Overview of webinar: Rechargeable, manganese-based, lithium-ion batteries (LiBs) are environmentally friendly, have a good safety record, and can be made at a lower cost than other metal-based LiBs. However, they have a shorter lifetime. Much research has been spent on improving product safety, cycle life, and product performance, yet understanding fundamental processes and degradation mechanism in LiBs remains a challenge. Identifying breakdown products and understanding degradation processes can lead to enhancing battery performance, improvements in product safety, and insight into component failure mechanisms.

1. 1
The world leader in serving science
Rosanne Slingsby, Kate Comstock, and Paul Voelker
March 18, 2015
Analysis of Phosphate and Manganese
Degradation Products in Aged Lithium
Ion Batteries
Part #: PP71583-EN 0315S

2. 2
Li-ion Battery Analysis: IC-HRMS
What Steps Are Involved?
IC-HRMS
Thermo Scientific™ Q Exactive™ Orbitrap™ MS
• Component Identification in Untargeted and Unknown Workflows
IC-CD
Time (min)
125 135 145 155 165 175 185
m/z
0
100
169.0272
C 4 H 10 O 5 P
155.0115
C 3H8O5P
125.0009
C2H6O4P
139.0166
C3H8O4P
Phosphate esters
Chemical
formula
Exact
mass
Delta
ppm
C2H6O4P 125.0009 -0.1
C3H8O4P 139.0166 0.2
C3H8O5P 155.0115 0.1
C4H10O5P 169.0272 0.4
Relativeabundance
1. IC Separation using a KOH eluent
2. Full scan MS/MS acquisition
3. Component ID based on HRAM
Data
4. Propose Structure
Source for Dimethyl phosphate image: CSID:2982799, http://www.chemspider.com/Chemical-Structure.2982799.html (accessed 00:59, Feb 5, 2015)

3. 3
Ion Chromatography Coupled to High Resolution Mass
Spectrometry
Eluent
Generator
(OH– or H+)
Conductivity
Detector
High-
Pressure
Non-Metallic
Pump
H2O
Autosampler
Electrolytic
Eluent
Suppressor
CR-TC
Separation
column
Pump
Solvent
/H2O
CD
Thermo Scientific
Q ExactiveTM
HRMS
C-trap HCD Cell
Segmented
Quadrupole
RF Lens
Injection flatapole
Electrospray inlet

4. 4
Methods
• IC Parameters
Column: Thermo Scientific™ Dionex™ IonPac™AG11, AS11 (2 mm)
Eluent: 1mM KOH from 0 to 5 minutes,
1-30 mM KOH from 5 to 25 minutes
30-65 mM KOH from 25.1-45 minutes
Eluent Source: Thermo Scientific Dionex EGC 500 KOH Cartridge
Flow Rate: 0.25 mL/min
Inj. Volume: 2.5 µL
Temperature: 30 ˚C
Detection: Suppressed Conductivity,
Thermo Scientific™ Dionex™ AERS™ 500 (2 mm) Suppressor
AutoSuppression, recycle mode
Post column solvent: 90/10 Acetonitrile/water, 0.25 mL/min
• MS Parameters
HRAM full scan MS and data dependent top 3 MS/MS were collected at resolution 70K and 17.5K, respectively
Stepped NCE setting were: 30, 40, 60.

5. 5
7. Methylsulfonate
8. Pyruvate
9. Chlorite
10. Valerate
11. Monochloroacetate
12. Bromate
13. Chloride
14. Nitrite
15. Trifluoroacetate
16. Bromide
17. Nitrate
18. Chlorate
19. Selenite
20. Carbonate
21. Malonate
22. Maleate
23. Sulfate
24. Oxalate
25. Ketomalonate
26. Tungstate
27. Phthalate
28. Phosphate
29. Chromate
30. Citrate
31. Tricarballylate
32. Isocitrate
33. cis-Aconitate
34. trans-Aconitate
Peaks:
1. Isopropylmethylphosphonate
mg/L
2. Quinate
3. Fluoride
4. Acetate
5. Propionate
6. Formate
0
10
µS
5 15Minutes 10
2
3 4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
3421
20
22
23
24
25
26
27
28
29
30
31
32
33
Monovalent Divalent Trivalent
Anion Exchange Gradients: Dionex IonPac AS11
Separation of Anions

6. 6
Lithium Ion Battery (LiB) Samples
• Overall Objectives
• Screen samples to identify changes among sample types
• Use ion exchange separation to help identify analyte properties
• Identify as many components as possible
• Samples
• Control
• Calendar aged 20% loss in capacity
• Cycle Aged 20% loss in capacity
• Additional Cycle Aged 45% loss in capacity
• Other Injections
• DI water blank
• Process control blank

7. 7
Preparation of LiB Anode Samples
• Anodes were cut to known weight
• Samples were sonicated and rinsed in deionized water
• Extracts were filtered thru Whatman PP 0.45 µm filters
• Weight losses were calculated
• Filtered extracts were injected into the IC-CD-HRMS
system

8. 8
IC-CD Chromatograms of Anode Samples
e:libnov20-runva-3-pp 11/20/14 21:49:03
AS11 2mm 250ul/min
RT: 0.00 - 55.00
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54
Time (min)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
µS
3.77
4.07
15.924.91
5.27
17.92
15.56
9.78 10.73 27.71 49.1524.688.15 14.94 26.675.81 23.01 54.8250.66 53.58
NL:
1.19E1
ECD_1 UV
MA-0-PP
RT: 0.00 - 54.99
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54
Time (min)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
µS
4.91
16.1415.89
22.94
14.21
17.925.22 27.79
24.10 49.1448.5710.73 26.66 41.6613.867.00 9.76 50.65 51.53 53.1919.66 28.64
NL:
1.54E1
ECD_1 UV
UA-1-PP
RT: 0.00 - 54.99
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54
Time (min)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
µS
4.91
16.14
15.87
22.95
14.20
27.77
17.92
5.17
49.7249.0226.6724.1313.86 50.67
NL:
3.21E1
ECD_1 UV
va-3-pp
Control
Calendar Aged 20% Loss
Cycle Aged 45% Loss
Sulfate
17.12
Phosphate
Monovalent Divalent Trivalent components

9. 9
IC-HRMS Chromatograms of Anode Samples
e:libnov20-runva-3-pp 11/20/14 21:49:03
AS11 2mm 250ul/min
RT: 0.04 - 55.00
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54
Time (min)
0
5
10
15
20
RelativeAbundance
5.32
9.82
8.21
4.11 16.2211.07
15.593.93 27.7424.7514.06
NL:
3.09E9
Base Peak F:
FTMS - p ESI
Full ms
[50.00-750.00]
MS MA-0-PP
RT: 0.00 - 54.99
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54
Time (min)
0
5
10
15
20
RelativeAbundance
23.02
4.16 5.31 16.19
14.237.04 8.163.76 9.81 15.576.22 27.77
24.13 41.7217.9911.07 24.30 49.7513.99
NL:
2.57E9
Base Peak F:
FTMS - p ESI
Full ms
[50.00-750.00]
MS UA-1-PP
RT: 0.09 - 55.00
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54
Time (min)
0
5
10
15
20
RelativeAbundance
23.00
14.24
5.294.20 16.19
27.7315.553.59 27.868.15
3.32 9.80
7.01 49.7926.7317.98 24.16 49.1913.95 41.7910.63 53.27
NL:
2.79E9
Base Peak F:
FTMS - p ESI
Full ms
[50.00-750.00]
MS va-3-pp
Monovalent Divalent Trivalent components
Control
Calendar Aged 20% Loss
Cycle Aged 45% Loss

10. 10
Anionic Compounds and Classes Found in LiB
Samples to Date
• Solvents- Methyl carbonate
• Inorganic Anions- sulfate, phosphate, hexafluorophosphate
etc
• Carboxylic acids- succinate, malate, malonate, oxalate etc
• Organic sulfonates – propylsulfonate
• Sulfate esters
• Phosphate esters
• Fluorophosphate esters

11. 11
Example Data Analysis - Identify Methyl Carbonate
E:LiBNov20-RunVA-3-PP 11/20/14 21:49:03
AS11 2mm 250ul/min
RT: 0.04 - 55.00
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54
Time (min)
0
5
10
15
RelativeAbundance
23.00
14.24
5.294.20 16.19
27.7315.553.59 27.868.153.32 9.80
7.01 49.7926.7317.98 24.16 49.1913.95 41.7910.63 53.2728.2118.86 47.442.23 37.581.26 38.48 50.6136.4529.7822.53 31.87 46.0833.04 42.33
NL:
2.79E 9
B as e
P eak
F :
F T MS
-­‐
p
E S I
F ull
ms
[50.00-­‐750.00]
MS
VA -­‐3-­‐P P
VA-3-PP #1865 RT: 4.21 AV: 1 NL: 1.41E8
T: FTMS - p ESI Full ms [50.00-750.00]
60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210
m/z
0
50
100
RelativeAbundance
75.0087
C2 H3 O3
122.9853
C2 H4 O4 P89.0245
C3 H5 O3
60.9930
C H O3
59.0137
C2 H3 O2
RT: 0.00 - 55.00
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54
Time (min)
0
20
40
60
80
100
RelativeAbundance
4.20
17.11
NL:
1.75E 8
m/z=
74.38-­‐75.38
F :
F T MS
-­‐
p
E S I
F ull
ms
[50.00-­‐750.00]
MS
VA -­‐3-­‐P P
VA-3-PP #1854 RT: 4.19 AV: 1 NL: 2.21E7
F: FTMS - p ESI d Full ms2 75.01@hcd45.00 [50.00-100.00]
60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210
m/z
0
50
100
RelativeAbundance
75.0088
C2 H3 O3
Full Scan c-gram
Peak at 4.20 minutes
EIC of 75.0088 m/z
Delta 0.4 ppm
MS2 at 4.20 min.
C2H3O3

12. 12
E:LiBNov20-RunVA-3-PP 11/20/14 21:49:03
AS11 2mm 250ul/min
RT: 0.09 - 55.00
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54
Time (min)
0
2
4
6
8
10
12
14
16
RelativeAbundance
23.00
14.24
5.29 4.20 16.19
27.7315.553.59 27.868.15
3.32 9.803.24
7.01 49.7926.7317.98 24.16 49.1913.95 41.7910.63 53.2718.31 18.48 28.21 47.442.23 37.581.26 38.48 50.6136.4529.78 31.87 44.9633.04 42.33
NL:
2.79E9
Base Peak F:
FTMS - p ESI
Full ms
[50.00-750.00]
MS VA-3-PP
VA-3-PP #1568-1694 RT: 3.58-3.84 AV: 32 NL: 5.89E7
T: FTMS - p ESI Full ms [50.00-750.00]
60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240
m/z
0
20
40
60
80
100
RelativeAbundance
169.0272
C4 H10 O5 P
139.0166
C3 H8 O4 P
125.0009
C2 H6 O4 P
155.0115
C3 H8 O5 P
185.0222
C11 H5 O360.9930
C H O3
153.0323
C4 H10 O4 P
119.0349
C4 H7 O4
133.0507
C5 H9 O4
89.0245
C3 H5 O3
179.0562
C6 H11 O6
110.9853
C H4 O4 P
163.0613
C6 H11 O5
103.0401
C4 H7 O3
RT: 0.00 - 55.00 SM: 7B
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54
Time (min)
0
20
40
60
80
100
RelativeAbundance
5.30
3.87
5.63
NL:
1.70E8
m/z=
138.51-139.51 F:
FTMS - p ESI
Full ms
[50.00-750.00]
MS VA-3-PP
Early Eluting Phosphate Esters
Phosphate esters
Chemical
formula
Exact mass Delta
ppm
C2H6O4P 125.0009 -0.1
C3H8O4P 139.0166 0.2
C3H8O5P 155.0115 0.1
C4H10O5P 169.0272 0.4
(RT 3.6-3.8 minutes)
EIC of 139.01 m/z
RT 3.6-3.8 minutes
Base peak chromatogram

13. 13
Later Eluting Phosphate Esters
e:libnov20-runva-3-pp 11/20/14 21:49:03
AS11 2mm 250ul/min
RT: 0.00 - 55.00
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54
Time (min)
0
50
100
0
50
100
0
50
100
17.16
23.0014.245.294.20 16.19 27.733.59 8.15 9.80 49.7926.7317.9813.95 41.79 53.27
14.24
3.65 17.065.94 23.03 28.94 30.9226.152.78 38.5335.459.80 52.9046.5313.78 41.0721.93 45.378.68 49.8019.24 33.70 41.99
14.39
24.333.36 27.0114.85 22.993.74 17.2310.01 47.1938.53 54.2640.0922.1211.97 49.420.86 36.8635.3130.26 43.50 45.56 50.9733.578.256.96
NL: 2.79E9
Base Peak F: FTMS - p
ESI Full ms
[50.00-750.00] MS
va-3-pp
NL: 3.23E7
Base Peak m/z=
282.49-283.49 F: FTMS
- p ESI Full ms
[50.00-750.00] MS
va-3-pp
NL: 2.70E7
Base Peak m/z=
212.51-213.51 F: FTMS
- p ESI Full ms
[50.00-750.00] MS
va-3-pp
va-3-pp #6257-6338 RT: 14.19-14.36 AV: 21 SB: 129 14.50-15.08 , 13.35-13.92 NL: 1.22E8
T: FTMS - p ESI Full ms [50.00-750.00]
60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300
m/z
0
10
20
30
40
50
60
70
80
90
100
RelativeAbundance
140.9958
C2 H6 O5 P
125.0009
C2 H6 O4 P
110.9852
C H4 O4 P
78.9590
O3 P
282.9991
C4 H13 O10 P2
267.0039
C4 H13 O9 P2
121.0295
C7 H5 O2
213.0170
C5 H10 O7 P
236.9935
C3 H11 O8 P2
96.9600
H O4 S
(RT14.2-14.4 minutes)

14. 14
Analysis of an Unknown- Ethanetricarboxylate
e:libnov20-runva-3-pp 11/20/14 21:49:03
AS11 2mm 250ul/min
RT: 0.04 - 55.00
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54
Time (min)
0
2
4
6
8
10
12
14
16
18
20
RelativeAbundance
23.00
14.24
5.294.20
16.19
27.733.59
8.15
3.32 9.80
7.01 49.7926.7317.98 24.16 49.1913.95 41.799.97 53.27
NL:
2.79E9
Base Peak F:
FTMS - p ESI
Full ms
[50.00-750.00]
MS va-3-pp
va-3-pp #12253-12393 RT: 27.65-27.96 AV: 36 SB: 131 28.41-29.16 , 26.94-27.39 NL: 5.27E7
T: FTMS - p ESI Full ms [50.00-750.00]
60 70 80 90 100 110 120 130 140 150 160 170 180 190 200
m/z
0
10
20
30
40
50
60
70
80
90
100
RelativeAbundance
117.0193
C4 H5 O4
103.0037
C3 H3 O4
161.0092
C5 H5 O6
59.0137
C2 H3 O2 118.9986
C3 H3 O5
133.0143
C4 H5 O5
73.0295
C3 H5 O2
60.9929
C H O3
178.9317
H2 O6 F P2
149.0092
C4 H5 O6
99.0088
C4 H3 O3
173.0092
C6 H5 O6
115.0037
C4 H3 O4
Delta
0.2 ppm
Trivalent elution region
C5H5O6

15. 15
Simple Case - Propylsulfonate
e:libnov20-runva-3-pp 11/20/14 21:49:03
AS11 2mm 250ul/min
RT: 0.04 - 55.00
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54
Time (min)
0
2
4
6
8
10
12
14
16
18
20
RelativeAbundance
23.00
14.24
5.294.20
16.19
27.733.59
8.15
3.32 9.80
7.01 49.7926.7317.98 24.16 49.1913.95 41.799.97 53.27
NL:
2.79E9
Base Peak F:
FTMS - p ESI
Full ms
[50.00-750.00]
MS va-3-pp
va-3-pp #3544-3662 RT: 8.00-8.26 AV: 30 SB: 131 28.41-29.16 , 26.94-27.39 NL: 6.20E7
T: FTMS - p ESI Full ms [50.00-750.00]
60 70 80 90 100 110 120 130 140 150 160 170 180 190 200
m/z
0
10
20
30
40
50
60
70
80
90
100
RelativeAbundance
123.0121
C3 H7 O3 S
79.9572
O3 S

16. 16
Chemical Formula for Propylsulfonate
Help from HRMS Data
Chemical formulae, Mass 123.01 Chemical formulae, Mass 123.0121
Formula Delta, ppm Formula Delta, ppm
1 C6H3O3 10.0 1 C3H7O3S -0.3
2 C3H7O3S -17.4 2 C6H3O3 27.1

17. 17
Summary: ESI(-) Mode Peaks from Sample VA
RT: 0.44 - 55.00
5 10 15 20 25 30 35 40 45 50 55
Time (min)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
RelativeAbundance
5.29
4.20
16.19
27.73
3.59
27.86
8.15
3.32 9.80
7.01 49.79
26.73
17.98
24.16
49.19
13.95 41.79
53.2718.21
18.66 47.4428.792.23 47.1537.58 50.6136.4529.78 41.34
NL:
2.79E9
Base Peak F:
FTMS - p ESI
Full ms
[50.00-750.00]
MS VA-3-PP
6.21
14.24
15.55
17.22
23.03
Retention time Masses Delta (ppm) Possible ID
3.3-3.8 several Phosphate esters
4.20 75.0088 0.4 CH3O3
Methyl carbonate
6.21 112.9810 0.6 CH3O3FP
Methylfluorophosphate
8.15 123.0121 -0.3 C3H7O3S
Propylsulfonate
14.24 several Phosphate esters
15.55 117.0193 0.3 C4H5O4
Succinate
16.19 103.0036 -0.2 C3H3O4
Malonate
15.62 133.0137 0.4 C4H5O5
Malate
17.22 98.9601 0 HSO4
23.03 98.9696 -0.2 H2PO4
27.73 161.0092 0.2 C5H5O6
41.79 176.9360 0.3 H3P2O7
49.19 175.0249 0.5 C6H7O6

18. 18
Summary
• Ion chromatography provides ion exchange separations of
anionic (or cationic) sample components
• The IC with a conductivity detector is coupled to HRMS to
provide information in the elucidation of unknowns
• Analytes are eluted in the order of
monovalent<divalent<trivalent<higher by ion exchange
separation so information is provided on key structural
features
• To date we have found components from the aging of LiB
anodes in several chemical classes including carboxylic
acids, esters, phosphate esters, fluorophosphate esters,
sulfate esters, as well as inorganic anions

19. 19
Lithium Ion Battery Anode Samples Analysis
• Anode samples
• Control Cell Shelf Aged.
• Calendar Aged. Exhibited 20% loss in capacity.
• Cycle Aged. Exhibited 20% loss in capacity.
• Additional Cycle Aged. Exhibited 45% loss in capacity.
• Objective
• To identify the impurity and degradant present in the sample group.
• To correlate the analysis results with the batteries performance.
• IC-HRMS Analysis and software
• Thermo Scientific Dionex IC combined with the Q Exactive HRMS was used
for separation and identification.
• Thermo Scientific™ SIEVE™ software used for component extraction and
differential analysis. The Chem Spider report with the high resolution data
base for known component screening. Thermo Scientific™ Mass Frontier™
was used for structural elucidation.

20. 20
Comprehensive Li-ion Battery Analysis Workflow : IC-HRMS
HR MS Analysis
Full Scan-MS/MS
Ion Separation
Components
Identified .
_________________
. _________________
. _________________
. _________________
. _________________
. _________________
Component ID
(Chem Spider and high
resolution ion database)
Sample Preparation
Thermo Scientific high resolution accurate mass ion database contains accurate masses for common anions and
elemental compositions. Users can quickly identify the common anions by database search.
Report
Thermo Scientific
Dionex ICS-2100 System
Q Exactive MS
SIEVE Software
Component Extraction
Differential Analysis
High Resolution Anion Database
. __________ .__________
. __________ .__________
. __________ .__________

21. 21
Schematic of Q Exactive Benchtop LC-MS/MS

22. 22
Q Exactive MS Specifications
• Max resolution: 140,000 at m/z 200
• Scan speed: up to 12 HZ (at 17.5K)
• Mass Accuracy
• < 3 ppm external
• < 1 ppm internal
• Mass range for full scans: 50 < m/z < 6000
• Intra-scan dynamic range: > 5000:1
• Sensitivity
• Full MS: 500 fg Buspirone on column S/N 100:1
• SIM: 50 fg Buspirone on column S/N 100:1
• Polarity Switching
• One full cycle in < 1 sec (one full scan positive mode and one full scan
negative mode at resolution setting of 35,000)
Resolution at
m/z 200
Max. Scan
Speed (Hz)
17.500 12
35.000 7
70.000 3
140.000 1.5

23. 23
Why Use Q Exactive HRMS?
• Q Exactive High Resolution Accurate Mass (HRAM) data
provides ultimate confidence for qualitative and
quantitative analysis.
• High sensitivity, rapid polarity switching ensure detection of
structurally diverse compounds at all level.
• The HRAM full scan and MS/MS provide rich information for
component identification and structure elucidation
• Coupled with SIEVE and other Thermo Scientific software,
QExactive MS is best suited for known and unknown
impurity and degradant analysis for Li-ion battery and other
industrial applications.

24. 24
Q Exactive Instrument Method
• MS Method
• ESI negative ion mode
• AGC target 1e6
• Full scan MS and data dependent top 3 MS/MS at resolution 70K
and 17.5K
• Stepped NCE: 30, 45, 60
• Scan range: 50 to 750 m/z

25. 25
HR-MS for Lithium Ion Battery Anode Analysis
• HR-MS unambiguously identifies ion species based on
HRAM data
• Unit mass vs. high resolution accurate mass
m/z
(-­‐)
Unit
mass
m/z
(-­‐)
HRAM
Formula
(-­‐)
Ionic
Species
97
96.9601
HSO4
Hydrogen
Sulfate
97
96.9696
H2PO4
DiHydrogen
Phosphate
139
139.0166
C3H8O4P
Phosphate
Ester
139
139.0071
C3H7O4S
Sulfate
Ester

26. 26
90 100 110 120 130 140 150 160 170 180 190
m/z
0
10
20
30
40
50
60
70
80
90
100
RelativeAbundance
139.0166
133.0507
110.9853
120 130 140 150 160 170 180
m/z
0
10
20
30
40
50
60
70
80
90
100
RelativeAbundance
139.0071
141.0029
UA-1-PP#1634 RT: 3.73
T:
50 60 70 80 90 100 110 120 130 140 150 160
m/z
0
10
20
30
40
50
60
70
80
90
100
RelativeAbundance
78.9591
O3 P
0.8 ppm
110.9853
C H4 O4 P
0.5 ppm
139.0166
C3 H8 O4 P
0.5 ppm
62.9642
O2 P
0.3 ppm
UA-1-PP#2322 RT: 5.26 AV: 1 NL: 2.84E7
T:
50 60 70 80 90 100 110 120 130 140 150 160
m/z
0
10
20
30
40
50
60
70
80
90
100RelativeAbundance
139.0072
C3 H7 O4 S
1.0 ppm
79.9575
O3 S
1.3 ppm
81.953264.9702
HO2 S
-1.4873 ppm
120.9965
C3 H5 O3 S
-0.1060 ppm
HRAM MS/MS Fragments for Structure Elucidation
(M-H)-(M-H)-
C3H7O4S
m/z (-) 139.0071
0.3 ppm
(-) C3H8O4P
m/z (-)
139.0166
0.4 ppm
MS/MS MS/MS
S
O
O
OOH
OH P
O
O
O
• HRAM MS/MS fragments for confident structure characterization

27. 27
HRAM MS/MS Fragments for Structure Elucidation
The structures of co-eluting peaks were identified by MS/MS fragments
O
P
O
O
O
O
P
O
O
O
OH O
P
O
O
O
OH O
P
O
O
O
OH
OH
ua-1-pp #1521 RT: 3.48 AV: 1 NL: 5.71E7
T: FTMS - p ESI Full ms [50.00-750.00]
80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290
m/z
0
10
20
30
40
50
60
70
80
90
100
RelativeAbundance
169.0272
155.0116
185.0222
125.0009
139.0166
183.012296.9601 112.9856
121.0295
163.0613 200.986589.024579.9574 190.9916
172.9915
133.0507 149.0456 255.2331217.0256101.0608 237.0148 283.2644274.9611 293.0074
ua-1-pp #1510 RT: 3.46 AV: 1 NL: 2.72E6
T: FTMS - p ESI d Full ms2 125.00@hcd45.00 [50.00-150.00]
60 80 100 120 140
m/z
0
10
20
30
40
50
60
70
80
90
100
RelativeAbundance
125.0010
62.9641
78.9591
111.9568
94.9905
ua-1-pp #1518 RT: 3.48 AV: 1 NL: 8.32E6
T: FTMS - p ESI d Full ms2 155.01@hcd45.00 [50.00-180.00]
60 80 100 120 140 160 180
m/z
0
10
20
30
40
50
60
70
80
90
100
RelativeAbundance
78.9591 110.9853
155.0117
122.9854
ua-1-pp #1502 RT: 3.44 AV: 1 NL: 1.82E7
T: FTMS - p ESI d Full ms2 169.03@hcd45.00 [50.00-195.00]
60 80 100 120 140 160 180
m/z
0
10
20
30
40
50
60
70
80
90
100
RelativeAbundance
78.9591
140.9960
169.0273
125.0010
ua-1-pp #1496 RT: 3.43 AV: 1 NL: 6.67E6
T: FTMS - p ESI d Full ms2 184.99@hcd45.00 [50.00-210.00]
50 100 150 200
m/z
0
10
20
30
40
50
60
70
80
90
100
RelativeAbundance
78.9591
122.9854
185.0223
140.9960

28. 28
IC-HRMS Result for Aged Anode
F:Li-Battary-PaulNov20-RunVA-3-PP 11/20/14 21:49:03
AS11 2mm 250ul/min
RT: 0.0 - 55.0 SM: 5G
0 5 10 15 20 25 30 35 40 45 50 55
Time (min)
10
20
30
40
50
60
70
80
90
100
RelativeAbundance
0
5
10
15
20
25
30
µS
4.0
17.1
4.9 16.1 22.914.2 27.817.95.2 49.748.626.724.113.9 50.7
17.2
23.0
14.25.34.2 16.2 27.73.6 27.88.1 9.83.3 49.87.0 26.718.0 24.2 49.213.9 41.810.6 53.3
NL:
3.21E1
ECD_1 UV
VA-3-PP
NL:
2.73E9
Base Peak F:
FTMS - p ESI
Full ms
[50.00-750.00]
MS VA-3-PP
IC Chromatogram
MS Base Peak Chromatogram
Cycle Aged Sample 45% Loss

29. 29
IC Chromatograms for All Samples
f:li-battary-paulnov20-runma-0-pp 11/20/14 23:59:15
AS11 2mm 250ul/min
RT: 0.0 - 30.0 SM: 7G
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Time (min)
0
10
20
µS
0
10
20
µS
0
10
20
µS
0
10
20
µS
0
10
20
µS
0
10
20
µS
17.1
3.8 4.1 15.94.9
3.9
17.1
4.9 16.1 22.9
3.9
17.1
4.9 15.9
17.1
4.9 16.1 22.914.2 27.8
NL:
2.50E1
ECD_1 UV
blk_1411202
25409
NL:
2.50E1
ECD_1 UV
pc-2-pp
NL:
2.50E1
ECD_1 UV
ma-0-pp
NL:
2.50E1
ECD_1 UV
ua-1-pp
NL:
2.50E1
ECD_1 UV
xa-2-pp
NL:
2.50E1
ECD_1 UV
VA-3-PP
Solvent Blank
Control Cell shelf aged
Calendar-aged 20% loss in capacity
Cycle aged 20% loss in capacity
Process Control
Cycle aged 45% loss in capacity
The IC chromatograms show the differences between samples

30. 30
HRMS Base Peak Chromatograph
f:li-battary-paul...blk_141120225409 11/20/14 22:54:09
AS11 2mm 250ul/min
RT: 0.0 - 55.0 SM: 5G
0 5 10 15 20 25 30 35 40 45 50 55
Time (min)
0
50
100
0
50
100
0
50
100
0
50
100
0
50
100
0
50
100
5.3 9.88.24.1 16.211.1 15.63.9 27.824.7
17.2
23.04.2 5.3 16.214.27.0 8.23.8 9.8 27.824.1 41.711.1 49.8
17.2
23.014.24.2 5.3 16.23.5 27.88.2 9.8 49.826.77.1 13.9
23.014.25.34.2 16.2 27.73.6 8.1 9.8 49.87.0 26.718.013.9 41.8
NL: 2.60E9
Base Peak m/z= 50.0000-6000.0000
F: FTMS - p ESI Full ms
[50.00-750.00] - m/z=
144.9640-144.9654 MS
blk_141120225409
NL: 2.60E9
Base Peak F: FTMS - p ESI Full ms
[50.00-750.00] MS pc-2-pp
NL: 2.60E9
Base Peak F: FTMS - p ESI Full ms
[50.00-750.00] MS ma-0-pp
NL: 2.60E9
Base Peak F: FTMS - p ESI Full ms
[50.00-750.00] MS ua-1-pp
NL: 2.60E9
Base Peak F: FTMS - p ESI Full ms
[50.00-750.00] MS xa-2-pp
NL: 2.60E9
Base Peak F: FTMS - p ESI Full ms
[50.00-750.00] MS VA-3-PP
Solvent Blank
Control cell shelf aged
Calendar-aged 20% loss in capacity
Cycle aged 20% loss in capacity
Process Control
Cycle aged 45% loss in capacity
See zoomed-in view in next slide (Full Scan Negative mode)

31. 31
F:Li-Battary-PaulNov20-RunVA-3-PP 11/20/14 21:49:03
AS11 2mm 250ul/min
RT: 0.2 - 54.5 SM: 5G
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54
Time (min)
0
20
40
60
80
100
RelativeAbundance
0
20
40
60
80
100
RelativeAbundance
0
20
40
60
80
100
RelativeAbundance
0
20
40
60
80
100
RelativeAbundance
9.8
8.2
4.1 16.211.1
15.63.9 27.824.713.812.9 18.33.6 26.7
23.0
4.2 5.3 16.2
14.27.0
8.2
4.0 9.83.5 6.2 15.6 27.8
24.1 41.711.1 24.3 49.814.0 18.1 49.228.1
23.014.2
4.2
5.3 16.2
4.0
3.5 27.815.68.2 9.8
49.826.77.1 13.913.2 24.2 49.218.2
14.2
5.34.2
16.2
27.73.6 15.5 27.88.1
9.83.3
49.87.0 26.718.0 24.2 49.213.9 41.813.4 53.318.6
NL:
2.60E8
Base Peak F:
FTMS - p ESI
Full ms
[50.00-750.00]
MS ma-0-pp
NL:
2.60E8
Base Peak F:
FTMS - p ESI
Full ms
[50.00-750.00]
MS ua-1-pp
NL:
2.60E8
Base Peak F:
FTMS - p ESI
Full ms
[50.00-750.00]
MS xa-2-pp
NL:
2.60E8
Base Peak F:
FTMS - p ESI
Full ms
[50.00-750.00]
MS VA-3-PP
Yellow –new or increasing
MS Base Peak Chromatograph
Blue – Decrease or disappearing
Control cell shelf aged
Calendar-aged 20% loss in capacity
Cycle aged 20% loss in capacity
Cycle aged 45% loss in capacity
MS show different profiles and more peaks
Zoomed-in View

32. 32
SIEVE Base Peak Alignments (MS Data)
0-30 min
Zoom In View
40-55 min

33. 33
SIEVE - Trend Intensities and XIC
Trend Intensities
RT =11 min
XIC
RT =11 min
Component m/z 124.9912 at RT 11.0 min with Elemental Formula C2H5O4S,
Ethyl sulfate. The Shelf aged control has high intensity.

34. 34
SIEVE PCA Showing Differences Between Sample Groups
Trend Intensities at RT =11 min m/z 124.9912
PCA plot for all six samples

35. 35
Control Cell Shelf Aged
E:GM-Li BatteryNov20-RunMA-0-PP 11/20/14 23:59:15
AS11 2mm 250ul/min
RT: 0.0 - 55.0 SM: 5G
0 5 10 15 20 25 30 35 40 45 50 55
Time (min)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
RelativeAbundance
5.3
9.8
8.2
4.1 16.2
11.1
15.63.9 27.8
24.713.8
NL:
2.95E9
Base Peak F:
FTMS - p ESI
Full ms
[50.00-750.00]
MS MA-0-PP
HRMS Base Peak Chromatogram
1
2
3
4
5
6
7
8
9
10
11
12
13

36. 36
Component Identified from “Control Cell Shelf Aged”
Components
idenPfied
in
Control
Sample
Peak
#
RT
(min)
m/z
Formula
(-­‐)
Delta
ppm
Name*
(Based
on
MS
results)**
1
3.9
89.0244
105.0193
119.0350
C3H5O3
C3H5O4
C4H7O4
0.3
-­‐0.4
-­‐0.3
lactate
2
4.1
75.0087
C2H3O3
-­‐0.4
Methyl
carbonate
3
5.3
139.0070
C3H7O4S
0
Propyl
sulfate
4
8.2
123.0121
C3H7O3S
-­‐0.1
Propyl
sulfonate
5
9.8
140.9864
C2H5O5S
0.3
2-­‐hydroxyethyl
sulfate
6
11.1
124.9914
C2H5O4S
-­‐0.3
Ethyl
sulfate
7
15.6
117.0193
C4H5O4
0.2
methyl
malonate
8
15.7
133.0143
C4H5O5
0.2
3-­‐carboxy-­‐3-­‐hydroxypropanoate
9
16.2
103.0037
C3H3O4
0
2-­‐carboxyacetate
10
17.2
96.9601
HO4S
-­‐0.2
hydrogen
sulfate
11
24.7
218.9639
C3H7O7S2
0.2
2-­‐hydroxy-­‐3-­‐sulfopropane-­‐1-­‐sulfonate
12
26.7
175.0249
C6H7O6
0.3
13
27.8
117.0193
C4H5O4
0.1
2-­‐carboxy-­‐propanoate
*
The
compounds
are
proposed
based
on
database
search
using
HRAM
data
.
The
other
possible
structures
are
not
show.
**
The
MS
data
were
acquired
in
ESI
negaPve
ion
mode.
The
ions
reported
there
are
all
HRAM
single
charged
negaPve
ions.
The
names
listed
here
are
corresponding
to
the
single
charge
ionic
species.
***
The
notes
here
apply
to
other
samples
in
this
experiment.

37. 37
Calendar Aged 20% Capacity Loss
E:GM-Li BatteryNov20-RunUA-1-PP 11/21/14 02:09:29
AS11 2mm 250ul/min
RT: 1.9 - 50.9 SM: 5G
5 10 15 20 25 30 35 40 45 50
Time (min)
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
RelativeAbundance
23.0
4.2 5.3
16.2
14.27.0
8.2
3.8 9.8
6.2 15.6
27.8
24.1
NL:
2.53E9
Base Peak F:
FTMS - p ESI
Full ms
[50.00-750.00]
MS UA-1-PP
MS Base Peak Chromatogram
1
2, 3
8
4 5
6
7
9
10
11
12, 13, 14
19
23
20
22
18
21
15,16, 17
24 25
29
26
28
27
30
31

38. 38
Component Identified from Calendar Aged Sample 45%
Capacity Loss
Components
IdenPfied
in
Calendar
Aged
Sample
Peak
#
RT
(min)
m/z
Formula
(-­‐)
Delta
ppm
Name
(Based
on
MS
results)*
1
3.4
To
3.6
125.0009
155.0116
169.0272
185.0222
C2H6O4P
C3H8O5P
C4H10O5P
C4H10O6P
0
0.6
0.6
0.6
Phosphate
Esters
2
3.7
139.0166
C3H8O4P
0.5
Phosphoric acid
3
3.9
153.0323
C4H10O4P
0.5
Phosphate
4
4.2
75.0088
C2H3O3
-­‐0.2
Methyl
Carbonate
5
5.3
139.0071
C3H7O4S
0.4
Propyl
sulfate
6
6.2
112.9810
CH3O3FP
0.3
Methyl
Phosphorofluoridate
7
7.0
126.9966
C2H5O3FP
0.1
Ethyl
phosphorofluoridate
8
8.2
123.0122
C3H7O3S
0.3
Propyl
sulfonate
9
9.8
140.9864
C2H5O5S
0.3
2-­‐hydroxyethyl
sulfate
10
10.7
110.9757
CH3O4S
-­‐0.3
methyl
sulfate
11
11.1
124.9914
C2H5O4S
0.1
Ethyl
sulfate
12
14.2
140.9958
C2H6O5P
0.1
2-­‐hydroxyethyl
hydrogen
phosphate
13
14.3
125.0009
C2H6O4P
-­‐0.1
ethyl
hydrogen
phosphate
14
14.4
110.9853
CH4O4P
-­‐0.2
methyl
hydrogenphosphate
15
15.3
131.0350
C5H7O4
0
3-­‐carboxy-­‐2-­‐methylpropanoate
16
15.6
117.0193
C4H5O4
0.2
Methyl
Malonate
17
15.7
133.0143
C4H5O5
0.2
3-­‐carboxy-­‐3-­‐hydroxypropanoate
18
15.9
117.0194
C4H5O4
0.2
Succinate
19
16.2
103.0037
C3H3O4
0.3
2-­‐carboxyacetate
20
16.6
98.9653
HO3FP
0.2
hydrogen
phosphorofluoridate
21
17.2
96.9601
HO4S
-­‐0.2
hydrogen
sulfate
22
23.0
96.9696
H2O4P
-­‐0.5
dihydrogen
phosphate
23
24.1
204.9674
C2H7O7P2
0.7
hydrogen
(1-­‐hydroxy-­‐1-­‐phosphono-­‐ethyl)-­‐phosphonate
24
24.3
190.9517
CH5O7P2
1.1
Methyl
trihydrogen
diphosphate
25
26.7
175.0249
C6H7O6
0.3
Ascorbate
26
27.8
161.0092
C5H5O6
0.1
Ethanetricarboxylate
27
27.9
103.0037
C3H3O4
0.3
28
28.1
133.0143
C4H5O5
0.4
29
41.7
176.9361
H3O7P2
0.9
Trihydrogen
diphosphate
30
49.2
175.0249
C6H7O6
0.6
Tricarballylate
31
49.8
204.9990
C6H5O8
0.1
Yellow –new or increasing
Blue –Decrease or disappearing

39. 39
Cycle Aged Sample 20% Capacity Loss
F:Li-Battary-PaulNov20-RunXA-2-PP 11/20/14 19:38:48
AS11 2mm 250ul/min
RT: 0.0 - 55.0 SM: 5G
0 5 10 15 20 25 30 35 40 45 50 55
Time (min)
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
RelativeAbundance
23.0
14.2
4.2
5.3 16.2
4.0
3.5
27.8
15.6
8.2
9.8
49.826.7
7.1
13.9
13.4 24.2 49.2
18.211.9 24.4
NL:
1.96E9
Base Peak F:
FTMS - p ESI
Full ms
[50.00-750.00]
MS XA-2-PP
MS Base Peak Chromatogram
1
2
4
5
6
8
9
3
19
26
14
18
21
24
30
31
29
10
11, 12, 13
15, 16, 17
20
7
23
25
28
22
32
27

40. 40
Component Identified from Cycle Aged 20% Loss in Capacity
Components
IdenPfied
in
Cycle
Aged
Sample
Peak
#
RT
(min)
m/z
Formula
(-­‐)
Delta
ppm
Name
(Based
on
MS
results)*
1
3.2-­‐3.6
125.0009
155.0116
169.0272
185.0222
C2H6O4P
C3H8O5P
C4H10O5P
C4H10O6P
0
0.6
0.6
0.6
Phosphate
Esters
2
3.8
139.0166
C3H8O4P
0.4
Phosphoric acid
3
4.0
89.0244
C3H5O3
0.1
4
4.2
75.0088
C2H3O3
-­‐0.2
Methyl
Carbonate
5
5.3
139.0071
C3H7O4S
0.4
Propyl
sulfate
6
6.2
112.9810
CH3O3FP
0.3
Methyl
Phosphorofluoridate
7
7.1
126.9966
C2H5O3FP
0.1
Ethyl
phosphorofluoridate
8
8.2
123.0122
C3H7O3S
0.3
Propyl
sulfonate
9
9.8
140.9864
C2H5O5S
0.3
2-­‐hydroxyethyl
sulfate
10
10.0
155.0020
C3H7O5S
-­‐0.3
11
14.2
140.9958
C2H6O5P
0.1
2-­‐hydroxyethyl
hydrogen
phosphate
12
14.3
125.0009
C2H6O4P
-­‐0.1
ethyl
hydrogen
phosphate
13
14.4
110.9853
CH4O4P
-­‐0.2
methyl
hydrogenphosphate
14
15.3
131.0350
C5H7O4
0
3-­‐carboxy-­‐2-­‐methylpropanoate
15
15.6
117.0193
C4H5O4
0.2
methyl
malonate
16
15.7
133.0143
C4H5O5
0.2
3-­‐carboxy-­‐3-­‐hydroxypropanoate
17
15.9
117.0194
C4H5O4
0.2
Succinate
18
16.2
103.0037
C3H3O4
0.3
2-­‐carboxyacetate
19
16.6
98.9653
HO3FP
0
hydrogen
phosphorofluoridate
20
17.1
118.9986
C3H3O5
21
17.2
96.9601
HO4S
-­‐0.2
hydrogen
sulfate
22
23.0
96.9696
H2O4P
-­‐0.5
dihydrogen
phosphate
23
24.2
204.9674
C2H7O7P2
0.7
hydrogen
(1-­‐hydroxy-­‐1-­‐phosphono-­‐ethyl)-­‐phosphonate
24
24.4
190.9517
CH5O7P2
1.1
Methyl
trihydrogen
diphosphate
25
26.1
131.0349
C5H7O4
-­‐0.4
26
26.7
175.0249
C6H7O6
0.3
27
26.9
147.0299
C5H7O5
0.3
4-­‐carboxy-­‐3-­‐hydroxybutanoate
28
27.8
161.0092
C5H5O6
0.1
Ethanetricarboxylate
29
27.9
103.0037
C3H3O4
0
30
41.7
176.9360
H3O7P2
0.3
Trihydrogen
diphosphate
31
49.2
175.0249
C6H7O6
0.3
Tricarballyllate
32
49.8
204.9312
C6H5O8
0.1
Yellow –new or increasing
Blue –Decrease or disappearing

41. 41
Cycle Aged 45% Loss in Capacity
F:Li-Battary-PaulNov20-RunVA-3-PP 11/20/14 21:49:03
AS11 2mm 250ul/min
RT: 0.0 - 55.0 SM: 5G
0 5 10 15 20 25 30 35 40 45 50 55
Time (min)
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0
10.5
11.0
11.5
12.0
12.5
RelativeAbundance
23.0
14.2
5.34.2
16.2
27.7
3.6
15.5
27.8
8.1
9.83.3
49.87.0
26.7
18.0
24.2 49.224.313.9 41.810.6 53.318.3
NL:
2.73E9
Base Peak F:
FTMS - p ESI
Full ms
[50.00-750.00]
MS VA-3-PP
MS Base Peak Chromatogram
1
2
4
5 6
8
9
3
18
19
21
10
12, 13, 14
15, 16, 17
20
7
22
11
23
24
25
26
27
29
28
30
31
32
33
34

42. 42
Component Identified from Cycle Aged 45% Loss in Capacity
Components
IdenPfied
in
Cycle
Aged
Peak
#
RT
(min)
m/z
(-­‐)
Measured
m/z
(-­‐)
Calculated
Delta
ppm
Formula
(-­‐)
Name
(Based
on
MS
results)*
1
3.2
To
3.6
125.0009
155.0116
169.0272
185.0222
125.0009
155.0115
169.0271
185.0220
0
0.6
0.6
0.6
C2H6O4P
C3H8O5P
C4H10O5P
C4H10O6P
Phosphate
Esters
2
3.9
139.0166
139.0166
0.4
C3H8O4P
Phosphoric acid
3
4.2
75.0088
75.0088
-­‐0.2
C2H3O3
Methyl
Carbonate
4
5.3
139.0071
139.0071
0
C3H7O4S
Propyl
sulfate
5
6.2
112.9810
112.9809
0.2
CH3O3FP
Methyl
Phosphorofluoridate
6
7.0
126.9966
126.9966
0.1
C2H5O3FP
Ethyl
Phosphorofluoridate
7
7.4
120.9965
120.9965
-­‐0.1
C3H5O3S
2-­‐Propene-­‐1-­‐sulfonic
acid
8
8.2
123.0122
123.0121
0.2
C3H7O3S
Propyl
sulfonate
9
9.8
140.9864
140.9863
0.3
C2H5O5S
2-­‐hydroxyethyl
sulfate
10
10.7
110.9757
110.9758
-­‐0.3
CH3O4S
methyl
sulfate
11
11.1
124.9914
124.9914
0.1
C2H5O4S
Ethyl
sulfate
12
14.2
140.9958
140.9958
0.1
C2H6O5P
2-­‐hydroxyethyl
hydrogen
phosphate
13
14.3
125.0009
125.0009
-­‐0.1
C2H6O4P
ethyl
hydrogen
phosphate
14
14.4
110.9853
110.9853
0
CH4O4P
methyl
hydrogenphosphate
15
15.3
131.0350
131.0350
0
C5H7O4
3-­‐carboxy-­‐2-­‐methylpropanoate
16
15.5
117.0193
117.0193
0.2
C4H5O4
methyl
malonate
17
15.7
133.0143
133.0143
0.2
C4H5O5
3-­‐carboxy-­‐3-­‐hydroxypropanoate
18
15.9
117.0194
117.0194
0.2
C4H5O4
Succinate
19
16.2
103.0037
103.0037
0.3
C3H3O4
2-­‐carboxyacetate
20
16.6
98.9653
98.9653
0
HO3FP
hydrogen
phosphorofluoridate
21
17.2
96.9601
96.9601
-­‐0.2
HO4S
hydrogen
sulfate
22
23.00
96.9696
96.9696
-­‐0.5
H2O4P
dihydrogen
phosphate
23
24.1
204.9674
204.9674
0.7
C2H7O7P2
hydrogen
(1-­‐hydroxy-­‐1-­‐phosphono-­‐ethyl)-­‐phosphonate
24
24.3
190.9517
190.9517
1.1
CH5O7P2
Methyl
trihydrogen
diphosphate
25
24.7
218.9639
218.9639
0.2
C3H7O7S2
2-­‐hydroxy-­‐3-­‐sulfopropane-­‐1-­‐sulfonate
26
26.1
175.0249
175.0249
0.5
C6H7O6
Ascorbate
27
26.7
175.0249
175.0249
0.3
C6H7O6
28
26.9
147.0299
147.0299
0.3
C5H7O5
4-­‐carboxy-­‐3-­‐hydroxybutanoate
29
27.7
161.0092
161.0092
0
C5H5O6
Ethanetricarboxylate
30
27.8
103.0037
103.0037
0
C3H3O4
31
41.8
176.9360
176.9360
0.3
H3O7P2
trihydrogen
diphosphate
32
49.2
175.0249
175.0249
0.3
C6H7O6
tricarballylate
33
49.8
204.9990
204.9990
0
C6H5O8
34
53.3
224.9312
224.9312
0.
HO3F6P2
F5P-­‐PO3H2F
Yellow –new or increasing
Blue –Decrease or disappearing

43. 43
Summary
• Ion chromatography coupled with the Orbitrap Q Exactive
mass spectrometer provides a powerful platform for Li-ion
battery anode impurity and degradant analysis.
• The HRAM full scan and ms/ms data with polarity switching
allows for unambiguous ionic species identification and
structure characterization.
• This IC-HR/AM MS-based platform provides comprehensive
results which can be used for QA/QC for Lithium-ion battery
manufacturers and performance evaluations.

44. 44
IC-ICP-MS, 55Mn
• Amount of irreversibly formed Mn species is correlated to aging
Zheng, H.; Sun, Q.; Liu, G.; Song, X.; Battaglia, V.S. Correlation between Dissolution Behavior and Electrochemical Cycling Performance for
LiNi1/3Co1/3Mn1/3O2-Based Cells. J. Power Sources 2012, 207, 134–140.

45. 45
MnxOy
z-
Mn2+
Cycle- or Calendar-Aged
LiB
H+
Mn2+
CathodeAnode
Anion Analysis of Cathode Dissolution
LiNi0.42Mn0.42Co0.16O2
Mechanistic Pathway
-Mn3+
Mn4+
+
Anode* Cathode**
* Mn2+ sol .in electrolyte, migrates to anode
** Mn4+ insol .in electolyte, remains on cathode
Manganese IC-ICP-MS Analysis of Aged Li-ion Batteries
Acid-Catalyzed Dissolution of Mn to Mn3+
and Disproportionation to Mn2+ and Mn4+

46. 46
Permanganate/Manganate Configurations
Manganate(VI)
Permanganate(VII)

47. 47
Control Anode and Calendar-Aged Anode Sample
Anion Analysis
Chromatographic Conditions:
Column: Dionex IonPac AS11, 2 × 250 mm
Eluent: 1 mM KOH 0–5 minutes,1–30 mM KOH 5–25 minutes
Eluent Source: Dionex EGC 500 KOH Cartridge
Flow Rate: 0.25 mL/min
Injection Volume: 2.5 µL
Temperature: 30 ˚C
Detection: Suppressed conductivity,
Dionex AERS 500 (2 mm) Suppressor,
AutoSuppression, recycle mode

48. 48
Manganate, Permanganate, Anion Standards, and
Calendar-Aged Anode Samples
100 ppm Manganate
100 ppm Permanganate
Anion Standard
Fluoride
Chlorite Bromate
Chloride
Nitrite
Sulfate
Carbonate
Bromide, Nitrate, Chlorate
0 10 20 30
-10
10
µS
Minutes
Aged Anode Sample

49. 49
IC Anion-Exchange Analysis of Aged Li-ion Battery Samples
Summary:
• Neither manganate nor permanganate are stable on the anion
exchange column
• They may be reacting on the column and degradation products
may be eluting in the vicinity of carbonate as well as earlier
• It is possible that carbonate is produced during a reaction on the
column

50. 50
Permanganate Standard
• Positive response to direct infusion HRMS in –ESI mode
• Negative response to IC-HRMS
O
Mn
O
O O
Theoretical Simulation
Experimental Result
116 117 118 119 120 121 122 123
m/z
0
20
40
60
80
100
0
20
40
60
80
100
RelativeAbundance
118.9181
116.9287 120.9221118.9541 119.9219117.9288 118.7880115.9206
118.9183
120.9225119.9225 122.9267121.9267

51. 51
Proposed Mechanism for Anionic Mn Species
• Compound 1 formed by the reaction of permanganate with a
succinic acid adduct, a plausible degradation product
• Compound 1 degrades under acidic conditions
Tetrahedron 65 (2009) 707–739
?

52. 52
Cycle Aged (45% Capacity Loss): IC-HRMS
• Positive response to a Mn containing product
• Proposed Mn species consistent with a retention time of 16-33 min
• pH 10-11 of the aq anode extract
• 2 decimal point m/z accuracy supports proposed species
• 4 decimal point m/z accuracy disputes proposed species
Experimental
m/z
Calculated
m/z
234.98 234.93
Experimental
m/z
Calculated
m/z
234.9779 234.9281
2 Decimal Point Accuracy 4 Decimal Point Accuracy

53. 53
IC-HRMS and Direct Infusion HRMS Analysis of Aged Li-
ion Battery Samples
Conclusions:
• Permanganate Standard
• Detected by direct infusion HRMS in –ESI mode
• Not detected by anion exchange IC-HRMS
• Proposed Mn Oxide complex
• Positive response by IC-HRMS for aged 40% capacity loss sample
• Proposed species was disproved by direct infusion HRMS in –ESI mode with 4
decimal point accuracy
• No anionic Mn containing products observed by IC-HRMS
• Next Steps
• Cation exchange IC with +ESI mode HRMS to validate presence of Mn2+ from
the degradation of permanganate

54. 54
Acknowledgement
• Chris Pohl, Thermo Fisher Scientific, Sunnyvale, CA, USA
• Charanjit Saini, Thermo Fisher Scientific, Sunnyvale CA, USA

55. 55
Questions?