Student name:Guanchong Chen Student number:6055850

University of Wollongong

MMMB940 Advanced Project

Master of Materials Engineering

Lithium-ion battery solid electrolyte

Student Name: Guanchong Chen

Student Number: 6055850

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Student name:Guanchong Chen Student number:6055850

content
Abstract……………………………………………………………………………………………
…………….3

1.Introduction…………………………………………………………………………
…………4
2.All-solid-state batteries (ASSB)
…………………………………………………………4
2.1inorganic solid electrolyte (ISE)
………………………………………………………………5

2.1.1
LISICON……………………………………………………………………………………………
…………6

2.1.2
NAISICON…………………………………………………………………………………………
……11

2.1.3 Perovskite-type
electrolytes……………………………………………………………………15

2.1.4 Argyrodite-type
electrolytes……………………………………………………………………18

2.1.5 Sulfide-type
electrolytes…………………………………………………………………………19

2.1.6 Garnet-type
electrolytes…………………………………………………………………………20

2.2 solid polymer electrolyte (SPE)

…………………………………………………………………20

3. Analysis of solid electrolyte

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defects………………………………………………………………22

4.Conclusions…………………………………………………………………………………
………………22

5. Future development trends and

directions……………………………………………………22

6.
References………………………………………………………………………………………
………….23

Abstract

For this science dissertation, the subject is the current state of solid electrolyte
research and some related analysis. The types and advantages of various solid
electrolytes are analyzed, such as the introduction of perovskite, LISICON, and
NASICON solid electrolytes, as well as some data and characterization results. At
the same time, the corresponding analysis of the material deficiencies, such as
ion conductivity, ion diffusion, and manufacturing cost are carried out.
Summarized various opinions on solid electrolytes, and concluded discussions
and future prospects at the end of this article

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1.Introduction:
The origin of lithium-ion batteries began in the 20th century and continues to
develop to the present. From the earliest lithium-ion battery model, the "rocking
chair battery concept" was formed and finally mass-produced. Scientists attach
great importance to the development of lithium-ion batteries. Compared with
other energy sources, the advantages of lithium-ion batteries are convenience,
low pollution, high energy density and long service life [1]. Combining these
advantages, lithium-ion batteries have begun to penetrate all aspects of human
society. For example, Tesla’s Modal S uses more than 6,000 18650-size lithium-
ion batteries as the battery pack for cars [2].
Due to the continuous development of liquid lithium-ion batteries,
corresponding problems continue to appear. With potential safety hazards,
problems such as the number of charging and discharging of batteries continue
to increase. Research on solid-state electrolyte lithium-ion batteries ushered in
development. In the past ten years, the corresponding solid electrolyte research
has continuously increased. From the initial appearance of solid electrolytes in
1900 to the continuous development of today, solid-state lithium-ion batteries
are becoming more and more likely as the next generation of energy[3].
Traditional lithium-ion batteries have some specific problems in current
research. Due to the particularity of the electrolyte of lithium ion batteries, the
solvent generally uses carbonate organics such as PC, DEC, EC/DMC. It can be
used normally within a certain temperature range, but in a lower temperature
range, the viscosity of the solvent will increase. In the higher temperature range,
the conducting salt will decompose and affect the efficiency of the battery. On the
other hand, due to flammable polymer components, liquid electrolyte lithium-ion
batteries have safety hazards.
For research in this direction, it is worth spending time and money to keep
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trying. Because the biggest advantage of solid electrolyte is that it can use a metal
negative electrode to complete the battery assembly. Pure metals have lower
electrode potentials, which means that solid electrolyte batteries can obtain
higher voltages. This can permanently reduce costs for the electric vehicle
industry[4].
Compared with liquid electrolyte batteries, inorganic solid electrolyte batteries
have strong advantages.
1. High energy density.
2. Because of the existence of metal lithium negative electrode. The electrode
potential of the negative electrode is greatly reduced. Make the redox around the
battery stronger.
3. Avoid excessive growth of lithium dendrites.
4. Small size, more convenient to use.
5. High safety in use, preventing leakage
At the same time, for the solid electrolyte, the requirements that should be met
are:
1. Improve ionic conductivity to the level equivalent to that of liquid electrolyte.
2. While meeting high ionic conductivity, it has extremely low electronic
conductivity
3. The metal lithium anode can be used stably[5].
Facing the emergence of various problems, and the possibility of obtaining a
lower electrode potential. All-solid-state batteries (ASSB) have become a new
research focus(Zheng et al.). For the electrolyte of all solid-state batteries, its
types can be divided into three types: inorganic solid electrolyte (ISE), solid
polymer electrolyte (SPE) and composite polymer electrolyte (CPE).

2. All-solid-state batteries (ASSB)

Due to the wide variety of all-solid-state electrolyte lithium-ion batteries, most
of the classifications can be divided into inorganic and organic types, which will
be discussed in this chapter

2.1 inorganic solid electrolyte (ISE)

The ion propagation of inorganic solid electrolyte relies on diffusion motion to
conduct ion. As the size and valence of the ion decrease, the ion conductivity will
gradually increase. This is caused by the interaction between ions[6].

2.1.1 LISICON
LISICON is a super-ionic conductor of Li. It has a very standardized
chemical composition, Li 2 + 2 x Zn 1- x GeO 4. It was discovered and published by
Huang in 1977. The discovery of LISICON means that lithium-ion batteries have
realized the possibility of solid electrolytes in the sense of development. For the
composition of the initial LISICON electrolyte, a very low resistivity at 300°C and
low ionic conductivity were achieved. This is because LISICON has a rigid three-
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dimensional structure in space, which allows Li ions to complete rapid ion

transport, and at the same time has the characteristics of covalent bond sharing,
which can increase ion mobility to a certain extent.

Fig1 LISICON spatial structure diagram [7]

However, in recent research studies, the traditional LISICON electrolyte
materials have been insufficient to meet the research of solid electrolytes. To a
greater extent is to improve LISICON.
In the improvement of LISICON, a more common solution is to use sulfur LISICON
material as the electrolyte of solid-state batteries. Thio-LISICON introduces
interstitial lithium ions of Zr 4+ partially substituted by Zn 2+ through solid-
phase reaction (Li 2 + 2 x Zn x Zr 1-x S 3; x = 0, 0.05, 0.1, 0.2, 0.4) [8]. ZnS, Li 2 S, sulfur
and zirconium powder are continuously mixed and distributed in a certain molar
ratio, and then placed in a glass tube, flushed with inert gas, and then heated on a
heating furnace at a certain temperature for 10 mm. The tube is slowly cooled to
room temperature, and the sample is finally obtained.
According to the experimental results, the conductivity of sulfide LISICON is
7.3×10-6Scm-1[8]. This result shows that the performance of thio LISICON is
better than some other electrolyte materials, and according to the conductivity
diffraction pattern, you can find the material The conductivity presents a
parabolic shape, so for some low-conductivity thio LISICON electrolyte materials,
the way to improve them is to replace them with heterovalent bonds to achieve
the desired goal. For example, to increase the value by one level, you can use
sulfur Replacement of silicon[9].
For other studies, a feasible method is to use inert gas to convert lithium ions
into lithium ion substructures at high temperatures to obtain better diffusion
pathways and ion transport channels. For the thio LISICON electrolyte with a
lithium ion structure, under the protection of Ar gas, the raw materials such as
LiS are continuously heated at a high temperature of 700°C to change the form of
lithium ions and become a lithium ion structure[10].
For the material characterization of LISICON with lithium substructure, due to
the particularity of the material, infrared spectroscopy powder diffraction cannot
be used to determine the value, and neutron diffraction is needed to locate the
existence of lithium substructure, so the results of neutron diffraction can be
seen. The molar volume area of Sn gradually increases with the appearance of
lithium subions, and Sn ions show a larger particle radius. Therefore, the overall
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ion transition ability increases. But at the same time, there is lattice movement
inside the molecule, which is caused by the compression between the unit cells,
so the low-temperature synthesis method should be used in temperature to be
more perfect.

Figure 2. The percentage of Sn derived from the neutron diffraction pattern, compared with the area of the
LISICON polyhedron (a) The rise of Li in LISICON and the effect of Sn on the volume (b) Li displayed when
the value of Sn is less than 0.75 (C) The amount of Li added (d) The overall area is increased due to the
increase of the lithium substructure of LISICON.[10]
Figure 2. The occupancy rate of refined tin extracted in Rietveld refining of
neutron diffraction data, changing the volume and plane area of Li polyhedron.
(a) Increase the volume of Li(1)S 4 with x in Li 4 Ge 1– x Sn x S 4. (b) Li(2)S 4 times the
capacity remains basically unaffected through Sn content of X ≤ 0.75, but exhibits
a significant reduction in X = 1 (c) increased Li (3) Volume 6 With Sn content. (d)
The surface area of the triangular plane formed by two adjacent Li (3)S6
octahedrons increases with the increase of Sn content. The volume of Li (3)S 6Li 4
SnS 4 and the surface area of the triangular plane are significantly increased.
Regarding the modification method of LISICON, other studies have shown that
pure phase materials like LISICON can be used as electrolytes in lithium-ion
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batteries. Li3 V 2 (PO 4) 3 is a successful LISICON-like structure electrolyte material.

It can carry out rapid migration between multiple ions at low temperatures, and
is very popular for electrolytes and anode materials for lithium-ion batteries. For
the synthesis method of this material, the raw materials are synthesized by Li 2
CO 3, V 2 O 5 and NH 4 H 2 PO 4 in a pure solution environment. Hydrolysis was
carried out by citric acid, and then heated to 80°C in a water bath. The product is
extracted and continuously calcined at a high temperature of 400°C. The high
temperature calcination at 750°C is carried out under the action of protective
gas, and finally the LISICON-like electrolyte material is obtained[11].

Figure3 electrolyte performance of LISIOCN-like materials in different temperature ranges[11]

For the electrochemical performance characterization of LISICON-like materials,
Figure 3 shows the electrolyte performance of LISIOCN-like materials in different
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temperature ranges
The electrochemical performance of LISICON-like materials has better
advantages than other LISICON materials. Its ion mobility and conductivity are
significantly higher than other materials. At the same time, due to its strong
electrical capacity, it can be used as an excellent negative electrode material for
solid-state lithium-ion batteries.
Li 11 AlP 2 S 12 is also a LISICON-like material with high performance. It has high
conductivity and low voltage window. It can be abbreviated as LAlPS. It has a
similar synthesis method to thio-LISICON. It uses Al 2S3 as the raw material for the
substituted synthesis conditions. The raw material grinding at 40°C is also
performed under the protection of inert gas Ar. And the preform is heated at 400
℃ for 18h, and finally a cooled chiral target product 400, 500, 600 can be
obtained.

Figure4 Schematic structure of LAlPS 500 [12]

In terms of the properties of the material, the analysis that can be drawn is that
due to the particularity of the material, it has similar performance characteristics
to thio-LISICON. LAlPS500 and 600 show conductivity similar to thioLISICON, but
the conductivity of LAlPS400 is higher than this value at 25°C. According to the
analysis, this should be the chiral structure of the material and the structural
characteristics of thio-LISICON.
In some other studies, the modification method of thio-LISICON can expand the
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Student name:Guanchong Chen Student number:6055850

ion channel by mixing other electrolytes to achieve the purpose of increasing ion
conductivity. Li2S-P2S 5 is a typical thio LISICON material, and its ionic
conductivity can reach 6.3×10 -4 S cm -1 at room temperature. But for lithium-ion
batteries, such ionic conductivity is not enough for commercial production. So
another modification method is to mix Li 3BO3 derivatives in it to achieve higher
ionic conductivity. Through the final test, the maximum ionic conductivity of the
mixed material can finally reach 1.03×10 -3 S cm -1. This is a very successful result
for solid-state lithium-ion batteries.
In the experiment, it is first necessary to prepare a variety of precursor
derivatives xLi 3 BO 3 (x≤5) by mechanical grinding. The precursor is melted and
mixed with thio LISICON, heated to a completely molten state at 800°C, quenched
to form a glassy mixture powder, and the powder is ground under the action of a
ball mill for 2 hours to obtain the final synthetic powder[13].

Figure5 Raman spectrum, comparison of the conductivity of the mixture and the conductivity of the single
thio LISICON material at 25℃[13]
Figure5 shows the conductivity test of the sample, (a) temperature and
conductivity test. (B) Comparison of ion conductivity at 25°C. According to the
figure, when the doped Li 3BO3 is 0, it can be seen that the conductivity of thio-
LISICON is 6.10×10 -4 S cm -1 and the activation energy is 24.7 kJ mol -1, but when
doped When xLi 3 BO 3 (x=3), the ionic conductivity increases significantly, and
the activation energy decreases. The ratio of increase and decrease in value is
nearly doubled. This shows that adding some other solid electrolytes to some
thio LISICON materials can strengthen the electrolyte as a whole. According to
theory, in the process of doping the electrolyte, the original vacancy of lithium
ions is enlarged, increasing the number of vacancies, which makes the number of
insertion and deintercalation of lithium ions increased. At the same time, due to
the introduction of other anions, the overall activation energy of the battery is
reduced, and the overall conductivity of the electrolyte is enhanced[13].

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2.1.2 NAISICON
NASICON and LISICON have similar structures, and they both belong to a class of
compounds. For NASICON, it is a sodium superionic conductor, and its chemical
formula is Na 1 + x Zr 2 Si x P 3-x O 12 (0≤x≤3) NASICON solid electrolyte
material has certain advantages, because it is in three dimensions There is a
rhombohedral structure in the space. The rhombohedral structure means that
NASICON has good stability and resistance to deformation. This is desirable for
lithium ion batteries that require ion migration. According to Figure 5,
NASICON’s phosphate and zirconate together form the eight sides of the
rhombohedron. When x is within a certain range, the entire single crystal
presents a stable morphology. At the same time, due to the commonality of ions,
the upper and lower tetrahedrons of the octahedron can pass through the
particles, and the permeability is good. When flowing ions diffuse in the
rhombohedral body, the activation energy of the reaction will be reduced. When
X≥0, the activation energy of NASICON will change from high to low due to the
movement of ions. This is due to the interaction between moving ions. As the
activation energy decreases, the diffusion of ions decreases, and the overall
diffusion window shrinks. This has a great effect on improving ion conductivity. It
has been confirmed in some experiments that the ionic conductivity of the
NASICON electrolyte material is 2×10 -1 S cm -1 at 300°C[5].

Figure 6Space diagram of NASICON single crystal[5]

The preparation method of NASICON can be achieved by using a para-
substitution reaction, by replacing phosphate (PO4) or zirconate (ZrO) with Li
ions. However, at room temperature, the conductivity of the NASICON electrolyte
material is not ideal. The ionic conductivity at room temperature is only 3.3×10-6
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S cm -1, because at low temperatures, the single crystal structure of the NASICON
material is unstable and the ion permeability is not satisfactory. Strong. But when
the temperature is higher than 200°C, the ion conductivity will gradually
increase. During the entire heating process, NASICON electrolyte material will
gradually change from amorphous to rhombohedral structure, and the ionic
conductivity will eventually stabilize at 1.2×10 -2 S cm -1 C. At the same time, due
to the temperature change, the phase separation will occur, and the overall
structure will change, and a low-temperature phase and a high-temperature
phase appear, and the ionic conductivity of the high-temperature phase is 5×10
-4 S cm -1.
For the study of NASICON-like electrolytes, experiments can find that Li 1+ x Al x
Ti 2- x (PO 4) 3 with a spatial rhombohedral structure can be used as a solid
electrolyte material in lithium-ion batteries. The advantage of LATP electrolyte
material is its good chemical stability and simple synthesis method. However,
due to the special structure of LATP electrolyte material, its ionic conductivity is
not high at room temperature or high temperature. Only liquid electrolyte
material ionic conductivity One-tenth of the rate. Therefore, the improvement of
the ionic conductivity of this material has become the main problem of NASICON.
In many studies, it has been concluded that there are many ways to improve ionic
conductivity, such as melting, hydrothermal, and sol-gel.... The common point of
these methods is that they can fundamentally improve the ionic conductivity of
LATP. . The following introduction is based on the sol-gel method to prepare the
precursor, using citric acid as an auxiliary additive. This is because citric acid as
an additive can densify the structure of the LATP electrolyte material, and the ion
diffusion channel will become larger, thereby increasing the ion conductivity.
However, due to the large amount of barriers at the material grain boundaries, it
is necessary to introduce doping of other elements to reduce the interaction
between the grain boundaries. According to a large number of experiments, the
introduction of other elements will improve the overall transport effect of Li ions.
This fundamentally increases the ionic conductivity of the electrolyte and
reduces the activation energy[13].
The preparation method of LATP is the sol-gel method. The solvent is dissolved
in distilled water, the titanium hydroxide solution is obtained by constant
stirring, and the titanium dioxide solution is obtained by evaporation to dryness.
The pure titanium dioxide solution is mixed with citric acid, and the ratio of
titanium dioxide to citric acid is 1:3. Through the action of citric acid, the entire
precursor can be safely and stably synthesized. Mix the obtained precursor with
LiNO 3 and NH 4 H 2 PO 4, and complete this step in deionized water. A flocculent
gel is obtained by stirring the solution. The gel is dried and processed at a high
temperature for 3 hours, and the obtained preformed powder is sintered at a
temperature above 800° C. under a fixed pressure for 5 hours. You can get LATP
powder[13].

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Figure 7 LATP synthesis route map

In the overall electrochemical performance test, by preheating LATP at different
temperatures, electrolyte particles of different shapes are obtained. By studying
their temperature and cross section, it can be found that with the rising
temperature, the overall The ion conductivity has not been improved. According
to theory, it can be obtained that there are still barriers of grain boundaries in the
electrolyte. Although the increase in temperature will make the crystal grains
larger, since the crystal grains have not reached the limit, the original grain
boundaries cannot be destroyed, hindering the overall conductivity. According to
Figure 8, it can be found that the ion conductivity does not change with the
expansion of the crystal grains. According to the above deduction, it can be
obtained that in LATP, the data with the best ion conductivity is 8×10 -5 S cm
-1[13].

Figure 8a. Schematic diagram of the cross-section of LATP. b. The overall impedance diagram of the material.
c. Graph of ion conductivity data. d. The overall circuit diagram[13]

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For other studies, it is possible to use LLTO and NASICON electrolyte materials to
blend to obtain a higher performance hybrid electrolyte. First, the precursor
LLTO needs to be obtained in preparation. The materials needed are Li 2 CO 3, La
2 O 3 and TiO 2. The three ingredients were blended and milled continuously for
6 hours. After the mixture is obtained, it is air-dried for more than 24 hours and
pressed into a green body. The finished product is sintered at a high temperature
and crushed into powder to obtain an LLTO-type perovskite mixture. The
preparation of NASICON-like is similar to that of LLTO, using germanium to
replace Na ions and Li ions to replace Zr ions to obtain LAGP precursor materials.
The traditional solid-phase method is used for the preparation of composite
materials of LLTO and LAGP. After 5 hours of grinding and air drying treatment,
continuous sintering for more than 10 hours to obtain a blend of LLTO-LAGP[14].
During the test, the impedance of the Nyquist chart shows that in the low
frequency region, the impedance of the LLTO mixed electrolyte can be shown on
the chart, but the high frequency region will exceed the overall range. The
explanation for this problem can be tested by equivalent short circuit. The test
results show that the overall value is all below 0.6×10 -3. The result that can be
obtained is that the impedance performance of LLTO is poor. Through the study
of the electrical conductivity function of the LLTO mixture, it can be found that
the maximum electrical conductivity is 4.04×10 -4 S cm -1. The explanation
based on this result is that the charge layer of the mixed material is affected.
According to Figure 9, it can be seen that the overall conductivity has changed,
but the germanium oxide and phosphate compound in it have not changed. Based
on this result, it can be inferred that the decomposition of LLTO has a greater
impact on the overall conductivity of the material, which will disrupt the
arrangement of the charge layer and produce a lot of by-products. This is
meaningless for the increase in ionic conductivity

Figure 9LLTO-LAGP mixture ion conductivity function relationship[14]

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2.1.3 Perovskite-type electrolytes

Perovskite-type materials are a general term for a class of materials. It is
composed of all calcium titanium oxide. The perovskite type material is stable
because it has a spatial octahedral structure. According to its basic forming law, it
exists in nature in the form of two cations and three anions (ABX 3). According to
many studies on perovskite-type materials, it can be shown that it can be used in
lithium-ion solid-state batteries. LLTO is the mainstream perovskite electrolyte
material. It can be seen from its structure that it has adjustable lattice
parameters to change its electrochemical performance. If the lattice parameters
can be expanded in some way, this will increase the overall ion conductivity
value. According to some experiments, it can be achieved that the overall ion
conductivity can be increased to 1.5×10 -3 S cm -1 by doping other ions at the
positions of Li and La. However, due to the substitution of Li ions, the undesirable
consequence of this is that the overall Li ion mobility and concentration decrease.
Therefore, Li ions cannot be completely replaced by other ions[15].
For many studies, it can be shown that the disadvantage of LLTO material as an
electrolyte is that its grain boundary conductivity is not high enough. This is
because the sinterability is not good and the lattice constant is determined.
Therefore, in order to improve the overall LLTO conductivity, we can start with
the improvement of the compactness of the LLTO film. Many studies can show
that improving the sintering time and using other techniques for sintering, such
as microwave radiation, can improve the density of LLTO films. However, these
methods cannot be commercial tools due to cost and time. Therefore, chemical
doping becomes the only mainstream method that can improve the conductivity
of perovskite-type electrolyte materials.
Many i researches have carried out the improvement of perovskite materials, and
most of the experiments use a single ion as the doping direction to increase the
lattice parameters and obtain better results. But the only disadvantage of this
method is that if the concentration of a single ion is too high (>0.1%), it will have
an impact on the overall ion conductivity. This is because the concentration of a
single ion will affect the concentration of Li ions and lead to the overall ion. The
conductivity is not ideal. So in order to change this status quo, dual-site doping
(Sr and Ta) can be used. According to the results, the final ionic conductivity of
LLTO can reach 1.4×10-4 S cm -1[16].
In order to prepare a high-performance electrolyte membrane, the overall
requirement of the experiment is to use LiOH·H 2 O, La 2 O 3, TiO 2 and Ta 2 O 5
as raw materials for blending and heating. During the entire calcination process,
there will be a large amount of Li ion loss, which will cause uneven material and
poor performance. Therefore, lithium hydroxide is added to the overall material
in the form of crystal water to obtain Li ion compensation. For the pretreatment
of La 2 O 3, the experiment uses high-temperature drying for decarburization,
and then mixes and grinds the dried powder with isopropanol for 2 hours. The
obtained ground powder was air-dried and heated at 900°C for 8 hours. Continue
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to grind the powder and sinter at high temperature. Due to the existence of a
large number of dust particles, adhesion to the surface of Li reduces the
volatilization of Li. The temperature will eventually continue to be heated to
1250°C and cooled. The formed dust is continuously polished and polished to a
transparent electrolyte membrane. Both sides of the membrane can conduct ions
through[16].
For the conductivity test of the double ion doped LLTO electrolyte membrane, it
can be found in the impedance spectrum by electrochemical impedance
spectroscopy. For conventional lithium ion solid electrolytes, the high-frequency
region and the low-frequency region are composed of two semicircles. And
straight lines. In calculation, the total ion conductivity is the sum of the ion
conductivity between grain boundaries. A quantitative analysis of conductivity
can be obtained by using an appropriate equivalent short circuit. It can be seen
from FIG. 10 that the part of the crystal grains in the grain boundary is
represented by Rb, and the part of the grain boundary having a parallel
relationship is represented by Rgb. Due to the interaction between molecules,
CPEe represents the polarization effect. Substituting these values can calculate
the ion conductivity by formula. In the experiment, in order to obtain the actual
effect of the double-doped LLTO electrolyte membrane, a comparative
experimental group was introduced. The performance comparison of the double-
doped electrolyte membrane was highlighted by introducing the traditional LLTO
perovskite battery and measuring the actual ion conductivity. According to the
conclusion, it can be found that the actual conductivity of the perovskite
electrolyte membrane is related to the grain boundary resistance. Due to the
introduction of particles, the size of the bottleneck between the LLTO grain
boundaries has changed. For the introduction of large ions, the size of the
bottleneck becomes smaller; for the introduction of small ions, the size of the
bottleneck becomes larger. The change in the size of the bottleneck will cause the
overall conductivity to change. So the choice of particles is something to be
considered when doping particles into LLTO

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Figure 10 LLTO electrochemical impedance spectroscopy[16]

Due to the diversity of substitutions of perovskite-type compounds (ABO3), in
other studies, the A and B positions can be replaced by other elements. For LLNO
perovskite-type compounds, since A and B have not been completely substituted
until its substitution, its ionic conductivity value has not reached a high level. Its
small ions still have a large number of vacancies inside the crystals of the
material, and these vacancies provide small ions with a movable vacancy
framework. So its shape is an orthorhombic crystal structure. In order to obtain
better ionic conductivity, a large amount of Nb is added to reduce the appearance
of vacancies and make the overall structure into a cubic structure.
Through XRD observation, Sr ions have a great effect on the ionic conductivity of
LLNO and can increase the degree of cells. When a single cell becomes larger, the
overall cell becomes less, which increases the expansion of the cell. Has better
ionic conductivity.[17].
In the analysis of the experiment, the traditional solid-phase reaction method is
used as the experimental method. Add all reagents to absolute ethanol, mix and
grind. The resulting mixture was heated continuously for 4 hours to make the
ingredients uniform, and then fully contacted with air and continued to be heated
for 15 hours. The obtained finished product was pelletized under standard
atmospheric pressure and sintered at 1175°C for 8 hours. Finally, it is cooled to
room temperature to obtain the finished product[17].
The crystal analysis of the electrolyte and the determination of the degree of
crystallinity are determined by XRD, and the diffraction pattern in the range of
10°-90° is determined. According to the microscopic analysis of the crystal, the
surface morphology of the material can be seen.

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Figure 11 XRD surface topography[17]

2.1.4 Argyrodite-type electrolytes

The molecular formula of siderite-type electrolyte material is Ag 8 GeS 6. In
2008, siderite was used as an electrolyte material for lithium-ion batteries for the
first time through a substitution reaction[18].Its chemical formula is Li 6 PS 5 X.
In the research on this material, in space, it forms more than 120 tetrahedral
space structures with 6 sulfur atoms and halogen elements. Due to the porosity
of the structure, the surface has a large number of micropores. In the pores, there
are a large amount of elements accumulated, such as sulfur atoms, halogen atoms
and some appropriate amount of lithium elements. Due to the arrangement of
atoms, all atoms are arranged in a certain order, but when the halogen elements
Br and Cl appear, the arrangement will be disrupted. It can be seen from the NMR
spectrum that when x exhibits more than 60% of halogen atoms and less than
40% of sulfur atoms, the arrangement is regular, and the spatial structure allows
the passage of lithium ions and the migration of lithium ions. The rate can reach
the maximum. Through further comparison experiments, Li 6 PS 5 I and Li 6 PS
are also placed at room temperature, and the ion conductivity is calculated. It can
be obtained that the ion conductivity of the former is significantly higher than
that of the latter[19].
According to other methods, ball milling and sintering are used to manufacture
siderite-type lithium ion battery electrolyte. First, the powder of about 15
nanometers made by grinding the sample is tested, and the ion conductivity of
the powder is 4.6×10 -4S/CM. Place the sample in a crucible and continue
sintering until annealing is complete. It can be found by testing the ionic
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Student name:Guanchong Chen Student number:6055850

conductivity of the finished product. Because the phase of siderite is more pure
and the size of the powder can reach about 90NM, the ion conductivity can be
reduced by about 10 times. At the same time, it can be seen from the results that
if the milling time is increased, the ion conductivity results are better. This is
because better ion channels and stable chemical windows can be obtained by ball
milling. According to the possible results of the analysis, the diffusion mechanism
of lithium ions is related to chemical bonds. Under normal circumstances, the
diffusion of lithium ions can undergo intercalation and deintercalation reactions
at the long double ends. However, the disadvantage of siderite electrolyte is that
as a battery, the activation energy of the reaction is low[20]~[24].
In order to increase the activation energy, halogen atoms are used to carry out
the corresponding substitution reaction. At the same time, the spatial order
should be disrupted to speed up the reaction. Through the understanding of solid
electrolyte materials for lithium-ion batteries, electrolyte materials exhibit strong
ionic conductivity under high temperature conditions. At 550℃, the ionic
conductivity of the siderite-like electrolyte material is 1.8×10 -3 S cm -1.
The experiment synthesized (100-x) (0.75Li 2 S·0.25P 2 S 5)·x LiBH 4 crystalline
phase through a series of methods. And tested its performance.
According to the situation of siderite, a mechanical synthesis method is adopted.
The fusion of raw materials is carried out by ball milling, and the rotation speed
is controlled to 200 rpm for continuous mixing for 45 minutes. The phase of the
mixture is obtained[25].
According to the data, the conductivity of the general heat-treated material is
1.9×10 –3 S cm –1, which has no change compared with the untreated sample.
However, the mechanically treated samples showed better ionic conductivity.
According to data analysis, the necessary condition for high ionic conductivity is
that the material has a glass ground state[25].

2.1.5 Sulfide-type electrolytes

Derivative materials for LISICON lithium-ion batteries include sulfide-type
electrolyte materials made by sulfur substitution reactions. The most common
molecular formula of sulfide-type materials is Li 4-x Ge 1-x P x S 4. According to
data, compared with oxides, sulfide electrolyte materials have better
performance, which is mainly reflected in ion conductivity and ion mobility.
According to the nature of the material, it can be roughly divided into three
categories. It has considerable prospects in the study of materials as electrolyte
materials for lithium-ion batteries[26]
According to actual conditions, ceramic sulfide electrolyte materials are very
common. It has been tested a lot in many studies. The material has good ionic
conductivity and good spatial properties, which is conducive to the migration of
lithium ions. Compared with most electrolyte materials, the methods and costs
obtained are suitable for commercial development. Various derivatives of
sulfides were synthesized for the first time in 2000, mainly Li 2 GeS 3, Li 4 GeS 4,
Li 2 ZnGeS 4, and the highest ionic conductivity can reach 2.17×10 -3 S cm at
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Student name:Guanchong Chen Student number:6055850

25°C -1. Among them, Li 4 GeS 4 can also be doped with other particles, such as P
element, on some atomic sites. According to experiments, with the introduction
of other elements, the ion conductivity can be doubled. For other tests, the
chemical stability of sulfide is better, and it has no effect on the migration of
lithium ions. This means that vacancy doping becomes a possibility, and other
particles are appropriately introduced to reduce the activation energy required
for the reaction.

Figure 12 a. Frame structure and movable lithium ion. b. Show the frame structure of one-dimensional chain.
c. The conduction path of lithium ions.[26]

2.1.6 Garnet-type electrolytes

Garnet-type compounds are generally arranged regularly. For garnet-type
compounds used in lithium-ion batteries, the main component is Li 3 Ln 3 M 2 O
12. Its first synthesis was discovered in 1980. Lithium-containing pomegranate
The lattice constant of a stone is affected by the atomic radius. It decreases with
the increase of ion radius. According to the crystal shape analysis, the possible
reason is that the garnet-type compound has a stable spatial octahedral
structure. Compared with the garnet-type electrolyte material without Ln, the
garnet electrolyte with Ln ions is more stable and has high ionic conductivity.
According to the literature, the first garnet-type compound Li 5 La 3 M 2 O 12 has
an ion conductivity of 10 -6 S cm -1 at 25°C. With the same type of electrolyte
materials, for example, LISICON electrolyte and NASICON electrolyte materials
have higher ionic conductivity while the overall reaction requires low energy.
According to classification, both garnet and garnet-like electrolyte materials are
isotropic conductors. According to the model, the mobility of lithium ions is good.
However, the disadvantage is that other elements cannot be freely introduced
into the corresponding sites because the material itself has poor reducibility.
However, it is worth mentioning that the conductivity of garnet-like materials can
be increased by about twice the value of raw materials. For the overall
performance of garnet materials, its development prospects are very
impressive[27].
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Student name:Guanchong Chen Student number:6055850

Figure 13 Lithium ion migration in garnet electrolyte materials[27]

2.2 solid polymer electrolyte (SPE)

SPE is a salt solution without adding solvent, and its main composition is
polymer material. The manufacturing method is highly similar to large-scale
industrial manufacturing and is suitable for mass production. It has good
plasticity and has stronger interface contact than ISE. However, the current
problem is that the ion conductivity of most SPEs is lower than that of ISE, and
the rate of ion conduction by polymer chains cannot reach the standard[28].
CPE is an improvement to SPE, which enhances ionic conductivity by
introducing fillers into polymer solutions[29].

In some experiments, metal lithium was directly used as the negative electrode of
the battery, the metal oxide was used as the positive electrode, and the polymer-
based solid electrolyte was used as a transport vehicle for lithium ions. It can be
found that the transmission efficiency of lithium ions is not lower than that of
solid electrolytes such as metal oxides, sulfides, and garnets. This is because a
new intermediate was used in the experiment to promote ion exchange between
lithium metal and polymer. And this intermediate does not react with the
polymer, and at the same time efficiently transfer lithium ions. Similar to ion
exchange membranes. It can continuously interact with the metal at one end and
the polymer at the other end at the same time without affecting each other. In the
experiment, the polymer component is an ether-based electrolyte, which can
effectively prevent the growth of lithium dendrites from destroying the battery
structure[30].

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Student name:Guanchong Chen Student number:6055850

3.Analysis of solid electrolyte defects

3.1 Ion conductivity

3.2 Operating temperature range

3.3 cost analysis

4.Conclusions
Based on all research conclusions. Research on solid electrolytes for lithium-
ion batteries currently has a good prospect. On the premise of very powerful
performance, it also has huge experimental feasibility. The basis of the
experiment is to strengthen the ionic conductivity of the electrolyte

5.Future development trends and directions

For future research directions, mainly improve the performance of the
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Student name:Guanchong Chen Student number:6055850

electrolyte and find new alternative materials to make the lithium ion solid
electrolyte battery more perfect

References

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16. Li, R., Liao, K., Zhou, W., Li, X., Meng, D., Cai, R., & Shao, Z. (2019). Realizing fourfold
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https://doi.org/10.1038/s41467-019-12423-y.

Work plan
Year :2020
24/10-14/11
Complete the second part of the content, and strengthen the connection
between the content, submit it to the supervisor, and get corresponding
suggestions for improvement
14/11-24/12
Change the content of the second part and start the literature review of the third
part

Year: 2021
24/12-24/1
Complete the third part, and submit the contents of the third part to the
supervisor to obtain corresponding opinions
24/1-24/2
Improve the content of the third part according to the supervisor, and start the
final summary part.And submit the full text to the supervisor
26
Student name:Guanchong Chen Student number:6055850

24/3-24/4
Perform detailed processing, document format, article format, title, catalog
beautification
24/4-14/5
Complete the paper and submit it to the supervisor
26/10-31/10
Carry out repetition rate inspection, and continue to change in depth and deal
with details
14/5-4/6
Complete the thesis

27