盖建丽

中国科学院青岛生物能源与
过程研究所
2018年1月16日
Content
1. Background
2. Growth and property of TiO2 nanomaterials based on Ti3Si0.9Al0.1C2 solid
solution
Dr.
3. Formation process and mechanism of low dimensional materials based on
the thermal stability of Ti-Si-Al-C

1. Background

2. Nb, Y codoped to improve the conductivity and air stability of Li7La3Zr2O12

Post Dr. electrolyte

3. Fabrication and property of cold-pressed LLZO(LATP)/PEO composite solid

electrolyte

4. Fabrication and property of LATP/PVDF-HFP/SN composite solid electrolyte

1.Background

Mn+1AXn
1.Background
Crystal structure of MAX phase-Hexaganal

Space group P63/mmc

A
X

Unique layered structure of MAX phase

1.Background

MI-A MI-X MI-MII MI-MI MII-X MII-X/MI-X

Ti3AlC2 2.878 2.089 2.997 3.072 2.207 1.056

Ti3SiC2 2.694 2.084 2.971 3.068 2.183 1.048
Ti3GeC2 2.710 2.093 2.981 3.077 2.193 1.048
Ti3SnC2 3.020 2.023 2.885 3.136 2.254 1.114
Ta3AlC2 2.854 2.201 3.138 3.100 2.210 1.004

※ The weak bond between MX unit and A atomic layer lead to the
decomposition of MAX phase, which can be described by the
following equation
Mn+1AXn → Mn+1Xn + A
Michel W. Barsoum, MAX phases Properties of Machinable Ternary Carbides and Nitrides, 2013 Wiley-
VCH, Verlag GmbH&Co. KGaA, Weinheim, Germany
1.Background

Formation of porous TiC after

the evaporation of Al in
Ti3AlC2

Formation of porous TiC TiC

after the evaporation of Si in
Ti3SiC2

X. H. Wang, Y. C. Zhou. Chem. Mater. 2003 I. M. Low, et al. J. Am. Ceram. Soc. 2007 J. Emmerlich, et al. Acta Mater. 2007
1.Background

Ga crystals from Cr2GaN In crystals from Zr2InC SiO2 nanofibers based on

Ti3SiC2

M. W. Barsoum, L. Farber. Science 1999 Z. M. Sun, et al. J. Mater. Res. 2005 AlN nanowires based on
M. W. Barsoum, et al. Phys. Rev. Lett. 2004 H. B. Zhang, et al. J. Mater. Res. 2007 Ti3Si0.9Al0.1C2
1.Background-From MAX to MXene

M. Naguib, et al. J. Am. Chem. Soc. 2013 M. Naguib, et al, Adv. Mater. 2014 Maria R. Lukatskaya, et al. Science 2013
2. Growth and property of TiO2 nanomaterials based
on Ti3Si0.9Al0.1C2 solid solution
2.1 Growth and mechanism of TiO2 nanowhiskers

Experimental Design
2.1 Growth and mechanism of TiO2 nanowhiskers
Surface morphology

900 oC 104Pa

1h 5h
10h 20h
2.1 Growth and mechanism of TiO2 nanowhiskers

Microstructure

Rutile-TiO2，<001> is the growth direction

 2.1 Growth and mechanism of TiO2 nanowhiskers
Relationship between whisker growth and the orientation of matrix

H.B. Zhang, et al. J. Nanomater. 2013

Activation energy of TiSi along Si

atomic layer is only 0.3 eV.

The initial growth of TiO2 nanowhiskers is based on the outward diffusion of Ti along (0001)
2.1 Growth and mechanism of TiO2 nanowhiskers
Cross-sectional morphology and the corresponding mapping scan
900℃ 1000℃

空气

Growth of TiO2 nanowhiskers is controlled by the

outward diffusion of Ti along the oxide layer, H.B. Zhang, Acta Mater. (2004)
which result in the slower growth velocity.
2.1 Growth and mechanism of TiO2 nanowhiskers
Influence factors: Temperature and air pressure

700 oC 1000 oC
104 Pa 104 Pa
20 h 20 h

900 oC 900 oC
5 ×104 Pa 200 Pa
20 h 20 h
2.1 Growth, mechanism and property of TiO2 nanosheets
Background

(001) (011) and (111)

光电转换效率 光电流密度
纳米片

纳米粉体

J. S. Chen, et al. Chem. Sci.,2011 C. Zhen, G. Liu, et al. Nanoscale, 2012

2.1 Growth, mechanism and property of TiO2 nanosheets

Experimental design
2.1 Growth, mechanism and property of TiO2 nanosheets

Surface morphology

10min 20min
1h 3h
2.1 Growth, mechanism and property of TiO2 nanosheets
Microstructure

1. There are Al and Si in the nanosheets

and they are dispersed evenly;
2.Lots of defects are observed；
4.The exposed facets are {010}。
2.1 Growth, mechanism and property of TiO2 nanosheets
Growth mechanism

(0001)Ti3Si0.9Al0.1C2//(010)TiO2 OR-1

Activation energy of TiSi along Si atomic layer is only 0.3 eV.

The initial growth of TiO2 nanosheets is based on the outward

diffusion of Ti along (0001)
950 oC, 10 min Y. C. Zhou, Z. M. Sun, J. Mater. Sci. 2000 H.B. Zhang, et al. J. Nanomater. 2013
2.1 Growth, mechanism and property of TiO2 nanosheets
生长机制
950 oC, 5h Growth of TiO2 is 1100 oC, 20h,空气
gradually controlled
by the outward
diffusion of Ti along
oxides layer instead
by prolonging the
growth time.

Z. J. Lin. J. Am. Ceram. Soc. 2006

H.B. Zhang, Acta Mater. (2004)
2.1 Growth, mechanism and property of TiO2 nanosheets

OR-1 (0001)Ti3Si0.9Al0.1C2 ∥(010) TiO2

dr / ds = m / n
F=2[(mds - ndr) / mds + ndr ]
F → lattice misfit
r →rutile TiO2 s →Ti3Si0.9Al0.1C2

Ti3Si0.9Al0.1C2 TiO2 Misfit (%)

202 56.65
002 40
0008
220 31.25
200 3.54
1 1 -2 0 001 3.32
2.1 Growth, mechanism and property of TiO2 nanosheets

Effect of temperature

850 oC, 5kPa 1000 oC,5kPa

Lower temperature -TiO2 nanowhiskers

Higher temperature-Large TiO2 grains
2.1 Growth, mechanism and property of TiO2 nanosheets

XPS result for the surface and core of TiO2 nanosheets

纳米片表层由于与O直接接触，Ti, Al, Si均以各自氧化物的形式存在，芯部的Al和Si

则以置换固溶的形式存在，Al和Si的固溶会导致晶格常数减小
2.1 Growth, mechanism and property of TiO2 nanosheets
Properties

Intensity
3. Formation process and mechanism of low dimensional
materials based on the thermal stability of Ti-Si-Al-C
3.1 Formation and mechanism of Al2OC whiskers based on bulk Ti3AlC2

制备方法:
原材：块体 Ti3AlC2
高温炉：石墨发热体
气氛: 流动氩气（ 含0.6 ppm O2 ）
温度：1250-1300 oC,
保温时间：10-30 min
3.1 Formation and mechanism of Al2OC whiskers based on bulk Ti3AlC2
表面相组成

1460oC
Ar,无C环境

高真空

含C环境促进Ti3AlC2的分解
X.H. Wang, Chem. Mater. 2003 J. Phys.: Conf. Ser. 2010
3.1 Formation and mechanism of Al2OC whiskers based on bulk Ti3AlC2
微观形貌

气-液-固形成
机制的标志
1250oC
-10min

1300oC
-30min
3.1 Formation and mechanism of Al2OC whiskers based on bulk Ti3AlC2
微观结构

1250-10min 1100oC-30min

1300-30min
晶须 Al (at. %) C (at. %) O (at. %)
尖端 31.44 14.67 52.6
颈部 44.93 24.93 27.33
3.1 Formation and mechanism of Al2OC whiskers based on bulk Ti3AlC2
截面形貌 含C环境促进Ti3AlC2的分解

In air，1300℃

X.H. Wang, Corro. Sci. 2003

3.1 Formation and mechanism of Al2OC whiskers based on bulk Ti3AlC2
形成机理

2Al+CO = Al2OC CO CO

Al 液滴 Al蒸汽 Al2OC
CO CO
Al蒸汽 Ti/Al碳氧化物层
TiC多孔层
I II III
Ti3AlC2(s) →2Ti(3-x)/2C(s)+Al(g)+xTi(g)
2C+O2=2CO
2Al+CO = Al2OC
含C环境中的CO促进了基体的分解
4.2 Growth of nanomaterials on bulk Ti3AlC2 in CO-containing atmosphere based

处理方法:
原材：块体 Ti3AlC2
高温炉：石墨发热体，高真空
气氛: Ar-10%CO
温度：1250-1400 oC,
保温时间：30 min
4.2 Growth of nanomaterials on bulk Ti3AlC2 in CO-containing atmosphere based

表面相组成

1300℃时开始有Al2OC生成；1350-1400℃时，Al4O4C和Al4C3生成
4.2 Growth of nanomaterials on bulk Ti3AlC2 in CO-containing atmosphere based
表面形貌

Al2OC纳米片

1250 oC 1300 oC
1350 oC 1400 oC

Element Al C O
1300 oC 47.05 27.90 25.05
1350 oC 48.79 19.79 31.43
1400 oC 49.82 24.98 28.09
4.2 Growth of nanomaterials on bulk Ti3AlC2 in CO-containing atmosphere based

截面形貌及元素组成

1250 oC 1300 oC 1350 oC 1400 oC

1250-1300℃为单层TiC和Al2O3混合物，1350-1400℃外层为Ti/Al的碳氧化物，
内层为多孔TiC，且孔排列整齐，两层间界面平整
4.2 Growth of nanomaterials on bulk Ti3AlC2 in CO-containing atmosphere based

六方结构

平行于Ti3AlC2片层的的孔是Al/Ti沿基面
的外扩散导致的。
(1 -2 1 0)面4个Ti(2), 2个Ti(1); (1 0 -1 0)面上Ti(2)
的个数分别为2个或0个,对应的Ti(1)个数分别
为0个或2个。因此，垂直于基面的孔是是通
过Ti(2)沿(1 -2 1 0)晶面的外扩散控形成的。

(1 -2 1 0) (1 0 -1 0)面上的投影 J. Emmerlich et al, Acta Mater. (2007)

4.2 Growth of nanomaterials on bulk Ti3AlC2 in CO-containing atmosphere based
预氧化改进热稳定性

950℃, 20 h

TiO2

Al2O3
4.2 Growth of nanomaterials on bulk Ti3AlC2 in CO-containing atmosphere based
To improve the
thermal stability by
pre-oxidizing

1350℃-30min,
Ar-10%CO

Element Atomic(%)
OK 27.52
C 33.97
Al K 17.56
Ti K 19.5

预氧化可有效抑制
基体与CO的反应，
进而提高材料热稳
定性
 Background

Lithium-ion batteries in energy storage

Some types energy storage technique engineering

A schematic diagram on a safety test of

Development trend of large scale lithium-
different lithium ion batteries
based cells in the next two decades
Background Garnet
Solid state electrolyte
PEO/PPO

Sulfide Inorganic: Polymers:

PEC/PPC/PTMC
Brittle Low conductivity
NASICON PDMS

Composites
Advantages：
High ionic conductivity； Disadvantage：
Wide electrochemical Instability with Li at
window； lower potential
Good air stability；
Cost-effective。
LATP
LLZO
Schematic illustration of an all-solid-state lithium cell.
Advantages： Disadvantage:
High ionic conductivity Bad air stability
Wide electrochemical
window
Good stability with Li
Background

Solid state electrolyte in Lithium batteries:

I: High conductivity

II: Low interfacial impedance with electrodes

III: High mechanical strength

IV: Good flexibility

2. Nb, Y codoped to improve the conductivity and air stability of Li7La3Zr2O12

Experimental Li2CO3, La2O3, Nb2O5, Y2O3, ZrO2

Ball milled for 8 h

Treated at 900oC for 8 h

Ball milled again

Cold-pressed

Treated at 1100-1230oC for 10-18 h

2. Nb, Y codoped to improve the conductivity and air stability of Li7La3Zr2O12
2. Nb, Y codoped to improve the conductivity and air stability of Li7La3Zr2O12

x σt (×10-4S cm-1) σt(×10-4S cm-1) Et(eV) RD (%)

(21 oC) (30 oC)
0 0.0529 0.0734 0.4264 84.1
0.125 1.75 2.11 0.3545 92.6
0.25 2.11 2.68 0.3581 91
0.5 6.53 8.29 0.3065 90.7
0.25Nb 3.88 4.82 0.3554 90
 2. Nb, Y codoped to improve the conductivity and air stability of Li7La3Zr2O12

Arrhenius plots of ionic conductivities for

Li7La3Zr2-2xNbxYxO12

Morphologies of fractured Li7La3Zr2-2xNbxYxO12 samples: (a) x=0, (b) 0.25Nb

doped LLZO, (c) x=0.125, (d, f) x=0.25, and (e, g) x=0.5
 2. Nb, Y codoped to improve the conductivity and air stability of Li7La3Zr2O12

Surface morphology of a. Li7La3Zr2O12, b. Li7La3Zr1.75Nb0.25O12, c. Li7La3ZrNb0.5Y0.5O12 and the corresponding EDS mapping scan results
 2. Nb, Y codoped to improve the conductivity and air stability of Li7La3Zr2O12
Li+↔H+ Li7La3Zr2O12 + xH2O → Li7-xHxLa3Zr2O12-x + xLiOH
Li7La3Zr2O12 + CO2 → Li7-xLa3Zr2O12-x + xLi2CO3

Initial: 6.53 × 10-4 S cm-1 at 21 oC

After 7.5 months: 2.18 × 10-4 S cm-1 at 21 oC

Wenhao Xia, ACS Appl. Mater. Interfaces2016, 8, 5335−5342

2. Nb, Y codoped to improve the conductivity and air stability of Li7La3Zr2O12

Fractured surface of Li7La3Zr2-2xNbxYxO12 samples (a. x=0.25, b. x=0.5) treated at 1230 oC for 18 h
2. Nb, Y codoped to improve the conductivity and air stability of Li7La3Zr2O12

The charge and discharge curves (a) and cycle performance (b) of LFP/Li7La3ZrNb0.5Y0.5O12/Li
cell at 0.1 C at ambient temperature (~28 oC)
3. Fabrication and property of cold-pressed LLZO(LATP)/PEO
composite solid electrolyte
LATP/PEO

LiOH.H2O、Al2O3、TiO2、H3PO4 and water

Mixture of raw
materials

Ball-milled React in oil bath

Sintered at
700 oC

LATP PEO LiTFSI

Mix and cold-pressed

3. Fabrication and property of cold-pressed LLZO(LATP)/PEO
composite solid electrolyte
LATP/PEO

Prepared
3. Fabrication and property of cold-pressed LLZO(LATP)/PEO
composite solid electrolyte
LATP/PEO

4.2V

4.7V

Arrhenius plots of ionic conductivities Electrochemical window

3. Fabrication and property of cold-pressed LLZO(LATP)/PEO
composite solid electrolyte
LATP/PEO

Charge, discharge and cycle performance of the solid state composite electrolyte at 25℃，0.05C
3. Fabrication and property of cold-pressed LLZO(LATP)/PEO
composite solid electrolyte
LATP/PEO

153.8, 150.4, 149.7 and 144.3 mAh /g

at 0.1, 0.2, 0.5, 1C

Rate and cycle performance of the solid state composite electrolyte at 60℃
3. Fabrication and property of cold-pressed LLZO(LATP)/PEO
composite solid electrolyte

Ionic liquid (PP14TFSI)

is introduced

113.8 142.5 157.6

Charge, discharge and cycle performance of the solid state composite electrolyte with
different amount of ionic liquid at 25℃,0.05C
3. Fabrication and property of cold-pressed LLZO(LATP)/PEO
composite solid electrolyte
LLZO/PEO

Experimental LLZO PEO LiTFSI

Mixed thoroughly

Cold-pressed

Composite solid electrolyte Li LiFePO4

Solid state battery

3. Fabrication and property of cold-pressed LLZO(LATP)/PEO
composite solid electrolyte
LLZO/PEO

60oC
55oC

Surface morphology (60LLZO-40(PEO/LiTFSI))

Arrhenius plots of ionic conductivities
3. Fabrication and property of cold-pressed LLZO(LATP)/PEO
composite solid electrolyte
LLZO/PEO

Rate and cycle performance of the solid state composite electrolyte with different
amount of ionic liquid at 60 ℃
4. Fabrication and property of LATP/PVDF-HFP/SN composite solid electrolyte

Experimental

Mixtrue of LATP/PVDF-HFP/SN and Acetone

Dropped onto PTFE mode

With/without PI

Dried at room
Li LiFePO4
temperature

Solid state battery

4. Fabrication and property of LATP/PVDF-HFP/SN composite solid electrolyte

Cycle rate performance of the composite solid electrolyte at 25oC

4. Fabrication and property of LATP/PVDF-HFP/SN composite solid electrolyte

(a) (b)

Surface morphology of the prepared composite solid electrolyte (a) the observe side, (b) the reverse side
4. Fabrication and property of LATP/PVDF-HFP/SN composite solid electrolyte

With PI
4. Fabrication and property of LATP/PVDF-HFP/SN composite solid electrolyte

Performance at 4 oC

0.2C