CN103401018A - Solid-state electrolyte material of lithium ion battery - Google Patents
Solid-state electrolyte material of lithium ion battery Download PDFInfo
- Publication number
- CN103401018A CN103401018A CN2013103479329A CN201310347932A CN103401018A CN 103401018 A CN103401018 A CN 103401018A CN 2013103479329 A CN2013103479329 A CN 2013103479329A CN 201310347932 A CN201310347932 A CN 201310347932A CN 103401018 A CN103401018 A CN 103401018A
- Authority
- CN
- China
- Prior art keywords
- electrolyte material
- solid electrolyte
- lithium ion
- solid
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a solid-state electrolyte material of a lithium ion battery. The general formula of the solid-state electrolyte material is (LimZn)MP2X12, and the solid-state electrolyte belongs to a triclinic crystal system and a P1 space group, wherein Z is a high-valence metal element, the cationic valence is more than +1 valence and less than or equal to +3 valence, and the high-valence metal element Z is at least one of Mg, Al, Ca, Ti, Cu, Zn, Ga, In, Sr, Ru, Rh, Pd, Ag, Cd, Ba, Os, Ir, Pt or Hg; M is at least one of Ge, Si, Sn, Al or P; and X is at least one of O, S or Se. The research on the micro structure characteristics of the solid-state electrolyte material (LimZn)MP2X12 indicates that the micro interaction mechanisms such as Coulomb force, Van der Waals force and the like have important effect on the structure stability of the solid electrolyte material; and by enhancing the Coulomb attraction effect among ions and enhancing the shielding of the Coulomb repulsion effect among the ions, the total energy of the material system is greatly reduced, thereby enhancing the structure stability of the solid electrolyte material.
Description
Technical field
The present invention relates to the lithium ion battery field, relate in particular to a kind of solid electrolyte material of lithium ion battery.
Background technology
Solid electrolyte replaces the conventional liquid organic bath to be applied among lithium ion battery, can greatly improve the security performance of traditional lithium ion battery, so solid electrolyte receives much concern for a long time.From the seventies in last century so far, the development experience of solid electrolyte three phases: first stage be seventies in 20th century to the nineties, the center of gravity of this research in period is polymer dielectric, the ionic conductivity under its normal temperature is approximately 10
-5S/cm, far below the ionic conductivity (about 10 of conventional liquid organic bath
-3S/cm); Second stage is in 20 years after the nineties in 20th century, the solid electrolyte material of this research in period is mainly perovskite oxide material, sulfuration crystallization lithium superionic conductors (thio-LISICON), glass ceramic material and vitreous material (for example, Li
3PO
4-Li
2S-SiS
2System), this class material ionic conductivity at normal temperatures is approximately 10
-4S/cm, still lower than the ionic conductivity of traditional liquid organic bath; Although these two solid electrolyte materials of studying period obtain certain applications in all solid state lithium ion battery, their ionic conductance performance still is inferior to the conventional liquid organic bath, thereby has significantly limited its extensive use.Three phases is for over the past two years to solid phase crystalline material Li
10GeP
2S
12The research of (being abbreviated as LGPS), this material can show very high ionic conductivity and very wide voltage window at normal temperatures.
2011, the quick ionic conductance crystalline material LGPS that is taken the lead in being developed into by Kanno group of Tokyo polytechnical university, can show at normal temperatures the ionic conductivity suitable with the conventional liquid organic bath, can reach 12S/cm, this size has even surpassed the ionic conductivity of some liquid organic bath, simultaneously, this crystalline material also has the voltage window wider than conventional liquid organic bath, its voltage window that can bear can surpass 5V, so the LGPS crystalline material has some idea of in the importance of application aspect all solid state lithium ion battery.
The Chinese patent application publication No. CN102823049A that announces on December 12nd, 2012 has announced the preparation method of a kind of sulfide solid electrolyte material, battery and sulfide solid electrolyte material, the method discloses a kind of solid electrolyte of sulfide, and it comprises lithium, germanium, p and s.Because this class sulfide material has good ionic conductance performance, so this class sulfide material is used as the solid electrolyte of all solid state lithium ion battery.
The disclosed LGPS crystalline material of Kanno group of Tokyo polytechnical university belongs to tetragonal crystal system and P42/nmc space group, and its lattice constant is
Between crystallographic axis, angle is α=β=γ=90 °.As shown in Figure 2, the spectrum peak position of intensity maximum is in 29 ° of left and right for the XRD spectrum of this LGPS crystal structure (utilizing CuK α line to measure).Li in its chemical formula, Ge, P and S atom show as respectively+1 valency ,+4 valencys ,+5 valencys and-divalent, phosphorus and germanium form PS with sulphur respectively
4And GeS
4Tetrahedron, these tetrahedrons are pressed the Z-shaped chain type and are arranged in the a-b face, integral body is relatively disperseed.Interaction between them is mainly manifested in following two aspects: the lithium ion between (1) tetrahedron and the Coulomb attraction effect between the sulphion in tetrahedron; (2) the multipole dipole moment that forms in polyhedron has caused the Van der Waals force between polyhedron to interact.It is two main causes that the LGPS material can stable existence that Coulomb attraction effect in the LGPS structural framing between lithium ion and sulphion and the Van der Waals force between polyhedron interact.
In addition, Ceder group of masschusetts, u.s.a Polytechnics also carried out the analog study based on density functional theory to architectural feature and the lithium ion diffusion of LGPS, and relevant achievement in research was published in energy and environment science (Energy& in 2012; Environment Science) on magazine, phase number of the edition and the page number are respectively 6 and 148-156.This achievement in research article they to LGPS material structure stability and the fast checking of lithium ion diffusion, and in the situation that the different elements of doping have been studied the structural stability of LGPS material and the situation of change of lithium ion diffusion.Although a series of analog study has been done to the LGPS material structure by Ceder group, verified the rapid diffusion performance of lithium ion in the LGPS material, it is clear that but they do not study the microcosmic effect mechanism between LGPS material Atom, thereby can not find the key factor that strengthens its structural stability from root.
On the other hand, also there are many problems in the application of LGPS material in all solid state lithium ion battery at present, one of them is exactly that it easily decomposes on the interface with electrode material contacts, thereby affected the chemical property of LGPS material, and its topmost reason is the easy decomposability of this body structure of LGPS material.Therefore, from experimentally directly finding the scheme that strengthens LGPS material structure stability, have great importance, but difficulty is large, cost is high and the cycle is longer.
Summary of the invention
In view of the problem that background technology exists, the object of the present invention is to provide a kind of solid electrolyte material of lithium ion battery, it can improve the solid electrolyte material structural stability.
To achieve these goals, the invention provides a kind of solid electrolyte material of lithium ion battery, wherein, the general formula of described solid electrolyte material is (Li
mZ
n) MP
2X
12, described solid electrolyte belongs to anorthic system and P
1Space group; Wherein, Z is the high-valency metal element, its cationic compound valency is greater than+1 valency and less than or equal to+3 valencys, and described high-valency metal element Z is at least a in Mg, Al, Ca, Ti, Cu, Zn, Ga, In, Sr, Ru, Rh, Pd, Ag, Cd, Ba, Os, Ir, Pt or Hg; M is at least a in Ge, Si, Sn, Al or P; X is at least a in O, S or Se.
Beneficial effect of the present invention is as follows:
The present invention is by research solid electrolyte material (Li
mZ
n) MP
2X
12Microstructure characteristic, shown that the interaction mechanism of the microcosmic such as Coulomb force and Van der Waals force is to (Li
mZ
n) MP
2X
12The important function of solid electrolyte material structural stability.In the present invention, pass through to strengthen (Li
mZ
n) MP
2X
12Coulomb attraction effect between the material intermediate ion and the enhancing shielding to interionic coulomb repulsion effect, significantly reduce the total energy of material system, thereby improve the structural stability of solid electrolyte material.
The accompanying drawing explanation
Fig. 1 is that structural framing and the electric charge between lithium ion and sulphion of solid electrolyte LGPS shifts schematic diagram;
Fig. 2 is that the space group of utilizing CuK α line to measure is P4
2The XRD spectrum of the LGPS crystal structure of/nmc;
Fig. 3 is that the space group of utilizing CuK α line to measure is P
1The XRD spectrum of LGPS crystal structure;
Fig. 4 is solid electrolyte Li
9Ca
0.5GeP
2S
12Structural representation, wherein calcium ion represents with the large ball of black;
Fig. 5 is that the space group of utilizing CuK α line to measure is P
1Li
9Ca
0.5GeP
2S
12The XRD spectrum of crystal structure;
Fig. 6 is solid electrolyte Li
8.5Ga
0.5GeP
2S
12Structural representation, wherein gallium ion represents with the large ball of Dark grey.
Embodiment
Below describe solid electrolyte material and the embodiment of the lithium ion battery according to the present invention in detail.
At first, in order to illustrate that Van der Waals force interacts to the material impact of LGPS material structure stability, at first the present invention is not considering in the interactional situation of Van der Waals force that to the disclosed LGPS structure of Kanno group the first principle that has carried out based on density functional theory calculates, and finds that its lattice parameter is
With the result of experimentally reporting
Difference is larger, and particularly the lattice constant error of c-axis has reached more than 20%.If consider that Van der Waals force interacts, the lattice parameter that can obtain this LGPS material is
Between crystallographic axis, angle is α=β=γ=90 °, and the disclosed report result of this result and Kanno group is coincide in the extreme, simultaneously, and PS
4With PS
4Tetrahedron and GeS
4With PS
4Distance between tetrahedron is respectively
With
With experimental result
With
Coincide equally in the extreme.Therefore, Van der Waals force interacts and in LGPS material structure stability, has played very crucial effect.
In addition, by the laboratory facilities such as XRD to lithium ion position in the LGPS material determine more difficult, in the LGPS structure of experiment report, the lithium ion occupy-place has certain uncertainty, and lithium ion distributes and directly affects the stability of material structure occupying of LGPS structure.Considering on the interactional basis of Van der Waals force, according to interionic Coulomb interactions principle and based on the first principle of density functional theory, calculate, compared the not total energy of isomorphism type of LGPS, further determined the settling position of lithium ion, thereby obtained the LGPS crystal structure (as shown in Figure 1) that in the present invention, structure is the most stable, in structure, the stoichiometric proportion of Li:Ge:P:S is still 10:1:2:12.From on the angle of system total energy, triclinic LGPS solid electrolyte material of the present invention on average on each molecular formula can be than approximately low 1.3 electronvolt of the LGPS solid electrolyte material of tetragonal crystal system, so triclinic LGPS solid electrolyte material of the present invention has better structural stability.Lithium ion according to its different positions that occupy, is denoted as lithium 1 (representative is positioned at along the lithium ion of the lithium diffusion admittance of c-axis), lithium 2 (representative is positioned at the lithium ion on the structure cell axial plane) and lithium 3 (representative is positioned at the lithium ion on structural framing or structure cell seamed edge) taxonomically in Fig. 1; Phosphorus, germanium and sulphur atom all represent with thin bar, and wherein phosphorus atoms is positioned on the intersection point of Dark grey thin bar, and germanium atom is positioned on the intersection point of black thin bar, and sulphur atom is positioned at white thin bar end.The place that in Fig. 1, dark translucent areas domain representation electric charge focuses on, and the place that light-coloured transparent region representation electric charge reduces.The lattice constant of this LGPS crystal is
Between crystallographic axis, angle is α=90.509 °, β=90.633 °, γ=89.875 °, so this LGPS crystal structure belongs to anorthic system and P1 space group.As shown in Figure 3, the spectrum peak position of intensity maximum is in 21 ° of left and right for the XRD spectrum of the crystal structure of this LGPS material.From the contrast of Fig. 3 and Fig. 2, can find out, the disclosed solid electrolyte material of LGPS solid electrolyte material of the present invention and Kanno group has diverse crystal structure characteristic, belongs to different crystallographic system and space groups.In LGPS crystal structure of the present invention, the Coulomb attraction effect in structural framing between lithium ion and sulphion has not only obtained maximum enhancing, and the coulomb repulsion effect between sulphion has also obtained maximum shielding.So the LGPS crystal structure in the present invention is more stable with respect to the disclosed LGPS structure of Kanno group.
Next illustrates the solid electrolyte material of lithium ion battery of the present invention.
In the solid electrolyte material according to lithium ion battery of the present invention; The general formula of described solid electrolyte material is (Li
mZ
n) MP
2X
12, described solid electrolyte belongs to anorthic system and P
1Space group; Wherein, Z is the high-valency metal element, its cationic compound valency is greater than+1 valency and less than or equal to+3 valencys, and described high-valency metal element Z is at least a in Mg, Al, Ca, Ti, Cu, Zn, Ga, In, Sr, Ru, Rh, Pd, Ag, Cd, Ba, Os, Ir, Pt or Hg; M is at least a in Ge, Si, Sn, Al, P; X is at least a in O, S, Se.
(the Li of these metallic elements after modification
mZ
n) MP
2X
12In material, all can show the cation of high price, thereby in the structure of this material, can improve better the interionic Coulomb attraction effect of contrary sign, and the interionic coulomb repulsion effect of shielding X.(the Li that obtains by high-valency metal element Z doping
mZ
n) MP
2X
12Crystalline material, it can strengthen ZX effectively
6Octahedron and MX
4Interaction between tetrahedron, also shielded the coulomb repulsion effect between the X ion simultaneously more strongly, thereby significantly reduce the material system total energy, strengthened the stability of material structure framework, thereby reached the purpose that improves on the whole material structure stability.
In the solid electrolyte material according to lithium ion battery of the present invention, m is 8～11 rational.Preferably, m is 9～10 rational.If (Li
mZ
n) MP
2X
12In material structure, the content of lithium very little, can reduce the transition position of lithium ion in diffusion process, affects the diffusion of lithium ion in this material.If (Li
mZ
n) MP
2X
12In material structure, lithium content is too many, must reduce other cationic chemical valences in this material, and then affects the stability of corresponding tetrahedral structure.
In the solid electrolyte material according to lithium ion battery of the present invention, n is 0～2 rational.Preferably, n is 0.5～1 rational.If the high volence metal ion content of doping is too many, because system will keep electric neutrality, (Li
mZ
n) MP
2X
12Lithium ion content in material will inevitably reduce in a large number, thereby affects the diffusion of lithium ion in this material.If the high volence metal ion content of doping very little, the high-valency metal element of doping will weaken to the lifting of the interionic Coulomb attraction effect of contrary sign and to the shielding of the interionic coulomb repulsion effect of jack per line, thereby reaches the whole (Li of raising
mZ
n) MP
2X
12The purpose of material structure stability.
In the solid electrolyte material according to lithium ion battery of the present invention, preferably, described M is at least a in Ge, Si, Sn.From microstructure characteristic, (Li
mZ
n) MP
2X
12M in material (M=Si, Ge or Sn) forms tetrahedral structure with X (X=S or Se) and forms local tetrahedron crystalline field, and Si, Ge and Sn are positioned at the same main group of periodic table, have similar peripheral electron to arrange, so they are at (Li
mZ
n) MP
2X
12In structural framing, can produce similar crystal field effects.
In the solid electrolyte material according to lithium ion battery of the present invention, preferably, described X is at least a in S, Se.From microstructure characteristic, (Li
mZ
n) MP
2X
12X in material (X=S or Se) forms tetrahedral structure with M (M=Si, Ge or Sn) and forms local tetrahedron crystalline field, and S and Se are positioned at the same main group of periodic table, have similar peripheral electron to arrange, so they are at (Li
mZ
n) MP
2X
12In material, can produce similar crystal field effects.
Next embodiment and Comparative Examples according to the solid electrolyte material of lithium ion battery of the present invention are described.
Comparative Examples
Under 550 ℃, purity is in 99.999% ar gas environment, by Li
2S, P
2S
5With GeS
2According to mol ratio, be that 5:1:1 is placed in the high-energy ball milling device and is milled to evenly, obtain the powder after ball milling; Then the powder after ball milling is placed in to the quartz ampoule that is full of argon gas, under 600 ℃, processes 8h, obtain Li
10GeP
2S
12Crystal grain (can referred to as the LGPS material), slowly cool to room temperature afterwards.
Embodiment 1
Under 550 ℃, purity is in 99.999% ar gas environment, by Li
2S, CaS, P
2S
5With GeS
2According to mol ratio, be that 4:1:1:1 is milled to evenly in the high-energy ball milling device, obtain the powder after ball milling; Then the powder after ball milling is placed in to the quartz ampoule that is full of argon gas, under 600 ℃, processes 8h, obtain Li
8CaGeP
2S
12Crystal grain, slowly cool to room temperature afterwards.Solid electrolyte material Li
8CaGeP
2S
12In doped with Ca
2+.The Ca of this doping
2+With respect to Li
+Can with its around S
2-Form stronger Coulomb attraction power, and can shield more strongly S
2-With S
2-Between coulomb repulsion power.Ca
2+Li doped
+Front and back, S
2-From Ca
2+The charge number that obtains on every side obviously will be higher than from Li
+The charge number that obtains on every side, i.e. Ca
2+With S
2-Between the Coulomb attraction effect than Li
+With S
2-Between the Coulomb attraction effect be eager to excel, S simultaneously
2-Between also conductively-closed better of coulomb repulsion effect, thereby Li
8CaGeP
2S
12The structural stability integral body of material system has obtained enhancing.
Embodiment 2
Under 550 ℃, purity is in 99.999% ar gas environment, by Li
2S, CaS, P
2S
5With GeS
2According to mol ratio, be that 4.5:0.5:1:1 is milled to evenly in the high-energy ball milling device, obtain the powder after ball milling; Then the powder after ball milling is placed in to the quartz ampoule that is full of argon gas, under 600 ℃, processes 8h, obtain Li
9Ca
0.5GeP
2S
12Crystal grain, slowly cool to room temperature afterwards.Solid electrolyte material Li
9Ca
0.5GeP
2S
12In doped with Ca
2+.The Ca of this doping
2+With respect to Li
+Can with its around S
2-Form stronger Coulomb attraction power, and can shield more strongly S
2-With S
2-Between coulomb repulsion power.Ca
2+Li doped
+Front and back, S
2-From Ca
2+The charge number that obtains on every side obviously will be higher than from Li
+The charge number that obtains on every side (seeing the contrast of Fig. 4 and Fig. 1), i.e. Ca
2+With S
2-Between the Coulomb attraction effect than Li
+With S
2-Between the Coulomb attraction effect be eager to excel, S simultaneously
2-Between also conductively-closed better of coulomb repulsion effect, thereby Li
9Ca
0.5GeP
2S
12The structural stability integral body of material system has obtained enhancing.Solid electrolyte material Li in the present embodiment
9Ca
0.5GeP
2S
12XRD spectrum as shown in Figure 5, with doping front space group be P
1The XRD figure (Fig. 3) of LGPS compare, can find that the characteristic spectrum peak position of Ca doping is in 42 ° of left and right, position as shown in five-pointed star in Fig. 5.This characteristic peak reflects that the Ca doping is to solid electrolyte material Li
9Ca
0.5GeP
2S
12The impact of structural stability, it can be along with lithium ion at Li
9Ca
0.5GeP
2S
12Diffusion and change.
Embodiment 3
Under 550 ℃, purity is in 99.999% ar gas environment, by Li
2S, CaS, P
2S
5With Al
2S
3According to mol ratio, be that 4.5:1:1:0.5 is milled to evenly in the high-energy ball milling device, obtain the powder after ball milling; Then the powder after ball milling is placed in to the quartz ampoule that is full of argon gas, under 600 ℃, processes 8h, obtain Li
9CaAlP
2S
12Crystal grain, slowly cool to room temperature afterwards.Solid electrolyte material Li
9CaAlP
2S
12In doped with Ca
2+.The Ca of this doping
2+With respect to Li
+Can with its around S
2-Form stronger Coulomb attraction power, and can shield more strongly S
2-With S
2-Between coulomb repulsion power.Ca
2+Li doped
+Front and back, S
2-From Ca
2+The charge number that obtains on every side obviously will be higher than from Li
+The charge number that obtains on every side, i.e. Ca
2+With S
2-Between the Coulomb attraction effect than Li
+With S
2-Between the Coulomb attraction effect obtained enhancing, S simultaneously
2-Between also conductively-closed better of coulomb repulsion effect, thereby Li
9CaAlP
2S
12The structural stability integral body of material system has obtained enhancing.
Embodiment 4
Under 550 ℃, purity is in 99.999% ar gas environment, by Li
2S, Ga
2S
3, P
2S
5With Al
2S
3According to mol ratio, be that 4:0.5:1:0.5 is milled to evenly in the high-energy ball milling device, obtain the powder after ball milling; Then the powder after ball milling is placed in to the quartz ampoule that is full of argon gas, under 600 ℃, processes 8h, obtain Li
8GaAlP
2S
12Crystal grain, slowly cool to room temperature afterwards.Solid electrolyte material Li
8GaAlP
2S
12In doped with Ga
3+.The Ga of this doping
3+With respect to Li
+Can with its around S
2-Form stronger Coulomb attraction power, and can shield more strongly S
2-With S
2-Between coulomb repulsion power.Ga
3+Li doped
+Front and back, S
2-From Ga
3+The charge number that obtains on every side obviously will be higher than from Li
+The charge number that obtains on every side, i.e. Ga
3+With S
2-Between the Coulomb attraction effect than Li
+With S
2-Between the Coulomb attraction effect obtained enhancing, S simultaneously
2-Between also conductively-closed better of coulomb repulsion effect, thereby Li
8GaAlP
2S
12The structural stability integral body of material system has obtained strengthening further.
Embodiment 5
Under 550 ℃, purity is in 99.999% ar gas environment, by Li
2S, Ga
2S
3, P
2S
5With GeS
2According to mol ratio, be that 4.25:0.25:1:1 is milled to evenly in the high-energy ball milling device, obtain the powder after ball milling; Then the powder after ball milling is placed in to the quartz ampoule that is full of argon gas, under 600 ℃, processes 8h, obtain Li
8.5Ga
0.5GeP
2S
12Crystal grain, slowly cool to room temperature afterwards.Solid electrolyte material Li
8.5Ga
0.5GeP
2S
12In doped with Ga
3+.The Ga of this doping
3+With respect to Li
+Can with its around S
2-Form stronger Coulomb attraction power, and can shield more strongly S
2-With S
2-Between coulomb repulsion power.Ga
3+Li doped
+Front and back, S
2-From Ga
3+The charge number that obtains on every side obviously will be higher than from Li
+The charge number that obtains on every side (seeing the contrast of Fig. 6 and Fig. 1), i.e. Ga
3+With S
2-Between the Coulomb attraction effect than Li
+With S
2-Between the Coulomb attraction effect obtained enhancing, S simultaneously
2-Between also conductively-closed better of coulomb repulsion effect, thereby Li
8.5Ga
0.5GeP
2S
12The structural stability integral body of material system has obtained strengthening further.
Embodiment 6
Under 550 ℃, purity is in 99.999% ar gas environment, by Li
2S, Ga
2S
3, GeS
2, P
2S
5With Al
2S
3According to mol ratio, be that 4.5:0.25:0.5:1:0.25 is milled to evenly in the high-energy ball milling device, obtain the powder after ball milling; Then the powder after ball milling is placed in to the quartz ampoule that is full of argon gas, under 600 ℃, processes 8h, obtain Li
9Ga
0.5Al
0.5Ge
0.5P
2S
12Crystal grain, slowly cool to room temperature afterwards.Solid electrolyte material Li
9Ga
0.5Al
0.5Ge
0.5P
2S
12In doped with Ga
3+.The Ga of this doping
3+With respect to Li
+Can with its around S
2-Form stronger Coulomb attraction power, and can shield more strongly S
2-With S
2-Between coulomb repulsion power.Ga
3+Li doped
+Front and back, S
2-From Ga
3+The charge number that obtains on every side obviously will be higher than from Li
+The charge number that obtains on every side, i.e. Ga
3+With S
2-Between the Coulomb attraction effect than Li
+With S
2-Between the Coulomb attraction effect obtained enhancing, S simultaneously
2-Between also conductively-closed better of coulomb repulsion effect, thereby Li
9Ga
0.5Al
0.5Ge
0.5P
2S
12The structural stability integral body of material system has obtained strengthening further.
Embodiment 7
Under 550 ℃, purity is in 99.999% ar gas environment, by Li
2S, Ga
2S
3, P
2S
5With Al
2S
3According to mol ratio, be that 4.75:0.25:1:0.5 is milled to evenly in the high-energy ball milling device, obtain the powder after ball milling; Then the powder after ball milling is placed in to the quartz ampoule that is full of argon gas, under 600 ℃, processes 8h, obtain Li
9.5Ga
0.5AlP
2S
12Crystal grain, slowly cool to room temperature afterwards.Solid electrolyte material Li
9.5Ga
0.5AlP
2S
12In doped with Ga
3+.The Ga of this doping
3+With respect to Li
+Can with its around S
2-Form stronger Coulomb attraction power, and can shield more strongly S
2-With S
2-Between coulomb repulsion power.Ga
3+Li doped
+Front and back, S
2-From Ga
3+The charge number that obtains on every side obviously will be higher than from Li
+The charge number that obtains on every side, i.e. Ga
3+With S
2-Between the Coulomb attraction effect than Li
+With S
2-Between the Coulomb attraction effect obtained enhancing, S simultaneously
2-Between also conductively-closed better of coulomb repulsion effect, thereby Li
9.5Ga
0.5AlP
2S
12The structural stability integral body of material system has obtained strengthening further.
Adopt the X-ray diffraction mensuration Comparative Examples of CuK α line and the diffracting spectrum of the solid electrolyte material in embodiment 1-7, draw (Li
mZ
n) MP
2X
12The lattice parameter of material, thus draw (Li
mZ
n) MP
2X
12The unit cell volume of material and corresponding volume change.In addition, with the lattice parameter that measures, build corresponding (Li
mZ
n) MP
2X
12The material structure model, calculate (Li
mZ
n) MP
2X
12The average bond length of Z ion and X ion in material structure, thereby according to Coulomb's law formula U=(kQ
1Q
2)/d
12, wherein k is the electrostatic force constant, Q
1, Q
2By ion electrically charged, d
12Be two kinds of average distances between ion.And with Li in LGPS
+With S
2-Between average Coulomb attraction can be reference value, draw the average Coulomb attraction energy between Z ion and X ion, result of calculation is as shown in table 1.
The test of the solid electrolyte material of table 1 Comparative Examples and embodiment 1-7 and result of calculation.
As can be seen from Table 1, the structural framing of the solid electrolyte material of embodiment 1-7 is quite analogous to the structural framing of the LGPS material before doping, before and after doping, the volume change of solid electrolyte material is very little, the diffusion admittance that has kept the lithium fast transferring on structure, guaranteed that the quick lithium-ion electric of solid electrolyte material is led.Simultaneously, in table 1, provide again in the structural framing of Comparative Examples and the solid electrolyte material of embodiment 1-7 the relative average Coulomb attraction energy that respectively adulterates between ion and sulphion, reflected the relative stability of the solid electrolyte material structure of the relative Comparative Examples of embodiment 1-7.Coulomb attraction take the lithium ion in Comparative Examples LGPS and sulphion can be as reference value, in table 1, provided in embodiment 1-7 the relative Coulomb attraction energy of cation and anion in the rear solid electrolyte material structural framing that adulterates, this energy more negative indication Coulomb attraction effect is stronger.As can be seen from Table 1, after the LGPS material is carried out to element doping, the Coulomb attraction of solid electrolyte material can obviously reduce (the coulomb repulsion effect in material between sulphion and sulphion has also obtained obviously weakening), so with respect to Comparative Examples, in embodiment 1-7, the total energy of solid electrolyte material will be lower, and its structure is more stable.
Claims (7)
1. the solid electrolyte material of a lithium ion battery, is characterized in that,
The general formula of described solid electrolyte material is (Li
mZ
n) MP
2X
12, described solid electrolyte belongs to anorthic system and P
1Space group;
Wherein, Z is the high-valency metal element, its cationic compound valency is greater than+1 valency and less than or equal to+3 valencys, and described high-valency metal element Z is at least a in Mg, Al, Ca, Ti, Cu, Zn, Ga, In, Sr, Ru, Rh, Pd, Ag, Cd, Ba, Os, Ir, Pt, Hg;
M is at least a in Ge, Si, Sn, Al, P;
X is at least a in O, S, Se.
2. the solid electrolyte material of lithium ion battery according to claim 1, is characterized in that, m is 8～11 rational.
3. the solid electrolyte material of lithium ion battery according to claim 2, is characterized in that, m is preferably 9～10 rational.
4. the solid electrolyte material of lithium ion battery according to claim 1, is characterized in that, n is 0～2 rational.
5. the solid electrolyte material of lithium ion battery according to claim 4, is characterized in that, n is preferably 0.5～1 rational.
6. the solid electrolyte material of lithium ion battery according to claim 1, is characterized in that, described M is preferably at least a in Ge, Si, Sn.
7. the solid electrolyte material of lithium ion battery according to claim 1, is characterized in that, described X is preferably at least a in S, Se.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310347932.9A CN103401018B (en) | 2013-08-09 | 2013-08-09 | Solid electrolyte material of lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310347932.9A CN103401018B (en) | 2013-08-09 | 2013-08-09 | Solid electrolyte material of lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103401018A true CN103401018A (en) | 2013-11-20 |
| CN103401018B CN103401018B (en) | 2016-08-10 |
Family
ID=49564594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310347932.9A Active CN103401018B (en) | 2013-08-09 | 2013-08-09 | Solid electrolyte material of lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103401018B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109314274A (en) * | 2016-03-11 | 2019-02-05 | 国立大学法人东京工业大学 | Sulfide solid electrolyte |
| CN109841898A (en) * | 2019-03-13 | 2019-06-04 | 宁德新能源科技有限公司 | Solid electrolyte and its preparation method and electrochemical appliance and electronic device comprising it |
| US10446872B2 (en) | 2015-08-04 | 2019-10-15 | Samsung Electronics Co., Ltd. | Solid electrolyte and lithium battery including the same |
| CN113948765A (en) * | 2021-10-14 | 2022-01-18 | 中国石油大学(华东) | Preparation method of solid electrolyte, solid electrolyte and lithium battery |
| US11264602B2 (en) | 2019-05-08 | 2022-03-01 | Samsung Electronics Co., Ltd. | Sulfide glass-ceramic lithium-ion solid-state conductor |
| CN114291845A (en) * | 2021-12-29 | 2022-04-08 | 北京卫蓝新能源科技有限公司 | Anion-cation co-doped lithium ion solid material and preparation method and application thereof |
| US11588174B2 (en) | 2019-01-23 | 2023-02-21 | Ningde Amperex Technology Limited | Solid electrolyte and preparation method thereof, and electrochemical device and electronic device comprising solid electrolyte |
| WO2023030026A1 (en) * | 2021-09-01 | 2023-03-09 | 上海屹锂新能源科技有限公司 | Method for preparing sulfide solid electrolyte material and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103000934A (en) * | 2011-09-16 | 2013-03-27 | 苏州宝时得电动工具有限公司 | Lithium-sulfur battery |
-
2013
- 2013-08-09 CN CN201310347932.9A patent/CN103401018B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103000934A (en) * | 2011-09-16 | 2013-03-27 | 苏州宝时得电动工具有限公司 | Lithium-sulfur battery |
Non-Patent Citations (4)
| Title |
|---|
| A.AATIQ, ET AL.: "Structural and Electrochemical Study of Li0.5Mn0.5Ti1.5Cr0.5(PO4)3", 《JOURNAL OF SOLID STATE CHEMISTRY》, vol. 158, 31 December 2001 (2001-12-31), pages 169 - 174, XP002975795, DOI: doi:10.1006/jssc.2001.9088 * |
| JIE FU: "Superionic conductivity of glass-ceramics in the system Li2O-Al2O3-TiO2-P2O5", 《SOLID STATE IONICS》, vol. 96, 31 December 1996 (1996-12-31), pages 195 - 200, XP004061485, DOI: doi:10.1016/S0167-2738(97)00018-0 * |
| R.H.P.FRANCISCO: "Compoud Formation and Local Structure in Ternary Metal-Phosphorus-Selenium Systems", 《JOURNAL OF SOLID STATE CHEMISTRY》, vol. 112, 31 December 1994 (1994-12-31), pages 270 - 276 * |
| SHYUE PING ONG, ET AL.: "Phase stability, electrochemical stability and ionic conductivity of the Li10±1MP2X12 (M = Ge, Si, Sn, Al or P, and X = O, S or Se", 《ENERGY&ENVIRONMENTAL SCIENCE》, vol. 6, 2 October 2012 (2012-10-02), pages 148 - 156 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10446872B2 (en) | 2015-08-04 | 2019-10-15 | Samsung Electronics Co., Ltd. | Solid electrolyte and lithium battery including the same |
| CN109314274B (en) * | 2016-03-11 | 2021-08-24 | 国立大学法人东京工业大学 | Sulfide solid electrolyte |
| CN109314274A (en) * | 2016-03-11 | 2019-02-05 | 国立大学法人东京工业大学 | Sulfide solid electrolyte |
| US11588174B2 (en) | 2019-01-23 | 2023-02-21 | Ningde Amperex Technology Limited | Solid electrolyte and preparation method thereof, and electrochemical device and electronic device comprising solid electrolyte |
| WO2020181848A1 (en) * | 2019-03-13 | 2020-09-17 | Ningde Amperex Technology Limited | Solid electrolyte and preparation method thereof, and electrochemical device and electronic device comprising same |
| US11050081B2 (en) | 2019-03-13 | 2021-06-29 | Ningde Amperex Technology Limited | Solid electrolyte and preparation method thereof, and electrochemical device and electronic device comprising same |
| CN109841898A (en) * | 2019-03-13 | 2019-06-04 | 宁德新能源科技有限公司 | Solid electrolyte and its preparation method and electrochemical appliance and electronic device comprising it |
| US11264602B2 (en) | 2019-05-08 | 2022-03-01 | Samsung Electronics Co., Ltd. | Sulfide glass-ceramic lithium-ion solid-state conductor |
| WO2023030026A1 (en) * | 2021-09-01 | 2023-03-09 | 上海屹锂新能源科技有限公司 | Method for preparing sulfide solid electrolyte material and application thereof |
| CN113948765A (en) * | 2021-10-14 | 2022-01-18 | 中国石油大学(华东) | Preparation method of solid electrolyte, solid electrolyte and lithium battery |
| CN113948765B (en) * | 2021-10-14 | 2024-05-14 | 中国石油大学(华东) | Preparation method of solid electrolyte, solid electrolyte and lithium battery |
| CN114291845A (en) * | 2021-12-29 | 2022-04-08 | 北京卫蓝新能源科技有限公司 | Anion-cation co-doped lithium ion solid material and preparation method and application thereof |
| CN114291845B (en) * | 2021-12-29 | 2024-06-11 | 中科超能(深圳)新能源科技有限公司 | Anionic-cationic co-doped lithium ion solid material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103401018B (en) | 2016-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103401018A (en) | Solid-state electrolyte material of lithium ion battery | |
| Deng et al. | Enhancing the lithium ion conductivity in lithium superionic conductor (LISICON) solid electrolytes through a mixed polyanion effect | |
| Li et al. | Progress and perspectives on halide lithium conductors for all-solid-state lithium batteries | |
| Vicente et al. | Methylammonium lead bromide perovskite battery anodes reversibly host high Li-ion concentrations | |
| Cai et al. | In situ lithiophilic layer from H+/Li+ exchange on garnet surface for the stable lithium-solid electrolyte interface | |
| Lopez-Aranguren et al. | Crystalline LiPON as a bulk-type solid electrolyte | |
| Ren et al. | Oxide electrolytes for lithium batteries | |
| Choi et al. | Enhanced Li ion conductivity in LiBH4–Al2O3 mixture via interface engineering | |
| Kato et al. | Synthesis, structure and lithium ionic conductivity of solid solutions of Li10 (Ge1− xMx) P2S12 (M= Si, Sn) | |
| Tang et al. | Effect of EMIMBF4 ionic liquid addition on the structure and ionic conductivity of LiBF4-complexed PVdF-HFP polymer electrolyte films | |
| Zeier et al. | Dependence of the Li-ion conductivity and activation energies on the crystal structure and ionic radii in Li6MLa2Ta2O12 | |
| Zhang et al. | Preparation and electrochemical properties of Li1+ xAlxGe2-x (PO4) 3 synthesized by a sol-gel method | |
| Palakkathodi Kammampata et al. | Cruising in ceramics—discovering new structures for all-solid-state batteries—fundamentals, materials, and performances | |
| Xu et al. | Lithium ion conductivity in double antiperovskite Li6. 5OS1. 5I1. 5: alloying and boundary effects | |
| CN100524927C (en) | Solid electrolyte material system for all solid state lithium battery and preparation method | |
| CN105742698B (en) | NASICON type sodion solid electrolytes materials and preparation method thereof | |
| Shao et al. | Recent research on strategies to improve ion conduction in alkali metal‐ion batteries | |
| Kim et al. | Thermally induced S-sublattice transition of Li3PS4 for fast lithium-ion conduction | |
| Park et al. | Chemically evolved composite lithium-ion conductors with lithium thiophosphates and nickel sulfides | |
| Yang et al. | Titanium dioxide doping toward high-lithium-ion-conducting Li1. 5Al0. 5Ge1. 5 (PO4) 3 glass-ceramics for all-solid-state lithium batteries | |
| CN109860700A (en) | A kind of Nasicon structure sodion solid electrolytes and its preparation method and application | |
| Yu et al. | A composite electrolyte with Na3Zr2Si2PO12 microtube for solid-state sodium-metal batteries | |
| Gao et al. | Sb‐and O‐Cosubstituted Li10SnP2S12 with High Electrochemical and Air Stability for All‐Solid‐State Lithium Batteries | |
| Zhang et al. | Advances in solid lithium ion electrolyte based on the composites of polymer and LLTO/LLZO of rare earth oxides | |
| Roh et al. | Enhanced Li-Ion Conductivity and Air Stability of Sb-Substituted Li4GeS4 toward All-Solid-State Li-Ion Batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 352100 Jiaocheng District of Ningde City, Fujian Province Zhang Wan Zhen Xingang Road No. 1 Applicant after: Contemporary Amperex Technology Co.,Ltd. Address before: 352100 Jiaocheng District of Ningde City, Fujian Province Zhang Wan Zhen Xingang Road No. 1 West Building 1F- research Applicant before: CONTEMPORARY AMPEREX TECHNOLOGY Ltd. |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |