with the sintering mold that above-mentioned sheet just expects, insulation 4h, the grinding of sheet sintered product is taken out evenly be less than the condition of 100ppm after cooling to room temperature with the furnace in water content under, obtain powder all solid lithium secondary battery lithium ion solid conductor material, i.e. 95% (75Li
2s25P
2s
5) 5%LiI (mol%) glass ceramics.
The Electrochemical Characterization that the present embodiment obtains all solid lithium secondary battery lithium ion solid conductor is tested according to the method for embodiment 1.Result shows, and under 25 DEG C of conditions, its lithium ion conductivity is 8.1 × 10
-4scm
-1, test result as shown in figure 11.
Embodiment 3
Under argon gas atmosphere protection, purity is respectively the Li of more than 99%
2s, P
2s
5after weighing according to mol ratio 75:25, pressing (75Li
2s25P
2s
5): the molar ratio of LiI=85:15 adds LiI, to be less than in water content under the condition of 10ppm with 300rpm rotating speed ground and mixed evenly, obtain powder after high-energy ball milling 22h under 30:1 ratio of grinding media to material condition and just expect, take out powder and just expect that porphyrize evenly adopts 10MPa pressure compressing tablet to obtain sheet afterwards and just expects, sheet is just expected load sintering mold.350 DEG C are heated to the heating rate of 2 DEG C/min by being equipped with the sintering mold that above-mentioned sheet just expects, insulation 8h, the grinding of sheet sintered product is taken out evenly be less than the condition of 100ppm after cooling to room temperature with the furnace in water content under, obtain powder all solid lithium secondary battery lithium ion solid conductor material, i.e. 85% (75Li
2s25P
2s
5) 15%LiI (mol%) glass ceramics.
The Electrochemical Characterization that the present embodiment obtains all solid lithium secondary battery lithium ion solid conductor is tested according to the method for embodiment 1.Result shows, and under 25 DEG C of conditions, its lithium ion conductivity is 6.2 × 10
-4scm
-1, test result as shown in figure 11.
Embodiment 4
Under argon gas atmosphere protection, purity is respectively the Li of more than 99%
2s, P
2s
5after weighing according to mol ratio 75:25, pressing (75Li
2s25P
2s
5): the molar ratio of LiBr=99:1 adds LiBr, to be less than in water content under the condition of 10ppm with 200rpm rotating speed ground and mixed evenly, obtain powder after high-energy ball milling 28h under 30:1 ratio of grinding media to material condition and just expect, take out powder and just expect that porphyrize evenly adopts 10MPa pressure compressing tablet to obtain sheet afterwards and just expects, sheet is just expected load sintering mold.200 DEG C are heated to the heating rate of 1 DEG C/min by being equipped with the sintering mold that above-mentioned sheet just expects, insulation 10h, the grinding of sheet sintered product is taken out evenly be less than the condition of 100ppm after cooling to room temperature with the furnace in water content under, obtain powder all solid lithium secondary battery lithium ion solid conductor material, i.e. 99% (75Li
2s25P
2s
5) 1%LiBr (mol%) glass ceramics.
The Electrochemical Characterization that the present embodiment obtains all solid lithium secondary battery lithium ion solid conductor is tested according to the method for embodiment 1.Result shows, and under 25 DEG C of conditions, its lithium ion conductivity is 6 × 10
-4scm
-1, test result as shown in figure 11.
Embodiment 5
Under argon gas atmosphere protection, purity is respectively the Li of more than 99%
2s, P
2s
5after weighing according to mol ratio 75:25, pressing (75Li
2s25P
2s
5): the molar ratio of LiBr=95:5 adds LiBr, to be less than in water content under the condition of 10ppm with 500rpm rotating speed ground and mixed evenly, obtain powder after high-energy ball milling 12h under 45:1 ratio of grinding media to material condition and just expect, take out powder and just expect that porphyrize evenly adopts 10MPa pressure compressing tablet to obtain sheet afterwards and just expects, sheet is just expected load sintering mold.250 DEG C are heated to the heating rate of 2 DEG C/min by being equipped with the sintering mold that above-mentioned sheet just expects, insulation 2h, the grinding of sheet sintered product is taken out evenly be less than the condition of 100ppm after cooling to room temperature with the furnace in water content under, obtain powder all solid lithium secondary battery lithium ion solid conductor material, i.e. 95% (75Li
2s25P
2s
5) 5%LiBr (mol%) glass ceramics.
The Electrochemical Characterization that the present embodiment obtains all solid lithium secondary battery lithium ion solid conductor is tested according to the method for embodiment 1.Result shows, and under 25 DEG C of conditions, its lithium ion conductivity is 1.93 × 10
-3scm
-1, test result as shown in figure 11.Carry out lithium stability test by embodiment 1 method to it, test result as shown in Figure 5.In 6000 minutes, prepare electrolyte, with between lithium metal, obvious electrochemical reaction does not occur, have good stability.Be assembled into all solid lithium secondary battery by example 1, its first charge-discharge curve chart sees Fig. 6.There is not obviously decay in 100 weeks in all-solid-state battery circulation, battery capacity conservation rate reaches 91.3%.
Embodiment 6
Under argon gas atmosphere protection, purity is respectively the Li of more than 99%
2s, P
2s
5after weighing according to mol ratio 75:25, pressing (75Li
2s25P
2s
5): the molar ratio of LiBr=90:10 adds LiBr, to be less than in water content under the condition of 10ppm with 300rpm rotating speed ground and mixed evenly, obtain powder after high-energy ball milling 10h under 55:1 ratio of grinding media to material condition and just expect, take out powder and just expect that porphyrize evenly adopts 10MPa pressure compressing tablet to obtain sheet afterwards and just expects, sheet is just expected load sintering mold.450 DEG C are heated to the heating rate of 2 DEG C/min by being equipped with the sintering mold that above-mentioned sheet just expects, insulation 3h, the grinding of sheet sintered product is taken out evenly be less than the condition of 100ppm after cooling to room temperature with the furnace in water content under, obtain powder all solid lithium secondary battery lithium ion solid conductor material, i.e. 90% (75Li
2s25P
2s
5) 10%LiBr (mol%) glass ceramics.
Chemical property and the structural characterization that the present embodiment obtains all solid lithium secondary battery lithium ion solid conductor is tested according to the method for embodiment 1.Result shows, and under 25 DEG C of conditions, its lithium ion conductivity is 2 × 10
-4scm
-1, test result as shown in figure 11.
Embodiment 7
Under argon gas atmosphere protection, purity is respectively the Li of more than 99%
2s, P
2s
5after weighing according to mol ratio 75:25, pressing (75Li
2s25P
2s
5): the molar ratio of LiCl=99:1 adds LiCl, to be less than in water content under the condition of 10ppm with 300rpm rotating speed ground and mixed evenly, obtain powder after high-energy ball milling 26h under 30:1 ratio of grinding media to material condition and just expect, take out powder and just expect that porphyrize evenly adopts 10MPa pressure compressing tablet to obtain sheet afterwards and just expects, sheet is just expected load sintering mold.200 DEG C are heated to the heating rate of 2 DEG C/min by being equipped with the sintering mold that above-mentioned sheet just expects, insulation 3h, the grinding of sheet sintered product is taken out evenly be less than the condition of 100ppm after cooling to room temperature with the furnace in water content under, obtain powder all solid lithium secondary battery lithium ion solid conductor material, i.e. 99% (75Li
2s25P
2s
5) 1%LiCl (mol%) glass ceramics.
The Electrochemical Characterization that the present embodiment obtains all solid lithium secondary battery lithium ion solid conductor is tested according to the method for embodiment 1.Result shows, and under 25 DEG C of conditions, its lithium ion conductivity is 7 × 10
-4scm
-1, test result as shown in figure 11.
Embodiment 8
Under argon gas atmosphere protection, purity is respectively the Li of more than 99%
2s, P
2s
5after weighing according to mol ratio 75:25, pressing (75Li
2s25P
2s
5): the molar ratio of LiCl=95:5 adds LiCl, to be less than in water content under the condition of 10ppm with 500rpm rotating speed ground and mixed evenly, obtain powder after high-energy ball milling 12h under 45:1 ratio of grinding media to material condition and just expect, take out powder and just expect that porphyrize evenly adopts 10MPa pressure compressing tablet to obtain sheet afterwards and just expects, sheet is just expected load sintering mold.250 DEG C are heated to the heating rate of 2 DEG C/min by being equipped with the sintering mold that above-mentioned sheet just expects, insulation 2h, the grinding of sheet sintered product is taken out evenly be less than the condition of 100ppm after cooling to room temperature with the furnace in water content under, obtain powder all solid lithium secondary battery lithium ion solid conductor material, i.e. 95% (75Li
2s25P
2s
5) 5%LiCl (mol%) glass ceramics.
Chemical property and the structural characterization that the present embodiment obtains all solid lithium secondary battery lithium ion solid conductor is tested according to the method for embodiment 1.Result shows, and under 25 DEG C of conditions, its lithium ion conductivity is 1.27 × 10
-3scm
-1, test result as shown in figure 11.Carry out lithium stability test by embodiment 1 method to it, test result as shown in Figure 7.In 6000 minutes, prepare electrolyte, with between lithium metal, obvious electrochemical reaction does not occur, have good stability.Be assembled into all solid lithium secondary battery by example 1, its first charge-discharge curve chart sees Fig. 8.There is not obviously decay in 100 weeks in all-solid-state battery circulation, battery capacity conservation rate reaches 92.3%.
Embodiment 9
Under argon gas atmosphere protection, purity is respectively the Li of more than 99%
2s, P
2s
5after weighing according to mol ratio 75:25, pressing (75Li
2s25P
2s
5): the molar ratio of LiCl=90:10 adds LiCl, to be less than in water content under the condition of 10ppm with 400rpm rotating speed ground and mixed evenly, obtain powder after high-energy ball milling 10h under 55:1 ratio of grinding media to material condition and just expect, take out powder and just expect that porphyrize evenly adopts 10MPa pressure compressing tablet to obtain sheet afterwards and just expects, sheet is just expected load sintering mold.450 DEG C are heated to the heating rate of 3 DEG C/min by being equipped with the sintering mold that above-mentioned sheet just expects, insulation 6h, the grinding of sheet sintered product is taken out evenly be less than the condition of 100ppm after cooling to room temperature with the furnace in water content under, obtain powder all solid lithium secondary battery lithium ion solid conductor material, i.e. 90% (75Li
2s25P
2s
5) 10%LiCl (mol%) glass ceramics.
The Electrochemical Characterization that the present embodiment obtains all solid lithium secondary battery lithium ion solid conductor is tested according to the method for embodiment 1.Result shows, and under 25 DEG C of conditions, its lithium ion conductivity is 3.1 × 10
-4scm
-1, test result as shown in figure 11.
Embodiment 10
Under argon gas atmosphere protection, purity is respectively the Li of more than 99%
2s, P
2s
5after weighing according to mol ratio 75:25, pressing (75Li
2s25P
2s
5): the molar ratio of LiF=99:1 adds LiF, to be less than in water content under the condition of 10ppm with 400rpm rotating speed ground and mixed evenly, obtain powder after high-energy ball milling 10h under 55:1 ratio of grinding media to material condition and just expect, take out powder and just expect that porphyrize evenly adopts 10MPa pressure compressing tablet to obtain sheet afterwards and just expects, sheet is just expected load sintering mold.200 DEG C are heated to the heating rate of 1 DEG C/min by being equipped with the sintering mold that above-mentioned sheet just expects, insulation 1h, the grinding of sheet sintered product is taken out evenly be less than the condition of 100ppm after cooling to room temperature with the furnace in water content under, obtain powder all solid lithium secondary battery lithium ion solid conductor material, i.e. 99% (75Li
2s25P
2s
5) 1%LiF (mol%) glass ceramics.
The Electrochemical Characterization that the present embodiment obtains all solid lithium secondary battery lithium ion solid conductor is tested according to the method for embodiment 1.Result shows, and under 25 DEG C of conditions, its lithium ion conductivity is 7.1 × 10
-4scm
-1, test result as shown in figure 11.
Embodiment 11
Under argon gas atmosphere protection, purity is respectively the Li of more than 99%
2s, P
2s
5after weighing according to mol ratio 75:25, pressing (75Li
2s25P
2s
5): the molar ratio of LiF=95:5 adds LiF, to be less than in water content under the condition of 10ppm with 500rpm rotating speed ground and mixed evenly, obtain powder after high-energy ball milling 12h under 45:1 ratio of grinding media to material condition and just expect, take out powder and just expect that porphyrize evenly adopts 10MPa pressure compressing tablet to obtain sheet afterwards and just expects, sheet is just expected load sintering mold.250 DEG C are heated to the heating rate of 2 DEG C/min by being equipped with the sintering mold that above-mentioned sheet just expects, insulation 2h, the grinding of sheet sintered product is taken out evenly be less than the condition of 100ppm after cooling to room temperature with the furnace in water content under, obtain powder all solid lithium secondary battery lithium ion solid conductor material, i.e. 95% (75Li
2s25P
2s
5) 5%LiF (mol%) glass ceramics.
Chemical property and the structural characterization that the present embodiment obtains all solid lithium secondary battery lithium ion solid conductor is tested according to the method for embodiment 1.Result shows, and under 25 DEG C of conditions, its lithium ion conductivity is 1.13 × 10
-3scm
-1, test result as shown in figure 11.Carry out lithium stability test by embodiment 1 method to it, test result as shown in Figure 9.In 6000 minutes, prepare electrolyte, with between lithium metal, obvious electrochemical reaction does not occur, have good stability.Be assembled into all solid lithium secondary battery by example 1, its first charge-discharge curve chart sees Figure 10, and all-solid-state battery circulation obviously decay did not occur in 100 weeks, and battery capacity conservation rate reaches 90.3%.
Embodiment 12
Under argon gas atmosphere protection, purity is respectively the Li of more than 99%
2s, P
2s
5after weighing according to mol ratio 75:25, pressing (75Li
2s25P
2s
5): the molar ratio of LiF=90:10 adds LiF, to be less than in water content under the condition of 10ppm with 300rpm rotating speed ground and mixed evenly, obtain powder after high-energy ball milling 22h under 35:1 ratio of grinding media to material condition and just expect, take out powder and just expect that porphyrize evenly adopts 10MPa pressure compressing tablet to obtain sheet afterwards and just expects, sheet is just expected load sintering mold.450 DEG C are heated to the heating rate of 3 DEG C/min by being equipped with the sintering mold that above-mentioned sheet just expects, insulation 6h, the grinding of sheet sintered product is taken out evenly be less than the condition of 100ppm after cooling to room temperature with the furnace in water content under, obtain powder all solid lithium secondary battery lithium ion solid conductor material, i.e. 90% (75Li
2s25P
2s
5) 10%LiF (mol%) glass ceramics.
The Electrochemical Characterization that the present embodiment obtains all solid lithium secondary battery lithium ion solid conductor is tested according to the method for embodiment 1.Result shows, and under 25 DEG C of conditions, its lithium ion conductivity is 6.1 × 10
-4scm
-1, test result as shown in figure 11.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. such as formula the lithium ion solid conductor material stable to lithium metal shown in (I),
(100-x) (yLi
2szP
2s
5) xM formula (I)
In formula (I): 0<x≤40, y:z=3:1;
M is lithium halide.
2. lithium ion solid conductor material according to claim 1, is characterized in that, 0<x≤20.
3. lithium ion solid conductor material according to claim 1, is characterized in that, 0.5<x≤16.
4. lithium ion solid conductor material according to claim 1, is characterized in that, M is LiF, LiCl, LiBr or LiI.
5., such as formula a preparation method for the lithium ion solid conductor material stable to lithium metal shown in (I), it is characterized in that, comprise the following steps:
A) by Li
2s, P
2s
5with M mixed grinding, obtain just expecting;
B) under the condition of inert gas, described just material is heat-treated, obtains such as formula the lithium ion solid conductor material shown in (I);
(100-x) (yLi
2szP
2s
5) xM formula (I)
In formula (I): 0<x≤40, y:z=3:1;
M is lithium halide.
6. preparation method according to claim 5, is characterized in that, described in be ground to mechanical lapping.
7. preparation method according to claim 6, is characterized in that, described mechanical lapping is high-energy ball milling, and the rotating speed of described high-energy ball milling is 200 ~ 500rpm, and the time is 5h ~ 60h, and ratio of grinding media to material is (1 ~ 60): 1.
8. preparation method according to claim 5, is characterized in that, described inert gas is selected from nitrogen or argon gas.
9. preparation method according to claim 5, is characterized in that, described heat treated temperature is 100 ~ 500 DEG C, and the time is 0.5 ~ 20h.
10. an all solid lithium secondary battery, it is characterized in that, comprise positive pole, negative pole and electrolyte, the lithium ion solid conductor material that described electrolyte prepares for the lithium ion solid conductor material described in Claims 1 to 4 or the preparation method described in claim 5 ~ 9.
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